Linden D., Reddy T.B. (eds.) Handbook of batteries
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LITHIUM BATTERIES 14.95
FIGURE 14.88 Discharge characteristics of Li / CuO button-type battery, 60-
mAh size. (a) Load characteristics. (b) Temperature characteristics. (c) Pulse dis-
charge characteristics. (Courtesy of Panasonic, Division of Matsushita Electric
Corp. of America.)
14.96 CHAPTER FOURTEEN
FIGURE 14.89 Typical discharge curves for Li / CuO AA-size battery at 20⬚C. (Courtesy of SAFT
America, Inc.)
FIGURE 14.90 Effect of temperature on Li/ CuO AA-size
battery, 1-k⍀ load. (Courtesy of SAFT America, Inc.)
FIGURE 14.91 Capacity of Li / CuO AA-size battery as a
function of discharge load and temperature. (Courtesy of SAFT
America, Inc.)
LITHIUM BATTERIES 14.97
The long-term storage capability of these Li/ CuO cells is illustrated in Fig. 14.92. Figure
14.92a shows that there is only a minimum loss of capacity after 10 years of storage at room
temperature, less than 0.5% per year. Performance after storage at high temperatures is
plotted in Fig. 14.92b. The retention of residual capacity in partially discharged cells is said
to be equivalent to that of fully charged cells.
FIGURE 14.92 Effect of storage on performance on Li / CuO cylindrical batteries. (a)
Discharges at 20⬚C before and after 10-year storage at 20⬚C. (b) Discharges at 20⬚C after
70⬚C storage. Curve 1—no storage; curve 2—6 months’ storage; curve 3—12 months’ stor-
age; curve 4—18 months’ storage. (Courtesy of SAFT America, Inc.)
14.98 CHAPTER FOURTEEN
High-Temperature Cells. Specially designed hermetically sealed batteries have been de-
veloped for use at the high temperatures encountered, for example, by the oil-well logging
industry, which uses down-hole tools operating to 150
⬚C, the maximum temperature at which
the Li /CuO cells can operate.
Spirally Wound Cells. Cylindrical batteries in C and D sizes have been designed with
spirally wound electrodes to meet higher drain requirements. Figure 14.93 shows the dis-
charge performance of a Li/ CuO D-size battery at various temperatures and at relatively low
and high discharge rates.
FIGURE 14.93 Performance of high- and low-rate Li / CuO D-size batteries.
(a) Discharge at 147 ⍀.(b) Discharge at 1.5 ⍀.
LITHIUM BATTERIES 14.99
14.11.4 Cell Types and Applications
The Li/CuO batteries that have been available in the button and small cylindrical (bobbin)
configurations are listed in Table 14.24. Under the low-drain conditions these batteries have
a significant capacity advantage over the conventional aqueous batteries. Combined with
their excellent storability and operation over a wide temperature range, these batteries provide
reliable power sources for applications such as memory backup, clocks, electric meters, and
telemetry and, with high-temperature cells, in high-temperature environments. Specially de-
signed units were also manufactured to meet higher drain applications. These batteries are
no longer available commercially.
TABLE 14.24 Characteristics of Lithium/ Copper
Oxide Batteries
Li/ CuO
Button†
1
⁄
2
AA AA
Nominal voltage, V 1.5 1.5 1.5
Dimensions (max)
Diameter, mm 9.5 14.5 14.5
Height, mm 2.7 26.0 50.5
Volume, cm
3
0.2 4.3 8.3
Weight, g 0.6 7.3 17.4
Rated capacity, Ah* 0.060 1.4 3.4
Specific energy/
Energy density
Wh/ kg 150 285 290
Wh/ L 450 485 610
Weight of lithium, g — 0.4 0.9
Maximum current, mA 0.3 20 40
*At approximately C / 1000 rate.
Source: SAFT America, Inc. and Panasonic Div.,
†
Matsu-
shiti Industrial Co.
14.12 LITHIUM/SILVER VANADIUM OXIDE BATTERIES
The lithium /silver vanadium oxide system has been developed for use in biomedical appli-
cations, such as cardiac defibrillators, neurostimulators and drug delivery devices. Electro-
chemical reduction of silver vanadium oxide (SVO) is a complex process and occurs in
multiple steps from 3.2 to 2.0 V. This system is capable of high power, high energy density
and high specific energy as is required for cardiac defibrillators, its principle application.
