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

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RECHARGEABLE LITHIUM BATTERIES (AMBIENT TEMPERATURE) 34.51

34.4.6 Rechargeable Lithium Alloy and Other Coin and Microcells

A number of coin-type rechargeable lithium batteries have been developed for portable ap-

plications as a power source for small electronic devices, for memory backup, or as a storage

device for solar or other types of auxiliary power sources. These batteries typically have a

higher voltage of about 3 V (thus reducing the number of cells required for a given voltage)

and a signiﬁcantly higher energy density, and are smaller and lighter than nickel-cadmium

and other conventional rechargeable batteries. The self-discharge rate of these cells is usually

less than 5% per year compared to about 30% per month for the nickel-cadmium cells. This

characteristic eliminates the need for recharging even after long storage periods. The cycle

life of most of these cells on deep discharge is relatively poor, but they give a long cycle

life and show good storage properties when shallow depths of discharge are used.

These lithium coin cells generally use a metal oxide intercalation compound for the

positive active material and a lithium alloy, such as lithium aluminum, which is less reactive

than metallic lithium, for the negative electrode. An organic solution is used for the electro-

lyte.

The energy density and speciﬁc energy of the different rechargeable lithium coin-type

batteries are summarized in Fig. 34.36.

FIGURE 34.36 Energy density and speciﬁc energy of re-

chargeable lithium coin-type batteries.

Lithium-Aluminum/ Manganese Dioxide Batteries. Figure 34.37 shows the construction

of a LiAl /MnO

cell. There is little difference in the design of this cell and that normally

found in primary lithium coin cells. A lithium-aluminum alloy, with special additives to

enhance the cycling performance and prevent cracking and blistering, is used for the anode.

The cathode consists of a mixture of MnO

and LiOH, which undergoes a heat treatment to

yield a high-porosity composite manganese oxide (MnO

⫹ Li

MnO

), as follows:

zz z

yMnO ⫹ zLiOH → y ⫺ MnO ⫹ Li MnO ⫹ HO

冉冊冉冊冉冊

22232

22 2

The characteristics of the composite allow the lithium ion to be removed easily from the

positive-electrode material during the charge cycle. The electrolyte uses a three-ingredient

solvent, consisting of ethylene carbonate, butylene carbonate, and DME. The separator is

polypropylene.

34.52 CHAPTER THIRTY-FOUR

FIGURE 34.37 Cut-away view of a LiAl / MnO

coin-

cell. (From Sanyo Energy Corp.)

The physical and electrical characteristics of coin-type batteries are listed in Tables 34.19

and 34.20. The discharge characteristics at several discharge currents and temperatures are

shown in Fig. 34.38 for a typical lithium alloy coin-type battery. The cell voltage is close

to 2.5 V because of the 0.3-V penalty associated with the use of the lithium-aluminum alloy.

TABLE 34.19 Rechargeable Lithium Aluminum / Manganese Dioxide Coin-

Type Batteries

Model ML 2430 ML 2016

Nominal voltage, V 3 3

Rated capacity, mAh 70 20

Diameter, mm 24.4 20

Height, mm 3.1 1.6

Weight, g 4 1.7

Operating temperature,

⬚C ⫺20 to 60 ⫺20 to 60

Self-discharge, %

⬍5 per year at 20⬚C

Cycle life 2000 cycles at 3 mAh

500 cycles at 12 mAh

200 cycles at 24 mAh

2000 cycles at 1 mAh

500 cycles at 4 mAh

200 cycles a 6 mAh

Source: Sanyo Energy Corp.

TABLE 34.20 Characteristics of Lithium-Aluminum/ Manganese Dioxide Coin-Type

Rechargeable Batteries

Model no.

Nominal

voltage

(V)

Nominal

capacity

(mAh)

Dimensions (mm)

External

diameter Height

Basic

battery

weight

(g)

Recommended

drain

(mA)

ML612S 3 2.3 6.8 1.2 0.15 0.01

ML616 3 2.0 6.8 1.6 0.20 0.01

ML616S 3 2.9 6.8 1.6 0.19 0.01

ML621 3 3.0 6.8 2.1 0.25 0.01

ML621S 3 4.5 6.8 2.1 0.23 0.01

ML2020 3 45.0 20.0 2.0 2.2 0.1

* Nominal capacity shown is based on standard drain and cut off voltage down to 2.0 V at 20⬚C (68⬚F)

Source: Panasonic Division of Matsushita Electric Corp. of America.

