Linden D., Reddy T.B. (eds.) Handbook of batteries

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20.12 CHAPTER TWENTY

FIGURE 20.9 Design of reserve Li/Li

CoO

battery for Hand-emplaced Wide Area Munitions (HWAM).

(Courtesy of Alliant Techsystems, Inc.)

FIGURE 20.10 High-power 1 KW Li/oxychloride reserve battery. (Courtesy of Eagle-Picher Technologies)

AMBIENT-TEMPERATURE LITHIUM ANODE RESERVE BATTERIES 20.13

FIGURE 20.11 Sandia National Laboratories Li-SOCl

reserve battery model MC3945.

Multicell Bipolar Construction with Single-Activator Reservoir. Lithium anode reserve

batteries, using bipolar construction, are relatively few in number and always developed for

speciﬁc applications. The bipolar construction—one component used as both the anode col-

lector of one cell and the cathode collector of the next cell in the stack—is not unique to

the lithium reserve battery, but an adaptation of techniques used in other types of batteries.

There are several advantages of the bipolar construction:

Very high energy and power density for high-voltage batteries

Rugged construction to withstand spin and setback forces from artillery ﬁring

Flexibility to adjust voltages in the cell stack

Adaptability to varying energy and power requirements

Figure 20.11 is an illustration of a reserve lithium/ thionyl chloride battery using a bipolar

plate construction. This battery weighs approximately 5.4 kg and has a volume of 2000 cm.

Activation of the reserve battery is accomplished by supplying an electric pulse to the

battery by ﬁring an electric squib or actuator or by some mechanical means. This type of

reserve battery has been used chieﬂy in artillery shells for electronic fuze power supplies

and in missiles for the electronic power supply. Therefore the electric pulse can be supplied

prior to ﬁring or at the time of launch. However, for artillery fuze power supplies, the battery

is usually activated by the launch acceleration (set back) and /or the spin forces. The accel-

20.14 CHAPTER TWENTY

eration force of the artillery shell releases a ﬁring pin which strikes and ﬁres a primer. The

primer can ignite a gas generator or directly release a stored gas by breaking open a metal

diaphragm.

Once the battery has been initiated as described, the gas pressure (such as from a gas

generator, stored gas/ liquid, or CO

) forces the electrolyte into each of the cells through a

manifold (electrolyte distribution network).

The electrolyte reservoir is generally made using a collapsible cup, a bellows, or a wound

tubing design. These serve to hold the electrolyte during the long inactive storage period

and act as the delivery mechanism during activation. Each reservoir has some type of dia-

phragm which is broken with high pressure or mechanical means to allow the electrolyte to

enter the cell-stack part of the battery hardware.

The bipolar cell stack with the electrolyte distribution manifold in the center comprises

the battery section. When electrolyte enters the center manifold, it is distributed to each cell

through holes or passageways in the housing encompassing the battery. The design of the

manifold is the key to controlling intercell leakage. For bipolar batteries, life requirements

are relatively short (seconds to several hours); therefore the manifolding is relatively simple.

But when longer life is needed, the parasitic leakage currents are controlled by the length

and area of the leakage path.

Another battery of this design was developed as a power source for the Extended Range

Guided Munition (ERGM). Ultimately, this design would be similar to the design shown in

Fig. 20.10. However, the development test ﬁxture used is shown in Fig. 20.12. It uses the

LI/ SOCl

chemistry but with a special lithium tetrachlorogallate electrolyte optimized for

performance. The test ﬁxture employs gas pressure to compress the bellows, rupturing the

diaphragm and activating the battery. In actual use, set-back forces on launch perform this

function.

Battery

Module

CRES Diaphram

Cover, Reservoir

2 Way Direct Lift

Solenoid Valve

Bellows Reservoir

Bulkhead

Reservoir Compartment

Battery Module Compartment

Cover, Battery Module

Liquid Nitrogen

FIGURE 20.12 Laboratory test ﬁxture for activation of Extended Range Guided

Missile (ERGM) battery using Li / SOCL

system. (Courtesy Yardney Technical

Products, Inc.)

TABLE 20.3 Speciﬁcations for ERGM Battery

Description Speciﬁcations

12 V Section Regulation • Load voltage Range: 9.5 to 16.0 V

• 60W Applied Continuously

28 V Section Regulation

• Load Voltage Range: 24 to 40V

• 15 W applied continuously

• 125 Pulses, 8 Amperes, 0.1 Sec.

Duration, Evenly Distributed

Operating Life

• 480 Seconds Minimum

AMBIENT-TEMPERATURE LITHIUM ANODE RESERVE BATTERIES 20.15

20.4 PERFORMANCE CHARACTERISTICS

20.4.1 Ampoule-Type Batteries

Voltage characteristics at the ‘‘time of activation’’ are unique and an important feature of

reserve batteries. This is especially true for military applications, where reserve batteries

must normally be designed to meet operational voltage in less than 1 s and in many cases

even less than s. For nonmilitary use, activation times to operating voltage level are

–

less critical. However, for a given reserve battery design and the electrochemical couple

used, the activation time is dependent on the discharge rate and temperature.

