Lifetime
H Wenzl, Clausthal University of Technology,
Clausthal-Zellerfeld, Germany
& 2009 Elsevier B.V. All rights reserved.
Introduction
All electrochemical power sources deteriorate over time.
In contrast to many other technologies, however, the
deterioration tends to be slow and predictable, and
catastrophic failure is rarely observed. Owing to the
gradual decline in performance, it is important to have a
clear definition of what constitutes end of lifetime.
The following terms are used to denote different as-
pects of lifetime (see Figure 1).
Service Life
Service life is the time between its initial use or com-
missioning of the power source in a complete system and
the end of its useful life. In some applications, e.g., in the
space industry or military, commissioning does not mean
the beginning of a discharge or recharge. During service,
there can be periods of rest, of standby operation, or
power delivery in any combination. The length of the
service life is influenced by maintenance issues, regular
servicing, and, where applicable, exchange of faulty parts
or components with a shorter life than the cells them-
selves, e.g., filters in fuel cell systems.
Sometimes the time of the actual operation of emer-
gency power sources is called operating life. In emer-
gency applications, for instance, the operating time may
be a few minutes or even seconds after many years of
shelf life, which in this case includes the standby time
after installing the battery.
Calendar Life
This term is generally used as a synonym for service life.
Capacity
End of life
Shelf
life Service life
Time
Figure 1 Schematic diagram of shelf life and service life
(calendar life).
552
Cycle Life
The cycle life is given in a number of cycles. Factors
influencing cycle life are the average state-of-charge
(SoC), the range of SoC during the cycles, and the depth
of discharge when starting with a fully charged battery.
Depending on chemistry, a full charge (e.g., lead–acid
batteries), or a maximum SoC at the end of charging (i.e.,
some types of lithium-ion batteries) is recommended for
lifetime reasons. Figure 2 shows a typical diagram for the
number of cycles that are possible within the lifetime as a
function of depth of discharge. Cycle life is the service
life of a galvanic cell or supercapacitor if the application
consists mainly of discharge and charge cycles and rest
periods, which occur in any application, do not contrib-
ute significantly to aging. In cyclic operation, a capacity
loss by 20% is often used as end-of-life criterion.
The term is not used for fuel cells and primary batteries.
Float Life
Float life is the service life of a galvanic cell or super-
capacitor under mainly float charging conditions, i.e., the
battery is maintained at a certain voltage or SoC for long
periods of time. Float life is most important in standby
applications where the energy content is seldom called
upon but the maximum energy content must always be
available. Here too, a capacity loss of 20% is often used
as end-of-life criterion and the term is not applicable to
fuel cells and primary batteries.
Shelf Life
Shelf life or storage time is the maximum storage time of
a battery under open-circuit voltage conditions. At the
100 000
Number of cycles
10 000
1000
100
0 10 20 30 40 50 60 70 80 90 100
Depth of discharge (%)
Figure 2 Schematic diagram of number of cycles vs depth of
discharge for a lead–acid battery for industrial applications.

