Linden D., Reddy T.B. (eds.) Handbook of batteries
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LITHIUM BATTERIES 14.105
19. H. Taylor, ‘‘The Storability of Li/SO
2
Cells,’’ Proc. 12th Intersociety Energy Conversion Engineering
Conf., American Nuclear Society, LaGrange Park, Ill., 1977.
20. D. Linden and B. McDonald, ‘‘The Lithium-Sulfur Dioxide Primary Battery—Its Characteristics,
Performance and Applications,’’ J. Power Sources 5:35 (1980), Elsevier Sequoia, Lausanne, Swit-
zerland.
21. R. C. McDonald et al., ‘‘Investigation of Lithium Thionyl Chloride Battery Safety Hazard,’’ Tech.
Rep. N60921-81-C0229, Naval Surface Weapons Center, Silver Spring, Md., Jan. 1983.
22. S. C. Levy and P. Bro, Battery Hazards and Accident Prevention, Sec. 10.3.2, Plenum Publishing
Corp., New York, N.Y. (1994).
23. ‘‘Tadiran Lithium Inorganic Cells,’’ Tadiran Electronics Industries, Inc. Port Washington, N.Y. 11050.
24. M. Babai and U. Zak, ‘‘Safety Aspects of Low-Rate Li / SOCl
2
Batteries,’’ Proc. 29th Power Sources
Conf., Electrochemical Society, Pennington, N.J., June 1980.
25. K. M. Abraham and R. M. Mank, ‘‘Some Safety Related Chemistry of Li/SOCl
2
Cells,’’ Proc. 29th
Power Sources Conf., Electrochemical Society, Pennington, N.J., June 1980.
26. R. L. Zupancic, ‘‘Performance and Safety Characteristics of Small Cylindrical Li /SOCl
2
Cells,’’
Proc. 29th Power Sources Conf., Electrochemical Society, Pennington, N.J., June 1980.
27. J. F. McCartney, A. H. Willis, and W. J. Sturgeon, ‘‘Development of a 200 kWh Li / SOCl
2
Battery
for Undersea Applications,’’ Proc. 29th Power Sources Conf., Electrochemical Society, Pennington,
N.J., June 1980.
28. A. Zolla, J. Westernberger, and D. Noll, Proc. 39th Power Sources Conf., pp. 64–68 (2000), Cherry
Hill, N.J.
29. C. Winchester, J. Banner, A. Zolla, J. Westenberger, D. Drozd and S. Drozd, Proc. 39th Power
Sources Conf., pp. 5–9 (2000), Cherry Hill, N.J.
30. K. F. Garoutte and D. L. Chua, ‘‘Safety Performance of Large Li /SOCl
2
Cells,’’ Proc. 29th Power
Sources Conf., Electrochemical Society, Pennington, N.J., June 1980.
31. F. Goebel, R. C. McDonald, and N. Marincic, ‘‘Performance Characteristics of the Minuteman,
Lithium Power Source,’’ Proc. 29th Power Sources Conf., Electrochemical Society, Pennington, N.J.,
June 1980.
32. D. V. Wiberg, ‘‘Non-Destructive Test Techniques for Large Scale Li/ Thionyl Chloride Cells’’ Proc.
Int. Battery Seminar, Boca Raton, Fla., 1993.
33. P. G. Russell, D. Carmen, C. Marsh, and T. B. Reddy, Proc. 38th Power Sources Conf., pp. 207–
210 (1998), Cherry Hill, N.J.
34. E. Elster, S. Luski, and H. Yamin, ‘‘Electrical Performance of Bobbin Type Li /SO
2
Cl
2
Cells,’’ Proc.
11th Int. Seminar Batteries, Boca Raton, Fla., March 1994.
35. S. McKay, M. Peabody, and J. Brazzell, Proc. 39th Power Sources Conf., pp. 73–76 (2000), Cherry
Hill, N.J.
36. C. C. Liang, P. W. Krehl, and D. A. Danner, ‘‘Bromine Chloride as a Cathode Component in Lithium
Inorganic Cells,’’ J. Appl. Electrochem, 1981.
37. D. M. Spillman and E. S. Takeuchi, Proc. 38th Power Sources Conf., pp. 199–202 (1998), Cherry
Hill, N.J.
38. H. Ikeda, S. Narukawa, and S. Nakaido, ‘‘Characteristics of Cylindrical and Rectangular Li/ MnO
2
Batteries,’’ Proc. 29th Power Sources Conf., Electrochemical Society, Pennington, N.J., 1980.