RECHARGEABLE LITHIUM BATTERIES (AMBIENT TEMPERATURE) 34.53

FIGURE 34.38 Discharge characteristics of LiAl / MnO

coin-type bat-

tery (ML2430 size): (a) discharge at 20⬚C, (b) at various temperatures,

discharge load: 5.6 k⍀.(From Sanyo Energy Corp.)

The basic charging design requires a current source with a voltage limit of 3.25 V. Figure

34.39 shows the charging characteristics of a constant-voltage method where the charge

current tapers as the battery voltage reaches the limit set by the charger. A protective resistor

is incorporated within the charger circuit to limit and control the charge rate during the initial

and long-term ﬂoat condition. Figure 34.40 shows the dependence of the cycle life on the

depth of discharge and the high cycle life obtained with a shallow depth of discharge.

68,69

These batteries are employed for memory back-up in applications such as mobile tele-

phones, memory cards, pagers and communications devices.

34.54 CHAPTER THIRTY-FOUR

FIGURE 34.39 Constant voltage charging of LiAl / MnO

coin-type

battery (ML2430 size), with a charging voltage of 3.25 V, at 20⬚C.

(From Sanyo Energy Corp.)

FIGURE 34.40 Cycle life vs. depth of discharge for a LiAl /

MnO

coin-type battery at 20⬚C. (From Sanyo Energy Corp.)

Lithium-Aluminum/ Vanadium Pentoxide Batteries. The LiAl /V

cell is another re-

chargeable lithium coin-type battery with a low self-discharge rate (2% per year at 20⬚C)

which can be used for low-drain loads. Over 1000 cycles can be obtained at 10% depth of

discharge. The construction is similar to the one illustrated in Fig. 34.37, except that V

is used for the active positive material.

The speciﬁcations for these batteries are listed in Table 34.21. The discharge character-

istics at several discharge rates and temperatures, illustrating the double-plateau discharge

proﬁle of these cells, are shown in Fig. 34.41. The ability of this cell to withstand overcharge

and overdischarge is shown in Fig. 34.42. The relationship of capacity and depth of discharge

is illustrated in Fig. 34.43

These batteries are employed as memory back-up power sources for applications such as

facsimile machines, memory cards, personal computers, telephones, tuners and video cam-

eras.

RECHARGEABLE LITHIUM BATTERIES (AMBIENT TEMPERATURE) 34.55

TABLE 34.21 Rechargeable Lithium-Aluminum / Vanadium Pentoxide Coin-Type Batteries

Model no.

Nominal

voltage

(V)

Nominal

capacity

(mAh)

Dimensions (mm)

External

diameter Height

Basic

battery

weight

(g)

Recommended

drain

(mA)

VL621 3.0 1.5 6.8 2.1 0.3 0.01

VL1216 3.0 5.0 12.5 1.6 0.7 0.03

VL1220 3.0 7 12.5 2.0 0.8 0.03

VL2020 3.0 20 20.0 2.0 2.2 0.07

VL2320 3.0 30 23.0 2.0 2.8 0.10

VL2330 3.0 50 23.0 3.0 3.7 0.10

VL3032 3.0 100 30.0 3.2 6.3 0.20

Charge/ discharge Cycle About 1000 times with a 10% discharge depth

Charge Constant voltage charging

Operating temperature

⫺20⬚C(⫺4⬚F) to 60⬚C(140⬚F)

Source: Panasonic Division of Matsushita Electric Corp. of America.

FIGURE 34.41 Discharge characteristics of a LiAl /

coin-type battery (VL2020 size): (a) discharges

at 20⬚C, (b) discharges at 30 k⍀ at various tempertures.

(From Panasonic Division of Matsushita Electric Corp.

of America.)

34.56 CHAPTER THIRTY-FOUR

FIGURE 34.42 Overcharge and overdischarge char-

acteristics of LiAl/ V

coin-type battery (VL2020

size): (a) overcharge characteristics, (b) overdischarge

characteristics (charge at 200 ⍀ for 48 h, discharge at

3k⍀). (From Panasonic Division of Matsushita Elec-

tric Corp. of America.)

FIGURE 34.43 Cycle life vs. depth of discharge (%) for

a LiAl /V

coin-type battery (VL2020 size) at 20⬚C.

(From Pansonic Division of Matsushita Electric Corp. of

America.)