In general, the voltage rise times for both Li /SOCl

and Li/ V

have similar charac-

teristics. Figure 20.13 shows the rise-time characteristics for the Li/SOCl

battery (illustrated

in Fig. 20.4) at ﬁve temperatures at a current density of 0.1 mA/ cm

(approximately a

C/ 500 rate). Rise times are typically below 20 ms at ambient (24

⬚C) and higher temperatures

but increase up to 500 ms at the lower temperatures. The ability to activate rapidly is pri-

marily due to the cell design, which allows the electrolyte to penetrate and wick into the

porous electrode and separator at the instant of ampoule breakage.

FIGURE 20.13 Rise-time characteristics after activation of Li / SOCl

reserve battery, Alliant

model G2659B1; load ⫽ 4.35 k⍀.(Courtesy of Alliant Techsystems, Inc.)

The voltage levels of both the Li/V

and the Li/SOCl

systems (batteries illustrated

in Figs. 20.3 and 20.4) under steady-state discharge conditions are shown in Fig. 20.14.

These two systems are very close in voltage at the lower temperatures, ranging from 3.3 to

3.0 V at current densities of less than 1 mA/ cm

. At higher temperatures, ambient and above

up to 74

⬚C, the Li/ SOCl

battery operates above 3.5 V, whereas the Li /V

batteries nor-

mally operate between 3.2 and 3.4 V. The higher voltage and increased capacity account for

the signiﬁcant increase in energy density of the SOCl

over the V

battery. As shown in

Fig. 20.14, the V

system has very little change in capacity over the wide temperature

range but is still much lower in capacity than the SOCl

battery when discharged at the same

rate, namely 0.1 mA /cm

. Although the capacity and voltage of the Li/SOCl

battery are

lower at cold temperatures, its output is still higher than that of most other systems and its

voltage proﬁle is characterized by a ﬂat single-step plateau. The high-temperature curve is

also extremely ﬂat and typically discharges above 3.6 V at a current density of 0.1 mA/

. The voltage characteristics on ambient temperature discharges are similar to those at

high temperature except for a slightly lower load voltage when discharged at the same rate,

20.16 CHAPTER TWENTY

FIGURE 20.14 Comparison of discharge proﬁles for reserve-type Li /V

(---) and Li / SOCl

(——) batteries. Current density ⫽ 0.1 mA/ cm

TABLE 20.4 Performance Comparison between Li/ SOCl

and Li /V

Systems

System Temperature, ⬚C

Cell

voltage, V

Capacity,

mAh

Cell

volume,

Cell

weight,

Speciﬁc

energy

Wh/kg

Energy

density

Wh/L

Li/V

* ⫺37

3.15

3.30

160

180

5.1

50.4

59.4

98.8

116.5

Li/ SOCl

† ⫺37

3.05

3.60

300

450

5.1

10.5

87.1

154.3

179.4

317.6

* Alliant model G2659.

† Alliant model G2659B1.

averaging 3.5 V. Table 20.4 compares the output parameters of the two systems with identical

hardware and shows the superior performance of the Li/ SOCl

battery. The similarity in

voltage and the fact that the same hardware is used for both systems permits a one-for-one

replacement.

Figure 20.15 shows the effect of inactive storage of up to 12 months at 71

⬚C on the

Li/ SOCl

battery performance over the temperature range of ⫺54 to 71⬚C. No signiﬁcant

effect on performance was found as a result of the storage. The slightly lower voltages during

discharge or the voltage delays when the load is ﬁrst applied on active (nonreserve) batteries

were not present with the reserve batteries. Figure 20.15 also gives a summary of the per-

formance of fresh batteries at various discharge loads and temperatures.

Figure 20.16 shows the discharge curves of the Li /SOCl

reserve A-size battery (illus-

trated in Fig. 20.2). The current drain capability of a reserve system signiﬁcantly exceeds

that of the corresponding active primary battery. Figure 20.16 shows the discharge charac-

teristics at 1.25 k

⍀ (about 3 mA) or 0.15 mA/cm

. Currents higher than 1.5 A (current

density of 100 mA/ cm

) can be obtained at voltages higher than 2.0 V for several minutes

⫺10⬚C. The speciﬁc energy of the cells, to a cutoff voltage of 2.0 V, as a function of the

discharge current at various temperatures is shown in Fig. 20.17. The performance at higher

temperatures is close to that for 25

⬚C.

AMBIENT-TEMPERATURE LITHIUM ANODE RESERVE BATTERIES 20.17

FIGURE 20.15 Effect of discharge rate and inactive storage on Li / SOCl

reserve

battery, Alliant model G2659B1. (Courtesy of Alliant Techsystems, Inc.)