39. T. B. Reddy and P. Rodriguez, ‘‘Lithium /Manganese Dioxide Foil-Cell Battery Development,’’ Proc.
36th Power Sources Conf., Cherry Hill, N.J., 1994.
40. A. Morita, T. Iijima, T., Fujii, and H. Ogawa, ‘‘Evaluation of Cathode Materials for the Lithium /
Carbon Monofluoride Battery,’’ J. Power Sources 5:111 (1980), Elsevier Sequoia, Lausanne, Swit-
zerland, 1980.
41. D. Eyre and C. D. S. Tuck, Modern Battery Technology, Sec. 5.3, C. D. S. Tuck, ed., Ellis Horwood,
N.Y. (1991).
42. R. L. Higgins and L. R. Erisman, ‘‘Applications of the Lithium / Carbon Monofluoride Battery,’’
Proc. 28th Power Sources Symp., Electrochemical Society, Pennington, N.J., June 1978.
43. T. R. Counts, Proc. 38th Power Sources Conf., 143–146 (1998), Cherry Hill, N.J.
14.106 CHAPTER FOURTEEN
44. T. Iijima, Y. Toyoguchi, J. Nishimura, and H. Ogawa, ‘‘Button-Type Lithium Battery Using Copper
Oxide as a Cathode,’’ J. Power Sources 5:1 (1980), Elsevier Sequoia, Lausanne, Switzerland.
45. J. Tuner et al., ‘‘Further Studies on the High Energy Density Li / CuO Organic Electrolyte System,’’
Proc. 29th Power Sources Conf., Electrochemical Society, Pennington, N.J., June 1980.
46. E. S. Takeuchi, Proc. 10th Int. Seminar on Primary and Secondary Battery Technology and Appli-
cations, Deerfield Beach, Fla., March 1993.
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48. H. Gan and E. S. Takeuchi, Abstract No. 332, Electrochemical Society Metting, Honolulu, HI, Oct.
17–22 (1999).
49. A Guide to Implantable Medical Batteries, Wilson Greatbatch Ltd., Clarence, N.Y.
50. R. A. Leising and E. S. Takeuchi, Chem. of Materials, 5:738 (1993).
51. C. F. Holmes and M. Visby, PACE 14:341 (1991).
52. E. S. Takeuchi, J. Power Sources 54:115 (1995).
15.1
CHAPTER 15
SOLID-ELECTROLYTE BATTERIES
Boone B. Owens, Paul M. Skarstad, Darrel F. Untereker, and
Stefano Passerini
15.1 GENERAL CHARACTERISTICS
Any battery consists of an electrochemically reactive couple separated by an ion-transport
medium, or electrolyte. In most familiar batteries the electrolyte is a liquid. However, the
availability of solids capable of being fabricated into electronically insulating elements with
fairly low overall ionic resistance has stimulated the development of solid-electrolyte bat-
teries. A few of these types of batteries have become available commercially and are im-
portant power sources at normal ambient temperatures (
⬃25⬚C) for heart pacemakers, for
preserving volatile computer memory, and for other low-power applications requiring long
shelf and service lives. A chronology of various types of solid-electrolyte cells developed
since 1950 is shown in Table 15.1. Two trends are indicated in this table. First, the low-
energy silver-based systems have been replaced largely by developments of high-energy
lithium anode-based batteries. Second, the batteries have gone from being pellet-based de-
vices with relatively thick electrolyte layers (on the order of a millimeter) to thin film devices
with electrolyte thicknesses on the order of micrometers. This reduction in the interelectrode
distance has been necessary in order to overcome the ohmic losses due to the more resistive
lithium-ion conducting electrolytes. Review articles which cover solid-electrolyte battery sys-
tems, including those not commercially available, are available in the literature.
1–10
Commercially available solid-electrolyte batteries use lithium anodes. Lithium is attractive
as an anode material for several reasons. First, it has a high specific capacity on both a
weight and a volume basis. Second, it is strongly electropositive; this leads to high voltages
when coupled with typical cathode materials. Finally, suitable lithium ion conductors are
available for use as solid electrolytes. Table 15.2 compares theoretical values of the equiv-
alent weight, equivalent volume, voltage, capacity density, and energy density for battery
systems forming metal iodide as the discharge product. Among the alkali metals, the small
equivalent volume of lithium more than compensates for the slightly higher voltages obtained
with the heavier members of the group in determining the theoretical energy density. On the
other hand, the high voltage with lithium compensates for the capacity advantage of the
polyvalent metals. Only metal I
2
batteries of Ca, Sr, and Ba have theoretical specific energies
approaching that of lithium. Moreover, no suitable conductive solid electrolytes are known
for the polyvalent metals in Table 15.2. Therefore lithium appears to be the anode material
of choice at the present time.
