Vol. 99, No.
8 ANNIVERSARY ISSUE ON P R I M A R Y
67. N. KAMEYAMA,AND A. NAKA, J. Soc. Chem. Ind. Japa~t,
39, 432 (1936) from C.A. 31, 4602 (1937).
68. M. E. WILKE, Trans. Electrochem. Sou., 90, 433 (1946).
69. Ref. (50) p. 146.
70. J. PARDEE, U.S. Geol. Surv. Bull. 725, Washington, D. C.,
p. 146-147 (1922).
71. A. E. KITSON, Am. Inst. Mining Met. Engrs,, Tech. Paper
1622-C-1 (1927).
72. C. F. BURGESS, U. S. Pat. 1,305,251, June 3, 1919.
73. C. F. BURGESS, U. S. Pat. 1,305,250, June 3, 1919.
74. C. DR~CKER-A. ]~INKELSTEIN, "Galvanische Elemente
u n d A k k u m u l a t o r e n , " p. 72 ft., Akad. Verlagsges.
m.b.H., Leipzig (1932).
75. Ref. (6) p. 179-183.
76. M. E. HOLMES, U. S. Pat. 1,148,230, July 27, 1915.
77. M. L. KAPLAN, U. S. Pat. 1,178,927, April 11, 1916.
78. M. L. KAPLAN, U. S. Pat. 1,287,041, Dec. 10, 1918.
79. Ref. (39); also ref. (61); H. F. McMURDIE, D. :N. CRAI(;,
AND G. W. VINAL, Trans. Electrochem. Sou., 90, 509
527 (1946).
80. Ref. (40); H. F. McMuRDIE, Trans. Eleclrochem. Sou.,
86, 313-26 (1944).
81. O. D'AGOSTINO, Ricera sci., 9, 195-206 (1938).
82. Z. HERMANNAND C. SLONIM,Monatsh., 70, 84-103 (1937).
83. P. W. SELV~rOOD,R. P. EISCHENS,M. ELLIS, AND K. WETtI-
INGTON, J. Ant. Chem. Sou., 71, 3039-3043 (1949).
84. O. F. TOWER, Z. physik. Chem., 18, 17 (1895).
85. M. DEKAYTHOMPSONAND E. C. CROCKER, Trans. Electro-
chem. Sou., 27, 155 (1915).
86. F. DAN1ELS, Trans. Electrochem. Sou., 53, 45-71 (1928).
87. B. M. THOMPSON, Ind. Eng. Chem., 20, 1176-8 (1928).
88. n . D. HOLLER AND L. ~:[. RITCHIE, Trans. Electrochem.
Sou., 37,607 (1920).
89. T. J. ~IARTIN AND A. J. HELFRECHT, Trans. Electroct~em.
Soe., 53, 83 (1928).
90. N. C. CAHOON, Trans. Electrochem. Sou., 68, 177 (1935).
91. N. C. CArtOON, J. Electrochem. Sou., (in press).
92. P. DUBOIS, Ann. chirr., 5, 411 482 (1936).
Magnesium Primary Batteries
C. K . M o r e h o u s e I
During the last quarter of a century, production techniques
have advanced until magnesium is now considered a common
metal, competitive on the basis of cost and supply with
such other metals as aluminum and zinc. Today it is ex-
tensively used in the structural fields, for cathodic protection,
Grignard reactions, and metallurgical treatments. Another
application which has been considered frequently during the
last fifty years is its use as the soluble electrode or anode of
priinary batteries. The amount of magnesium now being
used in primary batteries is small, but recent developments
point to the possibility of magnesium finding extensive use
in this field.
In Table I is given a comparison of some of the properties,
together with a few theoretical calculations, of several of the
more common metals which are now used as batter)' anodes
or could conceivably be used. I n making these calculations,
it is assumed that the electrode efficiency is 100 per cent and
that the electrode is not passivated during discharge, i.e.,
that it is able to operate at its reversible electrode potential.