end of storage, the battery must still be capable of ful-
filling all requirements without a prior recharge. Some
primary cells, e.g., lithium manganese oxide (LiMn2O4),
stored at 20 1C have a self-discharge rate of B1.5% per
year and can be used even after years of storage without
significant loss of capacity. Cells with conventional nickel
oxyhydroxide (NiOOH) electrodes, i.e., not low self-
discharge nickel oxyhydroxide electrodes, have a shelf
life of a few weeks after which they need to be recharged
before they can be used. Recharging at the end of the
shelf life may be able to restore a cell to a nearly new
condition as all reversible self-discharge reactions can be
removed provided that irreversible self-discharge re-
actions can be neglected. Sometimes, the term shelf life
or storage life is also used to describe the maximum time
of storage after which the cell can still be used if it is
recharged before use. Conventional sealed Ni–Cd or
Ni–MH cells are an example for this use of the term.
The cells need to be recharged after being purchased and
before use, and their shelf life is understood as the
maximum time of storage before irreversible self-dis-
charge processes lead to unacceptable performance
losses.
Figure 1 shows some of these concepts schematically.
After the end of the shelf life, the capacity as lead per-
formance value may decrease more quickly or more
slowly than before or may even increase sharply due to
recharging.
Aging Processes and Stress Factors
Any deterioration of performance is the result of changes
in the chemical composition, concentration, and spatial
distribution of active and passive components, collect-
ively called aging processes. Many of these changes are
irreversible, but a few are reversible. For example, elec-
trolyte stratification in lead–acid batteries may be re-
versed by stirring, or liquid water in proton-exchange
membrane fuel cell (PEMFC), which blocks the mass
transport, may be removed by purging. Any discussion of
aging must therefore take into account reversible effects
as well as irreversible effects. Their interaction is also
important. The investigation of individual aging pro-
cesses in isolation never allows the successful prediction
of lifetime of the power source.
Aging processes are caused by unfavorable values of
the operating conditions or state variables over time:
voltage, temperature, current density, concentration,
pressure, etc. and in particular their combination. Re-
versible processes are not considered to be aging
processes.
An individual value of a state variable such as voltage
alone does not necessarily provide information on the
rate of aging processes or the deterioration, which has
already been reached. A voltage of, for example, 2.4 V per
Batteries and Fuel Cells | Lifetime 553
cell during charging of a lead–acid battery is a desirable
value at a low SoC whereas the same value increases
corrosion and degradation of the active materials when
the battery is fully charged. H. Wenzl and coworkers have
introduced the term stress factor to describe combin-
ations of operating conditions, which induce or accelerate
aging. The concept stress factor is the bridge between the
state variables V(t), I(t), c(t), SoC(t), etc. and the know-
ledge that certain combinations of these have a particu-
larly detrimental effect. Such combinations are called for
instance overcharging, deep discharge, cycling at partial
SoC, etc. Other combinations of state variables can have a
very low impact on aging and lifetime.
The study of the long-term performance of power
sources typically focuses on two areas, diagnosis and
prognosis. Diagnosis involves the examination of power
sources and the determination of the nature and cir-
cumstances of their deterioration. Prognosis involves the
prediction of future performance and the eventual life-
time of the system.
Besides their intrinsic structure, electrochemical
power sources are commonly fitted with auxiliary com-
ponents, e.g., pumps for cooling, heating and fuel supply,
monitoring equipment, and connectors and reformers.
The malfunction of these components may also lead to
system deterioration. Lack of maintenance and abusive
conditions also lead to a decrease in lifetime but are not
treated here, although they are the cause of many power
source failures.
End of Lifetime
In many cases, a single technical parameter is used to
define the end of lifetime of an electrochemical power
source. For batteries and supercapacitors their charge
capacity is of most interest. Often, a battery with a cap-
acity below 80% of its nominal value, measured under
nominal conditions, is considered to have reached the
end of its life. In applications of lead–acid batteries for
uninterruptible power supply systems, a lower value such
as 60% is also used sometimes. These values are based on
the expectation that the rate of capacity loss increases