15.2 CHAPTER FIFTEEN
TABLE 15.1 Chronology of Solid-Electrolyte Batteries*
Date Electrolyte
Log conductivity,
⍀
⫺
1
䡠 cm
⫺
1
Typical cell system
1950–1960
1960–1965
1965–1972
1965–1975
1970–1975
1970–1980
1978–1985
1980–1986
1983–1987
1985–1992
1985–1992
1990–2000
1992–2000
AgI
Ag
3
SI
RbAg
4
I
5
Beta-alumina
LiI(Al
2
O
3
)
LiI
LiX-PEO
Li
0.36
I
0.14
O
0.007
P
0.11
S
0.36
MEEP
Plasticized SPE
Li
0.35
I
0.12
O
0.31
P
0.12
S
0.098
LiPON
LiPON
⫺5
⫺2
⫺0.5
⫺1.5
⫺5
⫺7
⫺7
⫺3.3
⫺4
⫺3
⫺4.7
⫺5.6
⫺5.6
Ag/V
2
O
5
Ag/I
2
Ag/Me
4
NI
5
Na-Hg/ I
2
,PC
Li/ PbI
2
Li/I
2
(P2VP)
Li/V
2
O
5
Li/TiS
2
Li/TiS
2
Li/V
6
O
13
Li/TiS
2
Li/ a-V
2
O
5
LiC
6
/Li
x
CoO
2
and LiC
6
/Li
x
NiO
2
PEO—polyethylene oxide: MEEP—poly(bis-(methoxy ethoxy ethoxide)): SPE—solid polymer electrolyte.
1
LIPON ⫽ Li
0.39
N
0.02
O
0.47
P
0.12
.
Recent data on rechargeable systems with solid electrolytes will be found in chapters 34 and
35.
TABLE 15.2 Theoretical Values for Capacity Densities and Energy
Densities of Balanced Metal / I
2
-Batteries*
Anode
metal
Anode
equivalent
weight,
g /eq
Anode
equivalent
volume,
cm
3
/eq E
0
,V
Cell
capacity
density,
Ah/cm
3
Cell
energy
density,
Wh/cm
3
Monovalent metals
Li
Na
K
Rb
Cs
Cu
Ag
Tl
6.9
23.0
39.1
85.5
132.9
63.5
107.9
204.4
13.0
23.7
44.9
55.9
71.1
7.1
10.3
17.2
2.8
3.0
3.4
3.4
3.5
0.7
0.7
1.3
0.69
0.54
0.38
0.33
0.28
0.82
0.75
0.63
1.9
1.6
1.3
1.1
1.0
0.59
0.51
0.81
Polyvalent metals
Be
Mg
Ca
Sr
Ba
Zn
Cd
Al
4.5
12.2
20.0
43.8
68.7
32.7
56.2
9.0
2.4
7.0
13.0
16.9
19.6
4.6
6.5
3.3
1.1
1.9
2.8
2.9
3.1
1.1
1.1
1.0
0.96
0.82
0.69
0.63
0.59
0.93
0.89
0.83
1.1
1.5
1.9
1.9
1.9
1.0
1.0
0.9
* Equivalent weights, densities, and cell voltages were obtained from data in
Weast.
11
SOLID-ELECTROLYTE BATTERIES 15.3
Complete solid-state batteries offer several advantages over those with fluid components.
They generally exhibit high thermal stability, low rates of self-discharge (shelf life of 5 to
10 years or better), the ability to operate over a wide range of environmental conditions
(temperature, pressure, and acceleration), and high energy densities (300 to 700 Wh/ L). On
the other hand, limitations associated with a complete solid-state battery include relatively
low power capability (microWatt range) due to the high impedance of most solid electrolytes
at normal ambient temperature, possible mechanical stresses due to volume changes asso-
ciated with electrode discharge reactions, and reduced electrode efficiencies at high discharge
rates (see Table 15.3). However, lithium polymer electrolyte batteries appear to have solved
some of these deficiencies.
