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

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LITHIUM BATTERIES 14.75

FIGURE 14.65 Pulse discharge characteristics of Li / (CF)

coin-type (165-mAh size) at

20⬚C. (Courtesy of Panasonic, Division of Matsushita Electric Corp. of America.)

The performance of the coin battery (165-mAh capacity) is summarized in Fig. 14.66.

Figure 14.66a shows the average load voltage (plateau voltage during discharge) and Fig.

14.66b shows the capacity for discharges at various loads and temperatures.

Figure 14.67 summarizes the discharge performance data for Li/(CF)

coin-type batteries

normalized for a 1-g and 1-mL battery. These data can be used to approximate the size or

performance of a battery for a particular application.

Cylindrical Cells. The cylindrical batteries are designed to operate at heavier discharge

loads than the coin batteries. Figure 14.68 shows the discharge characteristics at 20

⬚Cofa

cylindrical A-size cell rated at 1.2 Ah; Fig. 14.69 presents the discharge curves at other

–

discharge temperatures. In some cases an initial low voltage is observed with the Li/ (CF)

battery; that is, the voltage drops initially below the operating level on load and recovers

gradually as the discharge progresses. This is attributed to the fact that (CF)

is an insulator,

but the resistance of the cathode decreased during the discharge as conductive carbon is

produced.

The average load voltages for cylindrical batteries at various temperatures are given in

Fig. 14.70. The performance data are then summarized in Fig. 14.71, which shows the effect

of temperature and load on the service life of a battery normalized to unit weight (grams)

and volume (cubic centimeters).

The internal impedance of these cells is relatively low. For example, the internal resistance

of the BR A battery ranges between 0.4

⍀ at 25⬚C and 0.6 ⍀ at ⫺20⬚C, but rises toward

–

the end of the discharge, as shown in Fig. 14.72.

14.76 CHAPTER FOURTEEN

FIGURE 14.66 Discharge characteristics of Li / (CF)

coin-type battery (165-mAh size).

(a) Operating voltage vs. discharge load; voltage at 50% discharge. (b) Capacity vs. discharge

load; cutoff at 2.0 V. (Courtesy of Panasonic, Division of Matsushita Electric Corp. of

America.)

FIGURE 14.67 Service life of Li/ (CF)

coin-type batteries at various

discharge rates and temperatures; 2.0-V end voltage.

LITHIUM BATTERIES 14.77

FIGURE 14.68 Typical discharge curves for Li / (CF)

cylindrical bat-

tery, BR A size, at 20⬚C. (Courtesy of Panasonic, Division of Matsushita

–

Electric Corp. of America.)

FIGURE 14.69 Typical discharge curves of Li / (CF)

cylindrical battery at var-

ious temperatures; rated capacity 1.2 Ah; 300-⍀ discharge load. (Courtesy of

Panasonic, Division of Matsushita Electric Corp. of America.)

14.78 CHAPTER FOURTEEN

FIGURE 14.70 On-load plateau voltage vs. discharge rate of Li /

(CF)

cylindrical batteries. (Courtesy of Panasonic, Division of Mat-

sushita Electric Corp. of America.)

FIGURE 14.71 Service life of Li / (CF)

cylindrical batteries

at various discharge rates and temperatures; 1.8-V end voltage.

LITHIUM BATTERIES 14.79

FIGURE 14.72 Internal impedance during discharge of a Li / (CF)

cylindrical battery BR A size, at 20⬚C; 300-⍀ discharge load. (Cour-

–

tesy of Panasonic, Division of Matsushita Electric Corp. of America.)

High Temperature Coin-Type Batteries. The long shelf life and ﬂat discharge character-

istics of the Li/(CF)

system are utilized in coin-type batteries designed for mounting on PC

boards and used for long-term, low-drain or standby applications. The dimensions and per-

formance characteristics of this battery are given in Table 14.22a. These units are rated for

use from

⫺40 to ⫹150⬚C. The other Li /(CF)

cells are also capable of long-term discharge.