On the basis of watt-hour capacity per gram, sodium, alu-
minum, and magnesium are the most attractive. Sodium,
1 Olin Industries, Inc., New Haven, Connecticut.
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CELL SYSTEMS 187C
93. O. GLEMSER, Bet'., 72, 1879 (1939).
94. C. DROTSCHMANN,Batterien, 8, 1082 (1940).
95. F. SCHOSSBERGER,Batterien, 9, 17-20, 33 35 (1940).
96. M. FLEISCHER AND W. E. RICHMOND, Econ. Geol., 38,
269 (1943).
97. H. F. ~icMuRDIE, Trans. Electrochem. Sou., 86,346 (1944).
98. P. H. DELANO, Ind. Eng. Chem., 42, 523-7 (1950).
99. W. F. COLE, A. D. WADSLEY, AND A. WALKLEY, Trans.
Electrochem. Sou., 92, 133-158 (1947).
100. L. S. RAMSDELL,Am. Min. J., 17,143 (1932).
101. L. H. BERKELHAMER, U. S. Bur. Mines, Tech. Pub. 66~
(1945).
102. B. K. BROWN, Trans. Electrochem. Sou., 53, 113-18 (1928).
103. C. F~RY, Electrician, 80, 320 (1917), from C. A. 12, 565
(1918); Compt. rend., 172, 317-20 (1920).
104. F. CARHART, quoted by A. NASARISCHWILY,Z. Elektro-
chem., 29, 320 (1923).
105. L. MAICHE, British Pat. 1,940, Oct. 24, 1882; POLLAKAND
WEHR, French Pat. 170,411, July 31, 1885; A. VONWELS-
BACH, French Pat. 321,330, May 21, 1903; G. W. HEINE
(58); and many others.
106. K. KORDESCH AND A. MARKO, Oesterr. Chem. Ztg., 52,
125-31 (1951).
107. Ref. (45), p. 158 ft.
108. E. A. SCHUMACHER AND G. W. HEINE, J. Eleetrochem.
Sou., 99, 191C (1952).
109. C. DROTSCHMANN, Ref. (63), p. 360 ft.; R. C. PENNER,
U. S. Pat. 1,400,513, Dec. 20, 1921; R. C. PENNER AND
H. F. FRENCH, U. S. P~t. 1,438,084, Dec. 5, 1922; G. W.
HEINE, V. S. Pat. 1,484,779-80, Feb. 26, 1924.
110. R. C. PENNER, U. S. Pat. 1,438,085, Dec. 5, 1922.
111. H. F. FRENCH,U. S. Pat. 1,402,224, Jan. 3, 1922; 1,416,704,
May 23, 1922.
112. K. A. KOBE AND R. P. GRAHAM, Trans. Electrochem. Sou.,
73, 587-600 (1938); N. K. CHANEY, ibid. (Discussion),
p. 600 ft.
113. ~ . BOLEN AND B. H. WEIL, "Literature Search on Dry
Cell Technology," Georgia Institute of Technology,
Atlanta, Ga. (1948).
however, is incompatible in aqueous solutions and aluminum
has a definite disadvantage in that an oxide film is formed
on the surface which passivates the electrode. If this oxide
layer is removed, for example by amalgamation or by an
alkaline treatment, the aluminum becomes very reactive and
difficult to handle especially in the presence of aqueous
solutions.
Historical
The theoretical advantages of magnesium as an anode for
primary batteries were undoubtedly recognized even in the
days of Volta. As early as 1887, Heir (1, 2) described a
modified Bunsen cell which consisted of carbon and mag-
nesium electrodes immersed in a nitric acid solution and
magnesium sulfate. He also tried chromic acid as the mag-
nesium electrolyte, but he reported unfavorable results.
Heir makes reference to a modified Lec]anch6 cell consisting
of a magnesium anode, a manganese dioxide cathode, and an
electrolyte of an aqueous solution of magnesium chloride or
magnesium sulfate. However, little, if anything, of significance
had been published on a magnesium Leclanch6 type cell up
to the recent work of Kirk and Fry (3, 29).
From 1887 to about 1925 references to the use of mug-
 188C JOURNAL OF THE ELECTROCHEMICAL SOCIETY August 1952

nesium are infrequent and unimportant. Wood (4) in his
1928 patent describes a magnesium-manganese dioxide cell
of either the wet or so called "dry" type, using an electrolyte
comprising an aqueous solution of ammonium chloride, am-
monium nitrate, and sodium dichromate. The inventor states
that the dichromate and the nitrate provide a protective
film on the surface of the magnesium which reduces the
corrosion of the magnesium when the battery is not in use.