very quickly once such a low value has been reached.
Qualibat, a research project by a number of European
research organizations, provides information that this
expectation is not valid for certain types of applications.
For fuel cells, the cell voltage at a given temperature,
current, and fuel utilization is the key criterion. A 10%
voltage decrease is often taken as end-of-lifetime
criterion.
However, such a one-dimensional view does not take
into account that there may be a number of different
properties of interest in addition to sufficient capacity,
e.g., low self-discharge rate, good charge acceptance, and
554 Batteries and Fuel Cells | Lifetime
Lifetime as a multidimensional vector
100%
Starting of ICE
100%
Ca
pa
cit
y c
ld ac
Co cap
0%
tance
Charg
esis
tion r
Wa
Vibra
e
arg
100%
ter
sch
con
f-di
sum
Sel
ptio
100%
Lowest acceptable value to fulfill the function
Value for a new starter battery
Figure 3 Diagram showing schematically the end-of-lifetime
criteria for a starter battery as a multidimensional vector. ICE,
internal combustion engine.
low internal resistance for power. Some requirements
may even be nontechnical, such as economical fuel
utilization and a high electrical efficiency. Therefore,
end of life should be considered as a multidimensional
problem, each dimension corresponding to a function
that the power source has to fulfill. Failure to fulfill any
one of these functions may then be considered to mean
that the product has reached the end of its useful life.
Figure 3 illustrates this idea in the form of a multivector
plot for lead–acid batteries for automotive applications.
The concepts state-of-health (SoH) and state-of-
function (SoF) are useful when discussing end of lifetime.
An overview is given by E Meissner and G Richter for
lead–acid batteries. They use the terms as follows:
Cact  Cthreshold
SoH ¼
Cfresh  Cthreshold
where Cact is the capacity of the battery under reference
discharge and charge conditions, i.e., nominal discharge
current and nominal temperature after a full charge;
Cthreshold is the minimum capacity acceptable for the
application; and Cfresh is the capacity of a new battery
under reference discharge and charge conditions.
As the capacity of lead–acid batteries can increase
after cycling beyond the value of Cfresh, this definition of
SoH may lead to a value above 1. If the reference charge
conditions have been chosen well, the SoH in this def-
inition describes a battery where all reversible effects that
lead to a loss of performance have been removed and the
integral effect of all aging effects is measured in one
parameter.
There are other definitions used for SoH, for example
based on the voltage of a power source after N charge–
100% discharge cycles:
g
kin
r an ty
i Vn 2Vthreshold
SoH ¼
V1 2Vthreshold
e acc
where V1 is the voltage of the battery at a specified point
eptan
in the first discharge half-cycle, Vn is the voltage of the
ce
100% battery at the same point in the nth discharge half-cycle,
and Vthreshold is the minimum voltage acceptable for the
application.
End of life is reached if the value of SoH is zero.
n
The SoF describes the ability of an electrochemical
100% power source to fulfill certain functions, for instance,
starting of an internal combustion engine or providing
heat and power in stationary applications of fuel cells.
E. Meissner defined the SoF for starting as
Vmin  V1
SoF ¼
Vfresh  V1
where Vmin is the minimum voltage during the starting
process, V1 is the lowest acceptable voltage during the
starting process, and Vfresh is the minimum voltage of a
battery in new and good condition during the starting
process.
SoF describes the performance of the power source as
is and depends on the SoC, temperature, SoH, and re-
duction of performance due to reversible effects. For
each function that a power source has to fulfill (energy
that can be delivered or stored, power that can be sup-
plied or taken up, self-discharge rate, charge acceptance,
etc.), an appropriate definition of SoF has to be chosen.
End of life is reached when at least one function cannot
be carried out anymore, i.e., its SoF is zero.
Common Aging Processes
Aging processes that are the result of mechanical damage
or poor maintenance (water on the cell container leading
to self-discharge, lack of water in flooded aqueous sys-
tems) are not considered here. Also, aging effects as a
result of poor material choice, (e.g., cell containers or
other passive components, which leach materials and
poison the system) are not considered either.
Aging processes can be divided into those that affect
the functions used for the end-of-life criteria of the
battery directly and those that affect secondary require-
ments, such as the recharging characteristics or the ex-
change current density of the side reactions. Changes in
these secondary requirements have no direct effect on
performance values but make the use of the system more