Shelf Life. The Li/ (CF)

cells have extremely good storage characteristics. Tests over more

than 10 years of storage show a self-discharge rate of about 0.5% per year at 20

⬚C and less

than 4% per year at 70

⬚C. These rates decrease on longer term storage.

This cell is also

well-suited for applications requiring low current drain over an extended period of time. This

is illustrated in Fig. 14.73, which shows the discharge characteristics of the A-size cell at

–

a 20-

␮

A discharge rate over a period of 7 years. Voltage delay after storage is not apparent

with these cells, except under stringent discharge conditions.

FIGURE 14.73 Long-term discharge of Li / (CF)

cylindrical battery.

BR A size; 150-k⍀ discharge. (Courtesy of Panasonic, Division of

–

Matsushita Electric Corp. of America.)

14.80 CHAPTER FOURTEEN

TABLE 14.22(a) Characteristics of Lithium / Carbon Monoﬂuoride Li/ (CF)

Batteries

Coin batteries, 3V

Model

no. IEC

*Nominal

capacity

(mAh)

Pulse

(mA)

Recommended

drain

Standard

(mA)

Low

(

␮

Dimensions

Diameter

(mm)

Height

(mm)

Weight

(g)

BR1216 — 25 5 0.03 1 12.5 1.60 0.6

BR1220 — 35 5 0.03 1 12.5 2.00 0.7

BR1225 BR1225 48 5 0.03 1 12.5 2.50 0.8

BR1616 — 48 8 0.03 1 16.0 1.60 1.0

BR1632 — 120 8 0.03 1 16.0 3.20 1.5

BR2016 BR2016 75 10 0.03 1 20.0 1.60 1.5

BR2020 BR2020 100 10 0.03 2 20.0 2.00 2.0

BR2032 — 190 10 0.03 4 20.0 3.20 2.5

BR2320 BR2320 110 10 0.03 2 23.0 2.0 2.5

BR2325 BR2325 165 10 0.03 3 23.0 2.50 3.2

BR2330 — 255 10 0.03 5 23.0 3.00 3.2

BR3032 BR3032 500 10 0.03 10 30.0 3.20 5.5

14.9.4 Cell and Battery Types

The Li/(CF)

batteries are manufactured in a number of coin, cylindrical, and pin conﬁgu-

rations. The major electrical and physical characteristics of some of these batteries are listed

in Table 14.22a and b. Manufacturers’ speciﬁcations should be consulted for the most recent

listings of commercially available cells.

Larger sizes of cells and batteries

have also been developed for military, governmental

and space applications, as given in Table 14.22b. Spiral-wound and prismatic cells are used

to build the multi-cell batteries given in this table. The smaller cylindrical cells employ a

0.030 cm thick steel case but larger units, such as the 1200 Ah cell, are reinforced with an

epoxy-ﬁberglass cylinder to provide additional strength, with an increase in weight about

half that of increasing the steel wall thickness. All these cells employ a Zeigler-type com-

pression seal, a unique cutter vent mechanism and two layers of separator. The ﬁrst is a

microporous layer to prevent particulate migration, and the second is a non-woven poly-

phenylene sulﬁde material to provide high-strength, high-temperature stability and good elec-

trolyte wicking action. These low-rate designs provide a speciﬁc energy of 600 Wh /kg and

an energy density of 1000 Wh/L in the DD size and higher values for larger units. Capacity

to a 2.0 volt cut-off as a function of temperature at four rates from 0.04 to 1.00 A is shown

in Fig. 14.74 for the DD design. The capacity of this battery is relatively independent of

temperature at the three lower currents and above 10

⬚C, but decreases at the higher rate and

lower temperatures. Discharge curves for the 1200 Ah reinforced cylindrical battery at the

2000 hours (ca. 500 mA) and the 1000-hour rate (ca. 1.0 Amp) are shown in Fig. 14.75.

