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

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ZINC-CARBON BATTERIES 8.39

FIGURE 8.33 Polaroid P-80; battery voltage proﬁle at various discharge loads.

zinc particle size and amount of hydrogen present. The polarization effect occurs when

the load is held for some time period, as in the case of charging the camera strobe

circuit. Total resistance is then a summation of the two resistances, that is, the internal

resistance of the battery and the resistance due to polarization effect, the latter being very

time sensitive. To minimize polarization effect resistance, the pulse period for

⌬V mea-

surements was minimized.

The 56-day point is of interest, as that is the normal age when the battery is released for

assembly into ﬁlm packs. At that time, every battery is measured for electrical characteristics

and defective ones are screened.

The total internal resistance is expressed by the following:

⫽ R ⫹ R

tip

where: R

⫽ battery internal resistance, ⍀

⫽ polarization resistance effect, ⍀

For the P-80 battery, R

was 0.50 ⍀ and the R

was 0.12 ⍀.

•

Capacity: The capacity simulator mimics the energy used to charge the camera strobe. The

pulse consists of an open circuit voltage at rest, followed by a pulse at a 2-A load to result

in a 50 watt-second (50 Ws) pulse. The 50 Ws cycle test is maintained until the ﬁnal CCV

reaches the 3.7 cut-off voltage, where the number of cycles is determined.

During the time while the 50 Ws load is maintained, the polarization drop occurs. The

time to produce the 50 Ws increases with each cycle as the battery is ‘‘consumed.’’ A 30-s

rest between cycles is used. Initially, the voltage drop is fairly constant; however, near the

end of the test, the resistance increases. The test is maintained to 3.7 V to indicate the cut-

off point of the camera.

Figure 8.33 illustrates the voltage proﬁle at different discharge loads, and Figure 8.34

shows rate sensitivity of the batteries described above versus capacity.

8.40 CHAPTER EIGHT

FIGURE 8.34 Polaroid P-80 battery; rate sensitivity vs capacity (to 3.0-V cutoff).

8.8 TYPES AND SIZES OF AVAILABLE CELLS AND BATTERIES

Zinc-carbon batteries are made in a number of different sizes with different formulations to

meet a variety of applications. The single-cell and multicell batteries are classiﬁed by elec-

trochemical system, either Leclanche´ or zinc chloride, and by grade; general purpose, heavy

duty, extra heavy duty, photoﬂash, and so on. These grades are assigned according to their

output performance under speciﬁc discharge conditions.

Table 8.9 lists the more popular battery sizes with typical performance at various loads

under a two-hour per day intermittent discharge, except for the continuous toy battery test.

The performance of these batteries, under several intermittent discharge conditions, is given

in Table 8.10.

The AA-size battery is becoming the predominant one and is used in penlights, photoﬂash

and electronic applications. The smaller AAA-size is used in remote control devices and

other small electronic applications. The C and D-size batteries are used mainly in ﬂashlight

applications and the F-size is usually assembled into multicell batteries for lanterns and other

applications requiring these large batteries. Flat cell are used in battery assemblies, in par-

ticular, the 9-volt battery used in smoke detectors and electronic applications.

Table 8.11 lists some of the major multicell zinc-carbon batteries that are available com-

mercially. The performance of these batteries can be estimated by using the IEC designation

to determine the cell compliment (e.g. NEDA 6, IEC 4R25 battery consists of four F-size

cells connected in series). Table 8.12 gives cross-references to the zinc-carbon batteries and

manufacturer’s designations. The most recent manufacturer’s catalogs should be consulted

for speciﬁc performance data to determine the suitability of their product for a particular

application.

ZINC-CARBON BATTERIES 8.41

TABLE 8.9 Characteristics of Zinc-Carbon Batteries

Size IEC

ANSI,

NEDA

Weight

Maximum

dimensions,

Diameter Height

Typical service, 2 h/ d*

Leclanche´

Drain

Service

Zinc-chloride

Drain

Service

N R1 910 6.2 12 30.2 1 480

AAA R03 24 8.5 10.5 44.5 1

—

520

AA R6 15 15 14.5 50.5 1

100

300

950

0.6

100

300

1200

110

C R14 14 41 26.2 50 5

100

300

380

1.7

100

300

800

150

5.5

D R20 13 90 34.2 61.5 10

100

500

400

100

500

700

135

F R25 60 160 34† 92† 25

100

500

300

5.5

100

500

400

G R26 — 180 32† 105† —

No. 6 R40 905 900 67 170.7 5

100

500

8000

700

350

*Typical values of service to 0.9-V cutoff.

