Linden D., Reddy T.B. (eds.) Handbook of batteries
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18.8 CHAPTER EIGHTEEN
FIGURE 18.6 Effect of changing current density on battery voltage at 25⬚C. (Cour-
tesy of Eagle-Picher Industries.)
FIGURE 18.7 Discharge curves for high-rate zinc /silver oxide bat-
teries at 25⬚C. (Courtesy of Eagle-Picher Industries.)
18.4.2 Discharge Curves
A set of discharge curves for high-rate batteries is shown in Fig. 18.7 and for low-rate
batteries in Fig. 18.8. The designs for these two types of batteries are quite different, with
the principal difference being the thickness of the plates. The thin plates used in high-rate
cells provide more surface area for lower current density, thus better voltage control and also
more efficient utilization of the active material. At lower rates of discharge, as in Fig. 18.8,
the voltage level is higher and active material utilization is also excellent, both because of
lower current density. It will be noted that the low-rate discharge curves are above 1.6 V for
a period of time. This is the effect of the divalent oxide, which affects voltage only at low
rates. Most of the divalent capacity is obtained at high rates, but its voltage is decreased by
the higher current density imposed.
ZINC / SILVER OXIDE RESERVE BATTERIES 18.9
FIGURE 18.8 Discharge curves for low-rate zinc /silver oxide batteries at 25⬚C.
(Courtesy of Eagle-Picher Industries.)
FIGURE 18.9 Effects of temperature on high-rate zinc / silver oxide
primary batteries discharged at the 1-h rate. (Courtesy of Eagle-Picher
Industries.)
18.4.3 Effect of Temperature
The family of curves shown in Fig. 18.9 illustrates the performance obtained from a high-
rate battery when discharged over a range of temperatures. It should be understood that the
change in voltage levels caused by temperature is closely related to the changes caused by
current density. Thus the adverse effect of cold temperature can be improved by reducing
the current density of the cell, and the voltage and capacity of batteries discharged at high
current densities can be improved by increasing their operating temperature. Figure 18.10
shows a family of curves for low-rate batteries discharged at various temperatures. The two
sets of curves show that the zinc/silver oxide system is significantly affected at temperatures
below 0
⬚C and thus is not recommended for applications in this environment without heaters.
18.10 CHAPTER EIGHTEEN
FIGURE 18.10 Effects of temperature on low-rate zinc / silver oxide
primary batteries discharged at the 24-h rate. (Courtesy of Eagle-
Picher Industries.)
18.4.4 Impedance
Figure 18.11 shows the dynamic internal resistance (DIR) of a high-rate cell at various stages
of discharge and temperature. These curves show a declining (
⌬V/ ⌬I) ratio until the end of
discharge, at which time the dynamic resistance rises rapidly. The declining impedance is
caused by an improvement in the positive-plate conductivity and a temperature rise during
the discharge. This feature can vary considerably, depending on cell design, ambient tem-
perature of the discharge, and the point in time after the change of discharge rate when the
voltage change is observed.
FIGURE 18.11 Dynamic internal resistance of zinc / silver oxide primary bat-
teries. (Courtesy of Eagle-Picher Industries.)
ZINC / SILVER OXIDE RESERVE BATTERIES 18.11
FIGURE 18.13 Dry storage of zinc/ silver oxide primary
batteries. (Courtesy of Eagle-Picher Industries.)
18.4.5 Service
The performance of zinc/silver oxide batteries in Amperes per unit weight and volume versus
service time is given in Fig. 18.12. It can be noted, again, that this battery system is partic-
ularly sensitive to temperatures below 0
⬚C. These data are applicable, within reasonable
accuracy, for both high- and low-rate designs.
FIGURE 18.12 Service life of zinc / silver oxide primary batteries. (Courtesy of
Eagle-Picher Industries.)
18.4.6 Shelf Life
The dry shelf life of the zinc/silver oxide battery is shown in Fig. 18.13, which gives storage
data at 25, 50, and 74
⬚C for periods of up to 2 years. The losses shown are based on the
assumption that the positive active material is divalent silver oxide, which slowly degrades
to monovalent oxide at temperatures above about 20
⬚C. Degradation of the negative plate is
minimal. It is expected that the monovalent oxide level would be reached in about 30 months
when the storage temperature is 50
⬚C. Experience has shown that batteries stored at average
ambient temperatures of 25
⬚C or lower retain capacity at or above the monovalent oxide
level for a period of 25 years or longer.
18.12 CHAPTER EIGHTEEN
The wet shelf life of the zinc /silver oxide battery varies considerably with design and
method of manufacture. Figure 18.14 provides a guide to the expected performance of most
designs. The wet shelf-life degradation is caused principally by loss of negative-plate ca-
pacity (dissolution of the sponge zinc in the electrolyte) or development of short circuits
through the cellulosic separators.
FIGURE 18.14 Wet (activated) storage of zinc/ silver oxide primary batter-
ies. (Courtesy of Eagle-Picher Industries.)