The only current commercial inorganic solid-electrolyte battery system is Li /LiI /
I
2
(P2VP). The solid electrolyte LiI is formed in situ as the discharge product of the cell
reaction. The cathode is a mixture of solid iodine and a saturated viscous liquid solution
containing poly-2-vinylpyridine (P2VP) and iodine. The Li/LiI/I
2
䡠 (P2VP) battery can be
regarded as a quasi-solid-state system because of the high viscosity of the polymer-containing
liquid phase and the preponderance of solid iodine in the material. However, the viscous
liquid phase does impart a plasticity to the I
2
(P2VP) cathode, which makes these solid-state
cells better able to adapt to volumetric changes during cell discharge.
TABLE 15.3 Major Advantages and Disadvantages of Lithium Solid-Electrolyte Batteries
Advantages Disadvantages
Excellent storage stability—shelf life of 10 years or better
High energy densities
Hermetically sealed—no gassing or leakage
Wide operating temperature range, up to 200
⬚C
Shock and vibration-resistant
Low current drains (microamperes)
Power output reduced at low temperatures
Care must be exercised to prevent short-circuiting or
shunting of cell (which could be a relatively high drain
on cell)
15.2 Li/LiI(Al
2
O
3
)/METAL SALT BATTERIES
Lithium batteries with the dispersed phase electrolyte of LiI and Al
2
O
3
are no longer pro-
duced commercially, but the following description of these batteries, which were developed
at Duracell in the 1970s, is included for its technological interest. The battery
Li/ LiI(Al O )/metal salts
23
is a true solid-state battery. All components are solids, with no significant amount of liquid
or vapor component coexisting. It was commercially available in the 1980s, but has since
been withdrawn from the market.
15.2.1 General Characteristics
Solid-state batteries based on this system have the following properties: (1) long shelf life,
(2) low power capability, (3) hermetically sealed, no gassing, (4) broad operating temperature
range:
⫺40 to 170⬚C for pure lithium anodes, up to and beyond 300⬚C with compound
anodes, (5) high volumetric energy density, up to 0.6 Wh/ cm
3
in the system that were
produced
12,13
and up to 1.0 Wh /cm
3
in systems that were under development.
14,15
These batteries were recommended for low-rate applications. They were particularly
suited for applications requiring long life at low-drain or open-circuit conditions. Possible
ambient-temperature applications included watches, pacemakers, and monitoring devices.
The power characteristics and long shelf lives were well-suited to providing backup power
for preserving volatile computer memory.
15.4 CHAPTER FIFTEEN
15.2.2 Cell Chemistry
Two different cathodes were used in these commercial solid-state cells. The original battery
system used a mixture of PbI
2
and Pb for the cathode.
12
This was replaced by a mixture of
PbI
2
, PbS, and Pb.
13
A newer system, with increased energy density, used a mixture of TiS
2
and S as the cathode.
14
Properties of these battery systems are summarized in Table 15.4.
Other cathode materials have also been investigated in cells of this type. They include As
2
S
3
and various other metal sulfides.
15
TABLE 15.4 Practical Solid-State Lithium Battery Systems
Cell
Practical
energy
density,
Wh/cm
3
Cell reactions E
0
,V
Li/ LiI(AI
2
O
3
)/ PbI
2
, Pb 0.1–0.2 2Li ⫹ PbI
2
→ 2Lil ⫹ Pb 1.9
Li/ LiI(Al
2
O
3
)/ PbI
2
, PbS, Pb 0.3–0.6 2Li ⫹ PbI
2
→ 2Lil ⫹ Pb 1.9
2Li
⫹ PbS → Li
2
S ⫹ Pb 1.8
Li/ LiI(Al
2
O
2
)/TiS
2
, S 0.9–1.0 Li ⫹ TiS
2
→ Li
x
TiS
2
2Li ⫹ S → Li
2
S
2.5–1.9
2.3
Source: Duracell, Inc.
The solid electrolyte used in these solid-state cells is a dispersion of lithium iodide and
lithium hydroxide with alumina. Pure lithium iodide has a conductivity of about 10
⍀ 䡠
⫺
7
⫺
1
cm at room temperature.
16–18
The conductivity of lithium iodide can be enhanced by several
⫺
1
orders of magnitude by dispersal of substantial amounts (⬃50 mole percent) of high-surface-
area alumina in the lithium iodide. Lithium ion conductivities as high as 10
⍀ 䡠 cm
⫺
4
⫺
1
⫺
1
have been reported in such dispersions at 25⬚C.
15,19
The dispersed-phase lithium iodide with enhanced lithium ion conductivity remains a
good electronic insulator with the partial electronic (hole) conductivity approximately
10
⍀ 䡠 cm .
15
Thus this material is well-suited for application as a solid electrolyte.