Ferrabino (5, 6), an Italian, in his patents of 1930, describes
magnesium cells with calcium sulfate and magnesium chloride
electrolytes. In these patents reference is made to the use of
such materials as calcium ferroeyanide as inhibitors to reduce
the corrosion of magnesium. Manganese dioxide and lead
dioxide coupled with magnesium were suggested as cathode
material.
Gordon in his 1936 patent (7) describes a reserve-type
multiple-cell magnesium battery comprising a loosely-fitted
cellulose fibrous material as the separator, copper or silver as
the positive electrode, magnesium as the negative electrode,
and a solution of potassium iodide as an electrolyte. In his
other 1936 patents (8, 10), he describes a magnesium air-cell
type battery. This cell consisted of a carbon tube as the
positive electrode and one or more magnesium pins, or rods
of pure magnesium or of magnesium-aluminum-nlanganese
McNulty found, however, that when chromic acid solutions
were used alone as an electrolyte in the magnesium-carbon
primary cell, the voltages were very low. By the addition of
phosphoric acid and small concentrations of sulfate to the
chromic acid electrolyte, the cell voltage and capacity were
increased without excessively accelerating the open-circuit
corrosion attack. The best electrolytes were: 40% chromic
acid, 23% phosphoric acid, 37% water, and 40% chromic
acid, 15% phosphoric acid, 0.01% sulfuric acid, 44.99%
water. Cells of this type operated effectively at anode current
densities of 3 a m p / f t ~ (3 ma/cm ~) and 1.0 to 1.5 v. This
battery compares favorably with the Lalande type battery
(zinc-copper oxide), but because of the larger quantity of
electrolyte required per watt-hour, it does not compare so
favorably with the air-depolarized battery.
Additional references to cells containing a magnesium
anode and cathode of persulfate (19, 31) and magnesium (20)
or calcium (21) permanganate are found in the literature.
However, none of these electrochemical systems has been
developed to date into a practical battery.
Practical Batteries
One of the first practical primary ceils using magnesium
as the negative electrode was the silver chloride-magnesium

TABLE I
Reversible Metal req'd, per whr
Element Gram equiv ~ost pe Cost per
Electrode reaction electrode Density weight lb? kwhr*
potential grams* vol* (cc)

Na + + e = Na --2.714 0.97 22.997 0.31 0.32 ;0.17 $0.12

Mg Mg ++ + 2e = Mg --2.34 1.74 12.16 0.19 0.11 0.25 0.10
AI A1+ + + + 3 e = A1 --1.67 2.70 8.99 0.20 0.07 0.19 0.08
Zn (alkaline sys- ZnO2= + 2H:O + 2e = Zn + 4OH- --1.316 7.14 32.69 1.0 0.14 0.18 0.~
tem)
Zn (acid system) Zn ++ + 2e = Zn --0.761 7.14 32.69 1.6 0.22 0.18 0.63
Fe 2 e = Fe
9 F e ++ + --0.441 7.6 27.9 2.4 0.32 0.03 0.17
Cd Cd ++ + 2e = Cd -0.402 8.65 56.2 5.2 O.6O 2.55 29.2
Pb Pb ++ + 2e = Pb --0.126 11.34 103.6 30.5 2.7 0.17 11.42

* Calculations based on hydrogen as other electrode.

t Cost is based on price of unfabricated metal.

alloys as the negative electrode. Aqueous solutions of calcium
bromide or other halides were used as electrolytes. G. W.
Heise (11) in his 1933 patent also describes a magnesium
air-cell type battery.