18.5 CELL AND BATTERY TYPES AND SIZES
Single-cell units of the reserve zinc/ silver oxide type are available in sizes from about 1 Ah
as a minimum up to about 775 Ah. Table 18.1a and 18.1b provides the specifications for a
series of high-rate cells ranging in capacity from 1 to 250 Ah and a series of low-rate cells
ranging in capacity from about 2 to 2680 Ah. These are all manually activated.
Table 18.2 lists a number of automatically activated batteries which have been designed
to meet various specific applications. Most of these batteries are high-rate with a short wet-
life. The weight and volume of this type are more a function of the load requirements and
the space envelope provided than voltage and capacity.
18.13
TABLE 18.1a Zinc / Silver Oxide Manually Activated Batteries
High-rate cells, 15-mm rate
Cell type* Cap., Ah
Specific
Energy
Wh/kg
Energy
Density
Wh/ L Wt, g
Low-rate cells, 20-h rate
Cell type* Cap., Ah
Specific
Energy
Wh/kg
Energy
Density
Wh/ L Wt, g
Physical dimensions, cm
Length Width Height
SZH 1.0 1.0 57 104 25 SZL 1.7 1.7 84 171 30 1.09 2.69 5.16
SZH 1.6 1.6 66 110 35 SZL 2.8 2.8 88 201 50 1.25 3.07 5.72
SZH 2.4 2.4 66 116 55 SZL 4.5 4.5 92 220 75 1.42 3.50 6.32
SZH 4.0 4.0 66 128 90 SZL 7.5 7.5 97 250 120 1.63 4.00 7.09
SZH 7.0 7.0 66 134 160 SZL 16.8 16.8 106 305 240 2.00 4.95 8.48
SZH 16.0 16.0 66 140 370 SZL 43.2 43.2 125 397 520 2.54 6.27 10.39
SZH 68.0 68.0 80 196 1290 SZL 160.0 160.0 187 470 1330 3.73 9.27 15.09
SZH 250.0 250.0 154 410 2450 — — — — — 4.32 9.45 22.43
— — — — — SZL 410.0 410.0 210 560 3000 4.22 13.84 19.35
— — — — — SZL 775.0 775.0 276 957 4380 6.96 8.36 21.70
* Eagle-Picher Industries.
18.14
TABLE 18.1b Zinc /Silver Oxide Manually Activated Primary Batteries*
Cell Model† Type‡ Voltage§ Capacity Ah
Specific
Energy
Wh/kg
Energy
Density
Wh/ L Weight g
Dimensions, cm
Height Width Depth Volume L
PM1
PMV2
PM3
PML4
PM5
PMC5
PMC10
PM15
PMV16
PM30
PM58
PML100
PML140
PML170
PML400
PML2500
HR
HR
HR
HR
MR
MR
MR
HR
HR
HR
HR
LR
LR
LR
LR
LR
1.42
1.48
1.41
1.42
1.49
1.48
1.48
1.42
1.47
1.44
1.42
1.50
1.49
1.48
1.47
1.48
2.0
5.3
6.4
8.3
9.9
12.3
28
19
18
41
56
118
165
200
375
2680
92
103
106
113
119
141
152
92
72
98
85
180
197
197
218
221
147
184
187
208
187
231
312
180
141
169
162
376
439
469
566
721
31
76
85
104
124
129
272
292
365
600
938
982
1,250
1,500
2,525
17,960
5.13
6.42
7.26
8.53
7.36
7.36
12.00
12.55
15.57
16.64
18.42
13.74
16.36
18.44
16.10
47.90
2.74
4.37
4.37
4.37
5.28
5.28
5.89
5.89
5.84
8.28
8.26
9.70
9.70
9.70
15.27
10.72
1.37
1.52
1.52
1.52
2.03
2.03
1.88
2.03
2.06
2.54
3.23
3.53
3.53
3.53
3.96
10.72
0.019
0.043
0.048
0.057
0.079
0.079
0.133
0.150
0.187
0.350
0.491
0.470
0.560
0.631
0.974
5.505
* These batteries are normally used as primaries. However, they all can be recharged (typically 3 to 10 cycles).
† Yardney Technical Products.
‡HR
⫽ High rate, MR ⫽ Medium rate, LR ⫽ Low rate.
§HR
⫽ 15-minute rate, MR ⫽ 1-h rate, LR ⫽ 5-h rate.