SVO with the stoichiometry of AgV
2
O
5.5
is capable of providing 310 mAh /kg. Practical
cells can achieve up to 780 Wh/ L and 270 Wh/ kg
46,47
and are capable of 1 to 2 Amp pulses
as required by cardiac defibrillators.
14.100 CHAPTER FOURTEEN
14.12.1 Chemistry
SVO is produced by the thermal reaction of AgNO
3
and V
2
O
5
.
46
This material belongs to
the class of vanadium bronzes and possesses semi-conducting properties. It is reduced chem-
ically and electrochemically in a multi-step process in which V
⫹
5
is first reduced to V
⫹
4
in
a two-step reaction, followed by reduction of Ag
⫹
1
to Ag
0
and then by partial reduction of
V
⫹
4
to V
⫹
3
. These processes tend to overlap and plateaus are observed in the discharge
curves at 3.2, 2.8, 2.2 and 1.8 V. When discharged to 1.5 V, 3.5 equivalents of lithium per
mole of SVO are utilized based on the empirical formula AgV
2
O
5.5
. The following reactions
have been proposed to account for this stoichiometry:
⫹
3.5 Li → 3.5 Li ⫹ 3.5eAnode:
3.5e
⫹ Ag(I)V (V)O → Ag(0)V (IV,III)OCathode:
25.5 2 5.5
3.5 Li ⫹ AgV O → Li AgV OOverall:
2 5.5 3.5 2 5.5
Electrolytes which have been employed with this system are 1 molar LiBF
4
in propylene
carbonate (PC) and 1 Molar LiAsF
6
in 1:1 by volume PC-DME. The latter appears to be
the electrolyte of choice at present. The addition of CO
2
or substances such as dibenzyl
carbonate (DBC) or benzyl succinimidyl carbonate have been reported to reduce anode pas-
sivation which causes voltage delay and increased DC resistance between 40 and 70% depth
of discharge.
48
These materials are believed to operate by lowering the impedance of the
solid electrolyte interface (SEI) layer on the surface of the lithium anode.
14.12.2 Construction
Typical construction of a prismatic implantable Li/SVO cell designed for use in a cardiac
defibrillator where high power capability is required is shown in Fig. 14.94.
49
The case and
lid are made of 304L stainless steel and are the negative cell terminal. A glass-to-metal
(GTM) seal employs TA-23 glass and a molybdenum pin. Although this GTM seal is in-
trinsically corrosion resistant in lithium primary cells, an elastomeric material and an insu-
lating cap are added to the underside of the seal to provide an additional mechanical barrier
and enhanced protection for the GTM. Two layers of insulating straps, one a fluropolymer
and the other of mica are added to the underside of the lid to prevent contact of the cathode
lead to the lid. The anode is constructed of two layers of lithium foil pressed on a nickel
screen and heat sealed in a microporous polypropylene separator. The cathode consists of
SVO with added carbon, graphite and PTFE binder. A typical composition is 94% SVO, 1%
carbon, 2% graphite and 3% PTFE,
50
pressed on a finely meshed titanium screen under high
pressure and then heat sealed in a microporous polypropylene separator. One anode assembly
is wound around the individual cathode plates as shown in Fig. 14.94 and the anode tab
welded to the case. Six to eight cathode plates are welded to a cathode lead bridge and an
insulated tab connects the bridge to the Mo pin of the GTM seal. Following welding of the
lid to the case, the cell is filled with electrolyte through the fill hole and a stainless steel
ball inserted in the fill port, and an additional plug is then laser welded over the fill hole,
providing an hermetic cell.
LITHIUM BATTERIES 14.101
FIGURE 14.94 Construction of a Li/ SVO cell designed for use in a cardiac defibrillator. (Courtesy Wilson
Greatbatch, Ltd.)
14.12.3 Performance
A typical defibrillator operates by sensing fibrillation through two electrodes and delivering
25 to 40 Joule pulses to the heart, when necessary, to paralyze the heart which then recovers
to a normal beating rhythm. The power source is required to deliver 10 to 30 microamps
continuously for the sensing and /or pacing functions over many years. It must also be
capable of providing the energy required to charge the capacitors in the defibrillator. This
energy is typically delivered as 1 to 2 Amps for 10 seconds. A typical battery is therefore
tested to provide four 2.0 Amp, 10 second pulses with 15 second intervals between pulses.