Ruben (12) in his patent of 1933 describes a high-resistance
magnesium potential cell containing an electrolyte composed
of a glycol compound and a vanadium pentoxide cathode. In
his patents (13, 14) issued in 1941 and 1942 in which a
magnesium cell containing chromic acid electrolyte is de-
scribed, Ruben points out that magnesium becomes passive in
chromic acid, or alkali, or alkaline earth metal fluoride
solutions. He found that, when one or more of these metal
fluorides is added to the chromic acid, magnesium loses its
passive character during current flow, but returns to it when
not used if the proper fluoride is present in the correct pro-
portion. He recommended an electrolyte of the following
composition: 160 g chromic acid, 100 g water, 1 g magnesium
fluoride.
Anderson (15), Forsythe (16), and Barbian and McNulty
(17, 18) describe a primary cell with carbon and magnesium
electrodes and a chromic acid electrolyte. Chromic acid
solutions have some desirable features in t h a t they dissolve
the magnesium corrosion products formed during discharge
and yet do not attack the magnesium itself: Barbian and
water-activated cell described in Harriss's patent (22) and by
Mullen and Howard in their paper (23). A comparable
battery, silver bromide-magnesium water-activated, is de-
scribed in Lawson's patent (24, 25). This cell is the subject
of a separate review paper by I. C. Blake. (See p. 000C.)
R. C. Kirk, A. B. Fry, and P. F. George of the Dow
Chemical Company (3, 26--29) in their patents and papers
described some of the efforts to develop a magnesium dry
cell of the Leclanch6 type. This work, done under a Squier
Laboratory Signal Corps contract, is the most significant
development work which has been done leading toward a
practical magnesium primary battery. They made a system-
atic and thorough study of alloy compositions, electrolyte
compositions, and inhibitors. The alloy which gave the best
results was AZ31A (3% almninum, 1% zinc, 0.2% manganese,
0.15% calcium, and the remainder magnesium). Electrolytes
consisting of aqueous solutions of alkali and alkaline earth
bromides can be used, but magnesium bromide gave the best
performance with respect to anode corrosion on shelf and cell
capacity. Ammonium and lithium chromate inhibitors were
also found to be effective in lessening the open circuit cor-
rosion attack without affecting the discharge reaction.
The magnesium dry cells described by Kirk and F r y
contained a cathode consisting of a mix of manganese dioxide-

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 Vol. 99, No. 8 ANNIVERSARY ISSUE ON PRIMARY
acetylene black and electrolyte. The separator consisted
either of starch-flour gel or of Kraft paper, the latter being
preferred because of the increased capacity. This cell con-
struction is in many ways identical with the present zinc
Leclanch6 construction.
The current producing reactions of magnesium dry cells
may be written as follows:
Anode, Mg -~ Mg ++ + 2e
Cathode, 2Mn02 ~- H~0 § 2e ~ 5,IntO3 -t- 2 0 H -
Over-all, Mg + 2MnO~ + H20 -~ Mn203 + Mg(OH)2.
In their papers the authors presented results obtained on
actual magnesium dry cells discharged on standard dry cell
tests. They have shown that magnesium cells can be made
to give double the capacity of comparable zinc batteries on
such tests corresponding to flashlight, lantern, and radio
applications.
There are, however, some problems which have to be solved
before the magnesium dry cell as described supplants the
zinc dry cell. A few of these are:
1. Magnesium cans cannot be drawn as easily as zinc cans
and, although lighter in weight, are thicker than correspond-
ing zinc cans. However, the results which DoT has obtained
with impact extrusion of magnesium cans indicate that the
manufacture of magnesium cans by the impact extrusion
method is feasible. The difficulty is that most of the dry
battery industry is equipped with zinc can-drawing equip-
ment.
2. Another problem is the cleaning of the magnesium and
the preparation of the surface. The following steps are
necessary: (a) the lubricant used for coating the slug for
impact extrusion has to be removed (using an alkaline
solution) ; this is followed by (b) one or two pickling solutions
which clean the surface and stabilize it. Presumably a
chrome-type film forms over the metal which conditions i t s o
that it is more resistant to corrosion.
3. A third problem which has been pointed out in the
Kirk and F r y papers is that of delayed action. That is, when
the circuit of the cell is closed, a few seconds are required
for the magnesium cell to come up to operating voltage. This
m a y present difficulties in certain applications.