†Typical values.

8.42 CHAPTER EIGHT

TABLE 8.10 ANSI Standards for Zinc-Carbon and Alkaline-Manganese Dioxide Batteries

Size Use Ohms Schedule

Cutoff

voltage

Speciﬁcation requirements

Zinc-carbon

batteries

Initial*

Alkaline-

manganese

dioxide batteries

Initial*

N 910D 910A

Portable lighting

Pager

then

5.1

(10.0

3000.0

5 min/d

5 sec/hr,

3595 sec /h)

0.9

100 min

888 hr

AAA 24D 24A

Pulse test

Portable lighting

Recorder

Radio

3.6

5.1

10.0

75.0

15 sec /min 24 hr/ d

4 min/hr 8 hr/d

1 hr/d

4 hr/d

0.9

150 pulses

48.0 min

1.5 hr

24.0 hr

450 pulses

130.0 min

5.5 hr

48.0 hr

AA 15D 15A

Pulse test

Motor/ toy

Recorder

Radio

1.8

3.9

10.0

43.0

15 sec /min 24 hr/ d

1 hr/d

4 hr/d

0.9

0.8

0.9

100 pulses

1.2 hr

5.0 hr

27.0 hr

450 pulses

5hr

13.5 hr

60 hr

C 14D 14A

Portable lighting

Toy

Recorder

Radio

3.9

6.8

20.0

4 min/hr 8 hr/d

1 hr/d

4 hr/d

0.9

0.8

0.9

350 min

5.5 hr

10.0 hr

30 hr

830 min

14.5 hr

24.0 hr

60.0 hr

D 13D 13A

Portable lighting

Motor/ toy

Recorder

Radio

1.5

2.2

3.9

10.0

4 min/15 min 8 hr/d

4 min/hr 8 hr/d

1 hr/d

4 hr/d

0.9

0.8

0.9

150 min

120 min

5.5 hr

10 hr

33 hr

540 min

950 min

17.5 hr

26.0 hr

90.0 hr

9 Volt 1604D 1604A

Calculator

Toy

Radio

Electronic

180

270

620

1300

30 min /d

1 hr/d

2 hr/d

24 hr /d

4.8

5.4

6.0

380 min

7hr

23 hr

630 min

14 hr

38 hr

Smoke detector Currently under consideration.

6 Volt 908D 908A

Portable lighting

Barricade

3.9

6.8

4 min/hr 8 hr/d

1 hr/d

3.6

5hr

50 hr

165 hr

21 hr

80 hr

300 hr

* Performance after 12 month storage

zinc-carbon batteries: 80% of initial requirement

alkaline-manganese dioxide batteries: 90% of initial requirement

Source: ANSI C18.1M-1999.