Figure 14.95 shows the continuous discharge curve for a resistive discharge at the two-
year rate. Battery voltage is plotted against lithium equivalents per mole of SVO. Accelerated
discharge testing consists of applying a series of four 2.0 Amp, 10 second pulses with 15
second intervals superimposed on a low-rate resistive discharge. Figure 14.96 shows a dis-
charge curve for a 2.2 Ah Li /SVO battery subjected to a series of four pulses every 30
minutes. The voltage on the continuous background load is shown together with the mini-
mum voltage on the first and fourth pulses to a 1.5 V cut-off. Additional testing is carried
out with increased intervals between the pulse sequences. Figure 14.97 shows a discharge
curve in which four 1.5 Amp, 10 second pulses superimposed on a 17.4 K ohm load are
applied every two months to a 1.4 Ah battery. The continuous discharge voltage is plotted
as is the fourth pulse minimum voltage which is above 2.0 volts after 45 months.
51
14.102 CHAPTER FOURTEEN
FIGURE 14.95 Discharge of lithium/ silver vanadium oxide. Voltage is shown versus
equivalents of lithium for a cathode stoichiometry of AgV
2
O
5.5
.(Ref. 46.)
FIGURE 14.96 Discharge of a 2.2 Ah lithium / silver vanadium oxide defibrillator bat-
tery under a scheme of one pulse train of four pulses applied every 30 minutes. (Ref. 46).
LITHIUM BATTERIES 14.103
FIGURE 14.97 Life test of a 1.4 Ah Li / SVO battery with continuous discharge on a 17.4 kohm load is
shown by the solid curve. The minimum voltage on the fourth 1.5 Amp pulse applied every two months is
shown by the diamonds. (Ref. 51).
14.12.4 Cell and Battery Types
Single-cell batteries are produced in either prismatic or with a D-shaped cross-section similar
to the design of lithium/iodine pacemaker batteries. High-rate models are produced in a
prismatic design of 2.2 Ah capacity, weighing 27.9 g and occupying 10.3 cc. This unit
provides 410 Wh/L and 150 Wh /kg. A similar unit in a D-shaped cross-section provides
1.18 Amp-hours capacity, a specific energy of 140 Wh/kg and an energy density of 400
Wh/ L. These parameters were obtained under an accelerated pulse test regime to a 1.5 V
cut-off.
Moderate rate units are also available. A rounded prismatic unit provides 2.5 Ah capacity,
270 Wh /kg and 780 Wh/L. A D-shaped moderate-rate battery product provides 1.6 Ah
capacity with a specific energy of 250 Wh/kg and an energy density of 750 Wh/L. This
data was obtained under a continuous 499 ohm discharge to a 2.0 V cut-off.
14.12.5 Applications
High-rate designs are employed in cardiac defibrillators, while moderate rate units find ap-
plications in implantable neurosimulators and drug infusion devices. Lithium/SVO batteries
are employed for biomedical applications and as such must be produced under the Good
Manufacturing Practices (GMP) for medical devices of the U.S. Food and Drug Adminis-
tration.
Stability of the components and the electrochemical system provide self-discharge of 2%/
year. Batteries are tested under both standard and abusive conditions. Standard tests are
carried out on fresh, half-depleted and fully depleted units. Each battery is examined visually,
dimensionally and radiographically before and after each test.
52
Qualification tests for im-
plantable defibrillator batteries are: 1) high and low pressure exposure followed by mechan-
ical shock and vibration and then followed by high temperature exposure; 2) thermal shock
(70 to
⫺40⬚C); 3) four-week temperature storage (55 and ⫺40⬚C); 4) low-temperature stor-
age; 5) forced overdischarge (single cell at C/ 10 rate and a two-cell battery); and 6) short
circuit at 37
⬚C. Cells bulge but do not vent on short circuit and pass other tests without
failure. Abusive tests are conducted to determine the ability of the batteries to withstand
severe conditions, but do not have survival requirements. These consist of crush, recharge,
slow dent/ puncture and high-rate forced discharge tests.
14.104 CHAPTER FOURTEEN
Traceability of materials and components to individual units is required and each is se-
rialized. A comprehensive quality assurance program is also implemented. One to two per-
cent of cells built are tested under conditions similar to those seen under actual use conditions
as part of a quality assurance program.
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