20.18 CHAPTER TWENTY

FIGURE 20.16 Typical discharge curves on 1.25 kOhm of Li / SOCl

re-

serve battery, Tadiran model TL-5160. (Courtesy of Tadiran Industries,

Ltd ).

FIGURE 20.17 Speciﬁc energy as a function of discharge cur-

rent and temperature for Li / SOCl

reserve battery, Tadiran model

TL-5160. (Courtesy of Tadiran Industries, Ltd.)

AMBIENT-TEMPERATURE LITHIUM ANODE RESERVE BATTERIES 20.19

20.4.2 Multicell Battery Design

The performance characteristics of the Li /SO

multicell single-activation design battery are

shown in Fig. 20.18. The activation and discharge proﬁles for a 12-V, 100-Ah battery using

an LiAsF

in AN–SO

electrolyte are illustrated. Because the battery is activated manually,

the slower voltage rise time is expected because the cutting of the diaphragm in the center

bulkhead requires several turns on the activation bolt. The battery could easily be activated

with an electric or mechanical input to a piston actuator or squib to cut the diaphragm to

improve the voltage rise time. Although the operational life of the battery can be very short,

the data illustrate its capability for a long-term discharge at low discharge rates if a stable

electrolyte is used.

Typical discharge curves at several temperatures for the two types of single-cells used in

the Li /SOCl

reserve battery illustrated in Fig. 20.8 are shown in Fig. 20.19.

FIGURE 20.18 Activation and discharge voltage proﬁle for 12-V, 100-Ah Li / SO

battery; elec-

trolyte: LiAsF

in AN–SO

20.20 CHAPTER TWENTY

FIGURE 20.19 Discharge characteristics of Li/ SOCl

reserve batteries, Alliant model G3070A2. (a)Low-

rate-cell discharge proﬁle: (b) High-rate-cell discharge proﬁle. (c) Voltage characteristics of high-rate cell at

various temperatures and power levels. (Courtesy of Alliant Techsystems, Inc.)

REFERENCES

1. A. N. Dey, ‘‘Lithium Anode Film and Organic and Inorganic Electrolyte Batteries,’’ in Thin Solid

Films, vol. 43, Elsevier Sequoia, Lausanne, Switzerland, 1977, p. 131.

2. R. J. Horning, ‘‘Small Lithium/ Vanadium Pentoxide Reserve Cells,’’ Proc. 10th Intersoc. Energy

Convers. Eng. Conf., 1975.

3. W. B. Ebner and C. R. Walk, ‘‘Stability of LiAsF

-Methyl Formate Electrolyte Solutions,’’ Proc.

27th Power Sources Conf., 1976.

4. B. Ravid, A Reserve-Type Lithium-Thionyl Chloride Battery, Tadiran Israel Electronics Industries,

1979.

5. M. J. Domenicomi and F. G. Murphy, ‘‘High Discharge Rate Reserve Cell and Electrolyte,’’ U.S.

Patent 4,150,198, Apr. 17, 1979.

6. M. Babai, U. Meishar, and B. Ravid, ‘‘Modiﬁed Li /SOCl

Reserve Cells with Improved Perform-

ance,’’ Proc. 29th Power Sources Conf., June 1980.

7. P. M. Shah, ‘‘A Stable Electrolyte for Li /SO

Reserve Cells,’’ Proc. 27th Power Sources Symp.,

1976.

8. P. M. Shah and W. J. Eppley, ‘‘Stability of the LiAsF

:An:SO

Electrolyte,’’ Proc. 28th Power Sources

Symp., 1978.

AMBIENT-TEMPERATURE LITHIUM ANODE RESERVE BATTERIES 20.21

9. R. J. Horning and K. F. Garoutte, ‘‘Li /SO

Multicell Reserve Structure,’’ Proc. 27th Power Sources

Symp., 1976.

10. Hsiu-Ping Lin and K. Burgess, ‘‘Synthesis of Charged Li

CoO

(0 ⬍ x ⬍ 1) For Primary and

Secondary Batteries,’’ U.S. Patent 5,667,660 (1997).

11. W. J. Eppley and R. J. Horning, ‘‘Lithium / Thionyl Chloride Reserve Cell Development,’’ Proc. 28th

Power Sources Symp., 1978.

12. J. Nolting and N. A. Remer, ‘‘Development and Manufacture of a Large Multicell Lithium-Thionyl

Chloride Reserve Battery,’’ Proc. 35th International Power Sources Symp., 1992.

13. C. Kelly, ‘‘Development of HWAM Li

CoO

Reserve Battery,’’ Report No. NSWCCD-TR-98 / 005,

April 1997.

14. S. McKay, M. Peabody and J. Brazzell, Proc. 39th Power Sources Conf., pp. 73–76, 2000.

15. P. G. Russell, D. C. Williams, C. Marsh, and T. B. Reddy, Proc. 6th Workshop for Battery Explor-

atory Development, pp. 277–281, 1999.