ZINC-CARBON BATTERIES 8.43

TABLE 8.11 ANSI / NEDA Dimensions of Zinc-Carbon Batteries*

ANSI IEC

Diameter,

Max Min

Overall height,

Max Min

Length,

Max Min

Width,

Max Min

13C R20S 34.2 32.3 61.5 59.5

13CD R20C 34.2 32.3 61.5 59.5

13D R20C 34.2 32.3 61.5 59.5

13F R20S 34.2 32.3 61.5 59.5

14C R14S 26.2 24.9 50.0 48.5

14CD R14C 26.2 24.9 50.0 48.5

14D R14C 26.2 24.9 50.0 48.5

14F R14S 26.2 24.9 50.0 48.5

15C R6S 14.5 13.5 50.5 49.2

15CD R6C 14.5 13.5 50.5 49.2

15D R6C 14.5 13.5 50.5 49.2

15F R6S 14.5 13.5 50.5 49.2

24D R03 10.5 9.5 44.5 43.3

903 — 163.5 158.8 185.7 181.0 103.2 100.0

904 — 163.5 158.8 217.9 214.7 103.2 100.0

908 4R25X 115.0 107.0 68.2 65.0 68.2 65.0

908C 4R25X 115.0 107.0 68.2 65.0 68.2 65.0

908CD 4R25X 115.0 107.0 68.2 65.0 68.2 65.0

908D 4R25X 115.0 107.0 68.2 65.0 68.2 65.0

915 4R25Y 112.0 107.0 68.2 65.0 68.2 65.0

915C 4R25Y 112.0 107.0 68.2 65.0 68.2 65.0

915D 4R25Y 112.0 107.0 68.2 65.0 68.2 65.0

918 4R25-2 127.0 — 136.5 132.5 73.0 69.0

918D 4R25-2 127.0 — 136.5 132.5 73.0 69.0

926 — 125.4 122.2 136.5 132.5 73.0 69.0

1604 6F22 48.5 46.5 26.5 24.5 17.5 15.5

1604C 6F22 48.5 46.5 26.5 24.5 17.5 15.5

1604CD 6F22 48.5 46.5 26.5 24.5 17.5 15.5

1604D 6F22 48.5 46.5 26.5 24.5 17.5 15.5

Source: ANSI C18.1M-1999.

8.44 CHAPTER EIGHT

TABLE 8.12 Cross-Reference of Zinc-Carbon Batteries

ANSI IEC Duracell Eveready Ray-O-Vac Panasonic Toshiba Varta Military

13C R20 M13SHD EV50 GP-D — — — —

13CD R20 M13SHD EV150 HD-D UM1D — — —

13D R20 M13SHD 1250 6D UMIN R20U 3020 —

13F R20 — 950 2D UM1 R20S 2020 BA-30/ U

14C R14 M14SHD EV35 GP-C — — — —

14CD R14 M14SHD EV135 HD-C UM2D — — —

14D R14 — 1235 4C UM2N R14U 3014 —

14F R14 — 935 1C UM2 R14S 2014 BA-42 / U

15C R6 M15SHD EV15 GP-AA — — — —

15CD R6 M15SHD EV115 HD-AA UM3D — — —

15D R6 M15SHD 1215 5AA UM3N R6U 3006 —

15F R6 — 1015 7AA UM3 R6S 2006 BA-58 / U

24D R03 — 1212 — UM4N — — —

24F R03 — — — — — — —

210 20F20 — 413 — — — — BA-305 / U

215 15F20 — 412 — 15 — V72PX BA-261 / U

220 10F15 — 504 — W10E — V74PX BA-332 / U

221 15F15 — 505 — MV15E — — —

900 R25-4 — 735 900 — — — —

903 5R25-4 — 715 903 — — — BA-804/ U

904 6R25-4 — 716 904 — — — BA-207/ U

905 R40 — EV6 — — — — BA-23

906 R40 — EV6 — — — — BA-23

907 4R25-4 — 1461 641 — — — BA-429 / U

908 4R25 M908 509 941 4F — — BA-200/ U

908C 4R25 M908SHD EV90 GP-6V — — 430 —

908CD 4R25 M908SHD EV90HP — — — 431 —

908D 4R25 M908SHD 1209 944 — — 430 —

915 4R25 M915 510S 942 — — — BA-803/ U

915C 4R25 M915SHD EV10S — — — — —

915D 4R25 M915SHD — 945 — — — —

918 4R25-2 — 731 918 — — — —

918C 4R25-2 — EV31 — — — — —

918D 4R25-2 — 1231 928 — — — —

922 — — 1463 922 — — — —

926 8R25-2 — 732 926 — — — —

1604 6F22 — 216 1604 006P — 2022 BA-90/ U

1604C 6F22 M9VSHD EV22 GP-9V — — — —

1604CD 6F22 M9VSHD EV122 HD-9V 006PD — — —

1604D 6F22 M9VSHD 1222 D1604 006PN 6F22U 3022 —

Source: Manufacturers’ catalogs.

ZINC-CARBON BATTERIES 8.45

REFERENCES

1. Frost and Sullivan Inc., U.S. Battery Market, New York, N.Y. 1997.

2. The Freedonia Group, Inc., Industry Study #1193, Primary and Secondary Batteries, Cleveland,

Ohio, December 1999.

3. Samuel Rubin, The Evolution of Electric Batteries in Response to Industrial Needs, Dorrance, Phil-

adelphia, 1978, chap. 5.

4. George Vinal, Primary Batteries, Wiley, New York, 1950.

5. N. C. Cahoon, in N. C. Cahoon and G. W. Heise (eds.), The Primary Battery, vol. 2, chap. 1, Wiley,

New York, 1976.