The trailing knee in these discharge curves has been attributed to electrolyte starvation at

the end of the discharge. These batteries effectively demonstrate the ability of the lithium/

carbon monoﬂuoride system to provide very high speciﬁc energies and energy densities, in

these low rate designs.

LITHIUM BATTERIES 14.81

TABLE 14.22(a) Characteristics of Lithium / Carbon Monoﬂuoride Li/ (CF)

Batteries (Continued)

Coin type: High operating temperature, 3 V

Model no.

Dimensions

(mm)

Diameter Height

Nominal

capacity

(mAh)

Temperature

range

(

⬚C)

†BR1225A 12.5 2.5 48 ⫺40⬚C ⬃ 150⬚C

BR1632A 16.0 3.2 120

⫺40⬚C ⬃ 150⬚C

BR2330A 23.0 3.0 255

⫺40⬚C ⬃ 150⬚C

BR2477A 24.5 7.0 1000

⫺40⬚C ⬃ 125⬚C

Pin type, 3 V

Model no.

Nominal*

capacity

(mAh)

Recommended

drain

Pulse

(mA)

Standard

(mA)

Dimensions

Diameter

(mm)

Height

(mm)

Weight

(g)

Operating

temperature

range

BR425 25 4 0.5 4.2 25.9 0.55

⫺20⬚C ⬃ ⫹60⬚C

(

⫺4⬚F ⬃ 140⬚F)

BR435 50 6 1 4.2 35.9 0.85

⫺20⬚C ⬃ ⫹60⬚C

(

⫺4⬚F ⬃ 140⬚F)

Cylindrical type, 3 V

Model no.

Electrical

characteristics

(20

⬚)

§Nominal

capacity

(mAh)

Standard

drain

(mA)

Continuous

maximum

drain

(mA)

Max.

pulse

(mA)

Dimensions

(max.)

Diameter

(mm)

Approximate

height

(mm)

Weight

(g)

BR-C 5,000 150 300 1,000 26.0 50.5 42.0

BR-A 1,800 2.5 250 1,000 17.0 45.5 18.0

BR-2/ 3A 1,200 2.5 250 1,000 17.0 33.5 13.5

‡BR-AH 2,000 2.5 250 1,000 17.0 45.5 18.0

‡BR-AG 2,200 2.5 250 1,000 17.0 45.5 18.0

‡BR-2/ 3AH 1,350 2.5 250 1,000 17.0 33.5 13.5

‡BR-2/ 3AG 1,450 2.5 250 1,000 17.0 33.5 13.5

*Nominal capacity shown is based on standard drain.

†Under development

‡H and G versions are higher capacity

§Nominal capacity is based on standard drain and cutoff voltage down to 2.0V at 20

⬚C (68⬚F)

14.82 CHAPTER FOURTEEN

TABLE 14.22(b) Characteristics of Large Lithium/ Carbon Monoﬂuoride Li /(CF)

Batteries

Single-cell batteries

Part number Capacity (Ah)

Dimensions

(cm)

Diameter Height

Weight

(grams)

LCF-111 240 6.62 16.51 880

LCF-112 35 3.02 13.84 170

LCF-117 1200 11.43 26.67 3950

LCF-119 400 11.43 9.53 1575

LCF-122 18 3.37 6.06 —

LCF-123 35 3.37 11.72 —

LCF-313 40 6.45(L)

⫻ 3.43(W) ⫻ 7.09(H) 230

Multicell batteries

Part number

Capacity

(Ah)

Nominal

voltage

Dimensions

(cm)