4. Fourth, the high voltage of the magnesium cell HIay
cause inconveniences. Most equipment is designed around the
zinc Leclanch6 system and the introduction of a new cell
which has a higher operating voltage will undoubtedly present
a problem with respect to this equipment. I t is conceivable
that the solution may lie in lowering the cathode voltage of
the cell or increasing the internal resistance of the battery.
5. Finally, magnesium cans cannot be satisfactorily sol-
dered to give good interce]l connections. However, stranded
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CELL SYSTEMS 189C
wire has been spot-welded successfully to the magnesium
cans.
The problems as listed above are not believed unsolvable
and, in fact, the development of a magnesium dry cell has
progressed to the stage that extensive field tests are being
conducted by the military (30).
REFERENCES
1. G. HEIN, Elektrochem. Z., 8, 472, 517 (1887).
2. R. FICHTER, Chimia, 1, 141 (1947).
3. R. C. K~RK AND A. B. FRY, J. (and Trans.) Electrochem.
Soe., 94, 277 (1948).
4. R. T. WOOD (to American Magnesium Corp.), U. S. Pat.
1,696,873, Dec. 25, 1928.
5. G. FERRABINO, Swiss Fat. 137,015, March 1, 1930.
6. G. FERRABINO, Swiss Pat. 137,016, March 1, 1930.
7. C. J. GORDON, V. S. Pat. 2,040,255, May 12, 1936.
8. C. J. GORDON, U. S. Pat. 2,050,172, Aug. 4, 1936.
9. Jo W. SMITH, Light Metals, 1, 172 (1938) ; 9, 354 (1946).
10. C. J. GORDON, British Pat. 526,601, Dec. 12, 1940.
11. G.W. HEISE (to National Carbon Co.), U. S. Pat. 1,899,615,
Feb. 28, 1933.
12. S. RUBEN, U. S. Pat. 1,920,151, July 25, 1933.
13. S. RUBEN, U. S. Pat. 2,257,129, Sept. 30, 1941.
14. S. RVBEN, U. S. Pat. Re. 22,053, March 24, 1942.
15. E. L. AND L.. B. ANDERSON, U. S. Pat. 2,530,751, Nov. 21,
1950.
16. W. R. FORSYTHE (to Dow Chemical Co.), U. S. Pat.
2,301,390, Nov. 10, 1942.
17. H. A. BARBIAN AND R. E. McNuLTY, Trans. Electrochem.
Soc., 91,387 (1947).
18. H. K. DELONG XND H. A. BARBIXN (to DOT Chemical
Co.), U. S. Pat. 2,481,204, Sept. 6, 1949.
19. G. POLCICH, U. S. Pat. 1,771,190, July 22, 1930.
20. D. V. Lovzos (to Burgess Battery Co.), U. S. Pat.
2,535,742, Dec. 26, 1950.
21. P. MATARAZZO,Italian Pat. 190,791, Sept. 13, 1907.
22. L. H. HARRISS (to Burgess Battery Co.), U. S. Pat.
2,543,106, Feb. 27, 1951.
23. J. B. MULLEN AND P. L. HOWARD,Trans. Electrochem Soc.,
90, 529 (1946).
24. H. E. LAWSON (to Burgess Battery Co.), U. S. Pat.
2,428,850, Oct. 14, 1947.
25. H. E. LAWSON, V. S. Pat. 2,445,306, July 13, 1948.
26. A. B. FRY, R. C. KIRK, AND P. F. GEORGE (to DOW Chemi-
cal Co.), U. S. Pat. 2,547,907, April 3, 1951.
27. A. B. FRy, R. C. KIRK, AND P. F. GEORGE (to DOT Chemi-
cal Co.), U. S. Pat. 2,547,908, April 3, 1951.
28. P. F. GEORGE,A. B. FRY, AND R. C. KIRK (to DOT Chemi-
cal Co.), U. S. Pat. 2,547,909, April 3, 1951.
29. R. C. KIRK, P. F. GEORGE, AND A. B. FRY, J. Electrochem.
Soc., 99, 323 (1952).
30. Business Week, p. 67, April 26, 1952.
31. I. C. BLAKE AND J. B. MULLEN (to Burgess Battery Co.),
U. S. Pat. 2,534,403, Dec. 19, 1950.