6. Richard Huber, in K. V. Kordesh (ed), Batteries, vol. 1, chap. 1, Decker, New York, 1974.

7. A. Kozawa and R. A. Powers, ‘‘Electrochemical Reactions in Batteries,’’ J. Chem. Ed. 49:587 (1972).

8. R. J. Brodd, A. Kozawa, and K. V. Kordesh ‘‘Primary Batteries 1951–1976,’’ J. Electrochem. Soc.

125(7) (1978).

9. M. Bregazzi, Electrochem. Technol., 5:507 (1967).

10. C. L. Mantell, Batteries and Energy Systems, 2d ed., McGraw-Hill, New York, 1983.

11. ‘‘American National Standards Speciﬁcation for Dry Cells and Batteries.’’ ANSI C18.1M-1999,

American National Standards Institute, Inc., January 1999.

12. Eveready Battery Engineering Data; Information is available via the Internet at, www.Energizer.com;

Technical information website. This data is frequently updated and current.

13. M. Dentch and A. Hillier, Polaroid Corp., Progress in Batteries and Solar Cells, vol. 9 (1990).

9.1

TABLE 9.1 Major Advantages and Disadvantages of Magnesium Batteries

Advantages Disadvantages

Good capacity retention, even under

high-temperature storage

Twice the capacity of corresponding

Leclanche´ batteries

Higher battery voltage than zinc-carbon

batteries

Competitive cost

Delayed action (voltage delay)

Evolution of hydrogen during

discharge

Heat generated during use

Poor storage after partial dis-

charge

CHAPTER 9

MAGNESIUM AND ALUMINUM

BATTERIES

Patrick J. Spellman, Duane M. Larsen, Ron J. Ekern,

and James E. Oxley

9.1 GENERAL CHARACTERISTICS

Magnesium and aluminum are attractive candidates for use as anode materials in primary

batteries.* As shown in Table 1.1, Chap. 1, they have a high standard potential. Their low

atomic weight and multivalence change result in a high electrochemical equivalence on both

a gravimetric and a volumetric basis. Further, they are both abundant and relatively inex-

pensive.

Magnesium has been used successfully in a magnesium /manganese dioxide (Mg /MnO

)

battery. This battery has two main advantages over the zinc-carbon battery, namely, twice

the service life or capacity of the zinc battery of equivalent size and the ability to retain this

capacity, during storage, even at elevated temperatures (Table 9.1). This excellent storability

is due to a protective ﬁlm that forms on the surface of the magnesium anode.

*The use of magnesium and aluminum in reserve and mechanically rechargeable batteries

is covered in Chaps. 17 and 38.

9.2 CHAPTER NINE

Several disadvantages of the magnesium battery are its ‘‘voltage delay’’ and the parasitic

corrosion of magnesium that occurs during the discharge once the protective ﬁlm has been

removed, generating hydrogen and heat. The magnesium battery also loses its excellent

storability after being partially discharged and, hence, is unsatisfactory for long-term inter-

mittent use. For these reasons, the active (nonreserve) magnesium battery, while used suc-

cessfully in military applications, such as radio transceivers and emergency or standby equip-

ment, has not found wide commercial acceptance.

Furthermore the use of this magnesium battery is declining signiﬁcantly, as the present

trend is towards the use of lithium primary and lithium-ion rechargeable batteries.

Aluminum has not been used successfully in an active primary battery despite its potential

advantages. Like magnesium, a protective ﬁlm forms on the aluminum, which is detrimental

to battery performance, resulting in a battery voltage that is considerably below theoretical

and causing a voltage delay that can be signiﬁcant for partially discharged batteries or those

that have been stored. While the protective oxide ﬁlm can be removed by using suitable

electrolytes or by amalgamation, gains by such means are accompanied by accelerated cor-

rosion and poor shelf life. Aluminum, however, has been more successfully used as an anode

in aluminum /air batteries. (See chapter 38)

9.2 CHEMISTRY

The magnesium primary battery uses a magnesium alloy for the anode, manganese dioxide

as the active cathode material but mixed with acetylene black to provide conductivity, and

an aqueous electrolyte consisting of magnesium perchlorate, with barium and lithium chro-

mate as corrosion inhibitors and magnesium hydroxide as a buffering agent to improve

storability (pH of about 8.5). The amount of water is critical as water participates in the

anode reaction and is consumed during the discharge.