RECHARGEABLE LITHIUM BATTERIES (AMBIENT TEMPERATURE) 34.57

Carbon-Lithium Rechargeable Batteries. The carbon-lithium batteries use a lithium alloy

for the negative active material, a nonaqueous organic electrolyte, such as propylene car-

bonate, and activated carbon for the positive electrode. The battery is built in a discharged

state. The mode of operation and the reactions during charge and discharge are delineated

as follows:

Cell as constructed:

Sn-Bi alloy/LiClO

䡠 PC /C (activated charcoal powder)

charge

⫹

—— —



Negative Sb Bi ⫹ Li ⫹ e LiSn Bi

———



discharge

charge

⫹

—— —



Positive nC ⫹ LiClO C ClO ⫹ Li ⫹ e

———



n 4

discharge

The construction is also similar to the one shown in Figure 34.37, except that activated

carbon is used for the active positive material.

The carbon-lithium system has a low energy density but long cycle life and a low self-

discharge rate. It can be charged at a current as low as several microamperes. A key appli-

cation has been for small electronic equipment such as a remote controller requiring a low-

power, long-life power source. The carbon-lithium battery can be combined with a solar cell,

which will charge the carbon-lithium battery and maintain it in a charged condition. The

charging characteristics of the carbon-lithium battery at various light intensities are shown

in Fig. 34.44.

FIGURE 34.44 Charge characteristics of a carbon-lithium coin-type battery (CL2020 size) with

solar batteries. (From Panasonic Division of Matsushita Electric Corp. of America.)

The discharge characteristics of the carbon-lithium battery at various rates and tempera-

tures are shown in Fig. 34.45. The discharge proﬁle is sloping and the delivered capacity is

very dependent on the end voltage of the discharge. The cycle life, as shown in Fig. 34.46,

likewise is dependent on the extent of the discharge. More than 10,000 cycles can be obtained

on a very shallow discharge, for example, on a discharge to 0.1 mAh for a CL2020 cell.

The speciﬁcations are listed in Table 34.22. These products are no longer commercially

available.

34.58 CHAPTER THIRTY-FOUR

Lithium-manganese-titanium rechargeable coin-type batteries which operate at 1.5 V are

available commercially. These employ a lithiated manganese oxide positive material, an

organic electrolyte and a lower voltage lithium titanium oxide intercalation compound as the

negative electrode material. These are lithium ion systems in which the lithium ions shuttle

between the oxides as the battery is charged and discharged. Characteristics of these batteries

are listed in Table 34.23. These batteries are used as the main power supply for products

such as rechargeable watches and as memory backup power supplies for pagers and timers.

FIGURE 34.45 Discharge characteristics of carbon-lithium

rechargeable coin-type battery (CL2020 size): (a) discharge

at 20⬚C, (b) discharge at 10 k⍀.(From Panasonic Division

of Matsushita Electric Corp. of America.)

RECHARGEABLE LITHIUM BATTERIES (AMBIENT TEMPERATURE) 34.59

FIGURE 34.46 Cycle life vs. depth of discharge for a car-

bon-lithium coin-type battery (CL2020 size). (From Panasonic

Division of Matsushita Electric Corp. of America.)

TABLE 34.22 Rechargeable Carbon-Lithium Coin-Type Batteries

Model CL 1220 CL 2020 CL 2320 CL 2330

Nominal voltage, V 3333

Rated capacity (to 2 V), mAh 0.3 1.0 1.5 2.5

Diameter, mm 12.5 20 23 23

Height, mm 2.0 2.0 2.0 3.0

Weight, g 0.8 1.9 2.8 3.7

Operating temperature,

⬚C ⫺20 to ⫹ 60

Cycle life See Fig. 36.65

Recommended drain,

␮

A 1–30 1–100 1–200 1–200

Charging method Voltage control

Source: Panasonic Division of Matsushita Electric Corp. of America.

TABLE 34.23 Rechargeable Lithium-Manganese-Titanium Coin-Type Batteries

Model no.

Nominal

voltage

(V)

Nominal

capacity

(mAh)

Dimensions

(mm)

External

diameter Height

Basic

battery

weight

(g)

Recommended

drain

(mA)

MT516 1.5 0.9 5.8 1.6 0.15 0.1

MT616 1.5 1.05 6.8 1.6 0.2 0.1

MT621 1.5 1.5 6.8 2.1 0.3 0.1

MT920 1.5 4.0 9.5 2.0 0.5 0.2

MT1620 1.5 14.0 16.0 2.0 1.3 0.5

* Nominal capacity shown is based on standard drain and cut off voltage down to 2.0 V at 20⬚C (68⬚F).

Source: Panasonic Division of Matsushita Electric Corp. of America.

34.60 CHAPTER THIRTY-FOUR

ACKNOWLEDGMENT

Section 34.4.3 dealing with rechargeable lithium batteries using PEO-based electrolytes was

contributed by Stefano Passerini. Jeffrey R. Dahn and Sid A. Megahed provided material for

this chapter in the second edition of this Handbook.

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