⫺
40
⫺
1
⫺
1
The mechanism by which the high-surface-area alumina, itself a poor conductor, enhances
the conductivity of lithium iodide is not well understood. Enhanced interfacial conduction
has been suggested.
20
The Arrhenius plot of conductivity for LiI (Al
2
O
3
) (Fig. 15.1) in the
range
⫺50 to 300⬚C is characterized by a single activation energy (0.4 eV).
15
At 300⬚C the
conductivity reaches 0.1
⍀ 䡠 cm , allowing the construction of batteries with substantial
⫺
1
⫺
1
rate capability. High-temperature solid-state secondary batteries using this electrolyte have
been investigated for load-leveling and vehicle-propulsion applications.
15,21
SOLID-ELECTROLYTE BATTERIES 15.5
FIGURE 15.1 Ionic conductivity of LiI(Al
2
O
3
) electro-
lyte. (Courtesy of Duracell, Inc.)
15.2.3 Cell Construction
The dispersed-phase ionic conductor LiI(Al
2
O
3
) can be fabricated as a dense, conductive
solid electrolyte element by uniaxial compression at room temperature.
13
No high-
temperature sintering is required. The minimum thickness of an electrolyte element in a
practical cell construction is about 0.2 mm. The cell is designed in a button or circular disk
configuration, as shown in Fig. 15.2. The cell is fabricated by sequentially pressing the cell
components (cathode, electrolyte, and anode) at appropriate pressures into the cell in the
form of a thin circular disk. This cell can be incorporated in series-parallel combinations to
give batteries with the desired voltage and current characteristics. The battery is fabricated
by placing the cells in a stainless-steel container, holding the cells under spring pressure.
There is no need to encapsulate or isolate each cell as required in conventional batteries.
The energy density achieved in the cell and battery described in Table 15.5 is 0.4 Wh /cm
3
.
Energy densities up to 0.6 Wh/cm
3
have been achieved in practical cells with this chemical
system.
15.6 CHAPTER FIFTEEN
FIGURE 15.2 Cross section of solid-state battery. (Courtesy of Duracell, Inc.)
TABLE 15.5 Properties of Commercial Li/ Lil/ PbI
2
, PbS Batteries
E ⴖ,V
Capacity,
mAh
Diameter,
cm
Height,
cm
Volume,
cm
3
Weight,
g
Energy
density
Wh/cm
3
Specific
energy
Wh/g
1.9
3.8
350
350
2.90
2.97
0.25
0.58
1.5
4.0
7.25
15.86
0.445
0.332
0.92
0.94
15.2.4 Performance Characteristics
The discharge properties of these solid-state batteries are characterized by high practical
energy densities, low-rate capability, and low rates of self-discharge. From the linear polar-
ization curve (Fig. 15.3) it is apparent that the resistance is essentially ohmic. Bridge mea-
surements of cell resistance at 1 kHz are in agreement with values determined from polari-
zation curves.
Figure 15.4 shows the discharge curves for the 350-mAh battery at various discharge rates
at 20
⬚C. At discharge rates below 6
A, the discharge efficiency is close to 100% to a 1-V
cutoff. The discharge curves for the same battery at various temperatures are shown in Fig.
15.5 for discharges at 3
A (0.55
A/cm
2
of electrolyte area) and 12
A. The improved
performance attained at the higher discharge temperatures is evident. These batteries can be
discharged at higher temperatures than shown; however, for operation above 125
⬚C, a mod-
ified electrode structure is required. At lower temperatures the current capability of the solid-
state battery is reduced. In typical CMOS memory applications, however, the load current
requirement usually is similarly reduced and the cell output tracks the CMOS power require-
ments. The service life delivered by the 350-mAh battery at various discharge temperatures
and loads is given in Fig. 15.6. These data can be used to calculate the performance of the
battery under various conditions of use.
22
SOLID-ELECTROLYTE BATTERIES 15.7
FIGURE 15.3 Typical polarization curve (IX battery. 25⬚C, cell surface area 1cm
2
). (Courtesy
of Duracell, Inc.)
FIGURE 15.4 Discharge curves for solid-state battery. 350 mAh at 20⬚C.
(Courtesy of Duracell, Inc.)
15.8 CHAPTER FIFTEEN
FIGURE 15.5 Discharge curves for solid-state battery. 350 mAh. (a)3-
A
discharge. (b) 12-
A discharge. (Courtesy of Duracell, Inc.)
FIGURE 15.6 Service life of solid-state batteries. 350 mAh. to 1-V cutoff.
(Courtesy of Duracell, Inc.)