The discharge reactions of the magnesium/manganese dioxide battery are

⫺

Anode

⫹ 2OH ⫽ Mg(OH) ⫹ 2e

⫺

Cathode

2MnO

⫹ HO⫹ 2e ⫽ Mn O ⫹ 2OH

22 23

Overall

⫹ 2MnO ⫹ HO⫽ Mn O ⫹ Mg(OH)

22 23 2

The theoretical potential of the battery is greater than 2.8 V, but this voltage is not realized

in practice. The observed values are decreased by about 1.1 V, giving an open-circuit voltage

of 1.9–2.0 V, still higher than for the zinc-carbon battery.

The rest potential of magnesium in neutral and alkaline electrolytes is a mixed potential,

determined by the anodic oxidation of magnesium and the cathodic evolution of hydrogen.

The kinetics of both of these reactions are strongly modiﬁed by the properties of the passive

ﬁlm, its history of formation, prior anodic (and to a limited extent cathodic) reactions, the

electrolyte environment, and magnesium alloying additions. The key to a full appreciation

of the magnesium electrode lies in an understanding of the predominantly Mg(OH)

ﬁlm,

the factors which govern its formation and dissolution, as well as the physical and chemical

properties of the ﬁlm.

The corrosion of magnesium under storage conditions is slight. A ﬁlm of Mg(OH)

that

forms on the magnesium provides good protection, and treatment with chromate inhibitors

increases this protection. As a result of the formation of this tightly adherent and passivating

oxide or hydroxide ﬁlm on the electrode surface, magnesium is one of the most electropos-

itive metals to ﬁnd use in aqueous primary batteries. However, when the protective ﬁlm is

broken or removed during discharge, corrosion occurs with the generation of hydrogen,

⫹ 2H O → Mg(OH) ⫹ H

222

MAGNESIUM AND ALUMINUM BATTERIES 9.3

FIGURE 9.1 Voltage proﬁle of magnesium primary battery at

20⬚C.

During the anodic oxidation of magnesium, the rate of hydrogen evolution increases with

increasing current density due to destruction of the passive ﬁlm, which exposes more (ca-

thodic) sites on the bared magnesium surface. This phenomenon has often been referred to

as the ‘‘negative difference effect.’’ An appreciable rate of anodic oxidation of magnesium

can only take place on the bare metal surface. Magnesium salts generally exhibit low levels

of anion conductivity, and one could theoretically invoke a mechanism wherein OH

⫺

ions

migrate through the ﬁlm to form reaction product Mg(OH)

at the magnesium-ﬁlm interface.

In practice this does not occur at a sufﬁciently rapid rate and instead the ﬁlm becomes

disrupted, in all likelihood mechanically, as the result of anodic current ﬂow.

A theoretical

model for the breakdown of the passive ﬁlm has been proposed.

4–7

This model involves,

successively, metal dissolution at the metal-ﬁlm interface, ﬁlm dilatation, and ﬁlm break-

down. This wasteful reaction is a problem, not only because of the need to vent the hydrogen

from the battery and to prevent it from accumulating, but also because it uses water which

is critical to the battery operation, produces heat, and reduces the efﬁciency of the anode.

The efﬁciency of the magnesium anode is about 60 to 70% during a typical continuous

discharge and is inﬂuenced by such factors as the composition of the magnesium alloy,

battery components, discharge rate, and temperature. On low drains and intermittent service,

the anode efﬁciency can drop to 40 to 50% or less. The anode efﬁciency also is reduced

with decreasing temperature.

Considerable heat is generated during the discharge of a magnesium battery, particularly

at high discharge rates, due to the exothermic corrosion reaction (about 82 kcal per gram-

mole of magnesium) and the losses resulting from the difference between the theoretical and

operating voltage. Proper battery design must allow for the dissipation of this heat to prevent

overheating and shortened life. On the other hand, this heat can be used to advantage at low

ambient temperatures to maintain the battery at higher and more efﬁcient operating temper-

atures.

A consequence of the passive ﬁlm on these metals is the occurrence of a voltage delay—

a delay in the battery’s ability to deliver full output voltage after it has been placed under

load—which occurs while the protective ﬁlm on the surface of the metal becomes disrupted

by the ﬂow of current, exposing bare metal to the electrolyte (see Fig. 9.1). When the current

is interrupted, the passive ﬁlm does indeed reform, but never to the original degree of pas-

sivity. Thus both the magnesium and the aluminum batteries are at a signiﬁcant disadvantage

in very low or intermittent service applications.

This delay, as shown in Fig. 9.2, is usually

less than 1 s, but can be longer (up to a minute or more) for discharges at low temperatures

and after prolonged storage at high temperatures.