HLW

Weight

(grams) Comments

MAP-9036 23.5 39 17.1 20.3 14.0 4586 Former

shuttle

range safety

system

MAP-9046 3.74 (

⫻2) 30 (⫻2) 15.9 17.3 7.6 3405 2 indepen-

dent volt-

age sections

MAP-9225 240 15 24.9 30.7 6.5 6000

MAP-9257 80 18 12.4 18.5 14.8 —

MAP-9319 240 21 42.9 29.7 9.7 —

MAP-9325 120 / 7.2 12 /15 17.1 18.6 9.2 — Optional

casing

MAP-9334 80 6 16.8 7.6 4.8 — Minuteman

III GRP

batteries

MAP-9381 70 39 31.3 20.0 9.7 — Integrated

capacitor

bank

MAP-9382 80 /70 33/ 12 20.1 17.6 14.1 — 2 indepen-

dent volt-

age sections

MAP-9389 280 15 23.6 33.8 11

MAP-9392 40 39 17.1 20.3 14.0 X-33 Range

safety sys-

tem

Source: Eagle-Picher Technologies.

LITHIUM BATTERIES 14.83

-20 -10 0 10 20 30 40 50 60

Capacity (Ah)

Degrees Centigrade

0.04 Amp

0.10 Amp

0.25 Amp

1.00 Amp

FIGURE 14.74 ‘DD’ Li / (CF)

discharge performance as a function of

rate and temperature.

2000 Hour Rate

1000 Hour Rate

3.00

2.75

2.50

2.25

2.00

1.75

1.50

1.25

1.00

0.75

0.25

0.50

0.00

Voltage (V)

0 500 1000 1500 2000 2500

Time (hours)

FIGURE 14.75 Typical discharge curves for 1200 Ah Li/ (CF)

battery.

14.84 CHAPTER FOURTEEN

14.9.5 Applications and Handling

The applications of the Li/(CF)

battery are similar to those of the other lithium/ solid-

cathode batteries, again taking advantage of the high speciﬁc energy and energy density and

long shelf life of these batteries. The Li/ (CF)

coin batteries are used as a power source for

watches, portable calculators, memory applications, and so on. The low-capacity miniature

pin-type batteries have been used as an energy source for LEDs and for ﬁshing lights and

microphones. The larger cylindrical batteries can also be used in memory applications, but

their higher drain capability also covers use in radio sets, for telemetry, and for photographic

and similar general-purpose applications.

Handling considerations for the Li /(CF)

systems, too, are similar to those for the other

lithium/ solid-cathode systems. The limited current capability of the coin and low-capacity

batteries restricts temperature rise during short circuit and reversal. These batteries can gen-

erally withstand this abusive use even though they are not provided with a safety vent

mechanism. The larger batteries are provided with a venting device, but short circuit, high

discharge rates, and reversal should be avoided as these conditions could cause the cell to

vent. Charging and incineration likewise should be avoided for all batteries. The manufac-

turer’s recommendations should be obtained for handling speciﬁc battery types.

14.10 LITHIUM/IRON DISULFIDE (Li/ FeS

) BATTERIES

Iron sulﬁde, in both the monosulﬁde (FeS) and the disulﬁde (FeS

) forms, has been consid-

ered for use in solid-cathode lithium batteries. Only the disulﬁde battery has been commer-

cialized because of its performance advantage due to its higher sulfur content and higher

voltage. The monosulﬁde electrode has the advantage of reduced corrosion, longer life, and

a single voltage plateau compared to the disulﬁde electrode, which discharges in two steps.

These batteries have a nominal voltage of 1.5 V* and can therefore be used as replace-

ments for aqueous batteries having a similar voltage. Button-type Li/ FeS

batteries were

manufactured as a replacement for zinc /silver oxide batteries but are no longer marketed.

They had a higher impedance and a slightly lower power capability but were lower in cost

and had better low-temperature performance and storability.

Li/ FeS

batteries are now manufactured in a cylindrical conﬁguration. These batteries

have better high-drain and low-temperature performance than the zinc/alkaline-manganese

dioxide batteries. The performance of these two systems on constant-current discharge at

various discharge rates, in the AA size, is compared in Fig. 14.76.

*ANSI Standard C18.3M, Part 1-1999.