18.15
TABLE 18.2 Zinc / Silver Oxide Automatically Activated Batteries
Part
Number* Application
Weight,
kg
Volume,
L
Voltage,
V
Current,
A
Capacity,
Ah
Energy density
Wh/kg Wh/L
EPI 4331
EPI 4568
EPI 4500
YTP 15148
EPI 4567
EPI 4470
EPI 4445
YTP 15066
EPI 4569
YTP P-530
YTP P-515
YTP P-512
YTP P-468
YTP P-471
AIM-7
Peacekeeper
Pariot
Trident I
Peacekeeper
Harpoon
Torpedo
Trident I
Trident II
Minuteman
Sparrow
NMD
AGM130
Peacekeper
1.0
3.3
3.6
5.0
6.2
8.6
9.3
14.5
30.4
0.77
0.99
0.86
7.03
19.5
0.45
1.89
1.61
1.20
3.46
3.5
4.8
3.8
19.9
0.36
0.45
0.30
2.70
12.1
26
30
51
28
30
28
28
30, 31
30, 31
30
24
30
28
76, 31
10.0
2.0
18.0
6.0
11.0
27, 40
30
15, 23
18, 42
10.0
11.0
13.0
30
16.7, 40
0.8
3.8
1.5
12.0
16.0
8, 12
20
4, 10
20, 10
0.46
0.45
0.30
12.08
5.46, 40.90
21
35
21
65
77
65
60
30
30
17.9
10.9
10.5
45.0
86.3
46
60
48
284
139
160
117
112
46
38.3
24.0
30.0
117.0
139.3
* EPI—Eagle-Picher Industries; YTP—Yardney Technical Products.
18.16 CHAPTER EIGHTEEN
18.6 SPECIAL FEATURES AND HANDLING
Both manually and automatically activated zinc/silver oxide batteries were developed to meet
highly stringent requirements with regard to performance and reliability. The time and tem-
perature of storage prior to use are of importance, and records should be maintained to
ensure use within allowable limits. Special care must be exercised to ensure that the proper
amount of the specified type of electrolyte is added to each cell of a manual-type battery
and that, after activation, the unit is discharged within the shelf-life limitation at the proper
temperature. Some battery containers have pressure-relief valves or heaters, or both, and
these must be carefully maintained and monitored.
Automatically activated batteries require special preinstallation check out of gas generator
ignitor circuits, heater circuits, and vent fittings. For long-term installations, there should be
monitoring of the ambient temperature to prevent degradation caused by exposure to high
temperatures. Periodic checks should be made to ensure that the ignitor circuits are intact
because some circuits are sensitive to electromagnetic fields. After activation, if the battery
is not discharged within the specified time, it must be replaced.
The proper electrical performance of these batteries is best ensured by operating them at
temperatures at or slightly above room temperature. Temperatures below 15
⬚C can adversely
affect the voltage regulation of high-rate batteries, and below 0
⬚C there is also considerable
loss of capacity for both types.
18.7 COST
The cost of high-performance primary zinc/ silver oxide batteries is dependent on the spec-
ifications to which they are built and the quantity involved. Manual-type batteries may cost
anywhere from $5 to $15 per Watthour; remote-activated types will cost about $15 to $20
per Watthour. When the price of silver is high, material cost becomes one of the chief
disadvantages of these batteries. There are many applications, however, in which no other
technology can meet the high energy density of the zinc/ silver oxide primary system.
BIBLIOGRAPHY
Bauer, P.: Batteries far Space Power Systems, U.S. Government Printing Office, Washington, D.C., 1968.
Cahoon, N. C., and G. W. Heise: The Primary Battery, Wiley, New York, 1969.
Chubb, M. F., and J. M. Dines: ‘‘Electric Battery,’’ U.S. Patent 3,022,364.
Eagle-Picher Industries, Joplin, MO, brochure.
Fleiseher, A., and J. J. Lander: Zinc Silver Oxide Batteries, Wiley, New York, 1971.
Hollman, F. G., et al.: ‘‘Silver Peroxide Battery and Method of Making,’’ U.S. Patent 2,727,083.
Jasinski, R.: High Energy Batteries, Plenum, New York, 1967.
Yardney Technical Products, Pawcatuck, CT, brochure.
19.1
CHAPTER 19
SPIN-DEPENDENT RESERVE
BATTERIES
Asaf A. Benderly
Revised by Allan B. Goldberg
19.1 GENERAL CHARACTERISTICS
Various military, and a few civilian, applications with long shelf-life requirements must turn
to reserve batteries for their electric power. This is particularly true when the system requires
that the power supply be integrally packaged with the electronics and not replaced throughout
the storage life of the system. Typical of such applications are fuzing, control, and arming
systems for artillery and other spin-stabilized projectiles.
High spin forces, such as those encountered in artillery projectiles, may produce a difficult
environment for many battery designs. However, special designs for liquid-electrolyte reserve
batteries have evolved that take advantage of spin to bring about their activation and then
keep the electrolyte within the cell structure.
A typical spin-dependent reserve battery is illustrated in Figs. 19.1 and 19.2. The electrode
stack consists of electrodes and cell spacers of an annular configuration packaged dry and
therefore capable of long-term storage. A metal ampoule, inserted in the center hole of the
stack, houses the electrolyte. Upon firing of the gun, the ampoule opens; the electrolyte is
released and is then distributed into the annular-shaped cells centrifugally, thereby causing
the battery to become active.
FIGURE 19.1 Cross-section of lead / fluoboric acid / lead dioxide multi-
cell reserve battery showing ‘‘dashpot’’ cutter for copper ampoule. (Cour-
tesy of U.S. Department of the Army.)