difficult and thus may cause indirectly a loss of per-
formance values. An increase in the side reactions during
charging, for instance, increases the temperature during
charging and slows down the charging process. Ultim-
ately it is difficult to achieve full charge, particularly if
charging time or power is restricted as in vehicles and
renewable energy systems, and the battery may begin to
age as a result of these effects.
Although aging processes are technology specific,
most can be considered under a few general sections, as
follows.
Corrosion of Grids, Internal Connectors
of the Cell, and Catalysts
Corrosion of grid materials and catalysts is a function
mainly of local voltage, local concentrations of reactants,
and temperature. The corrosion rate is usually highly
nonlinear with voltage. Within certain voltage ranges,
corrosion processes may be extremely slow or non-
existent. Elsewhere, they can be very high indeed.
• ohmic
Corrosion of grid materials leads to an increased
resistance and an uneven current distribution.
In batteries, if the current path is disrupted as a result
of corrosion, the internal resistance of the battery may
become very high and the battery may fail completely.
If explosive gases are present, there is a danger of
explosion in the instance when the current path breaks
down.
• The corrosion of the catalysts in fuel cells leads to a
reduction in the active surface area and increases the
overpotential for a given current.
• The effect of corrosion can lead to mechanical dam-
age of the cell. In lead–acid batteries, the positive pole
expands and may cause rupture of the cell container
and leakage of the electrolyte.
• Corrosion processes may also leach impurities from
various components and thereby cause catalytic poi-
soning (or catalyze side reactions).
Changes in the Microstructure of Materials
Many electrochemical power sources depend on
high-porosity or high-surface-area materials. In super-
capacitors, the electrodes typically consist of finely
divided carbon, which must be able to absorb electrolyte
solution easily. In fuel cells, the catalyst on the membrane
must be very finely dispersed and must also provide a
multitude of three-phase boundaries where the ion-
conducting material and the electron-conducting ma-
terial meet, and where the fuel is freely available. In
batteries, the active mass can best be described as an
intimate mixture of electrochemically active solid par-
ticles interspersed with ionically conducting electrolyte
solution.
Batteries and Fuel Cells | Lifetime 555
The microstructures of various power sources may be
damaged in the following ways:
• Ostwald ripening
This describes the thermodynamic tendency of large
numbers of small particles to grow into a small
number of large particles, having a smaller surface
area. The catalysts in fuel cells and the lead sulfate in
lead–acid batteries are well known to be affected by
this problem.
• Changes as a result of the charging and discharging process
(batteries only)
The charged and discharged materials may have very
different properties. In addition to changes of the spe-
cific volume, which affect all electrochemical couples
used in batteries, there may be differences in crystal
structure and electrical conductivity. The change of
specific volume tends to crack and destroy the active
mass. Certain lithium alloys for instance suffer a volume
increase of as much as 700% between its maximum and
minimum loading with lithium and the electrode
structure is destroyed. In lead–acid batteries, a number
of aging processes are due to the fact that lead sulfate
has twice the specific volume of lead dioxide and lead.
• Loss of contact with active mass particles in the electrode
The electrical conductivity of the active mass depends
on physical contact between constituent particles.
Changes in the particle size distribution of active
materials, and the volumetric changes during charge/
discharge, can damage the electrical contact and may
also lead to a reduced mechanical stability of the
electrode materials.
In a few exceptional cases, the microstructure can be
regenerated by an appropriate discharging and charging
regime. The well-known ‘memory effect’ of Ni–Cd bat-
teries is an example of this.
Contact Problems between Electrolyte Solution
and Active Materials
The electrical contact resistances between all com-
ponents must be as low as possible and very uniform. In
addition, the wetting properties of the electrolyte solu-
tion inside the active mass and the separator must be very
good. Usually there are few problems, but whenever the
electrolyte solution is immobilized in a matrix (gel in
certain types of lead–acid batteries, or polymer in lith-
ium-ion cells), physical contact problems may arise. The
delamination of the membrane electrode assembly in
PEMFCs is another example of such contact problems.
Effect of Impurities
Impurities can affect the catalytic properties at the elec-
trode/electrolyte interface, leading to chemical reactions
and changes of crystal structure in active and passive
556 Batteries and Fuel Cells | Lifetime

BCI 2005 survey failure modes of batteries removed from service battery life
100%
South
90%
North
80% Combined

70%
Cumulative battery life
60%

50%

40%

30%

20%

10%

0%
0 12 24 36 48 60 72 84 96 108 120 132
Months in service

Figure 4 Starting, lighting, ignition (SLI).

Pass/no pass = end of lifetime

Effect on performance/state of function
Filter

Battery
properties

n
Ageing mechanisms

tio

rs
ma

cto
for
ce

ne
n

rfa
n
sio

rite
din

on
tio

su
rro

ll c
nd
ed
lfa

AM
Co

De

Ce
Su

Sh
Operating conditions

Temperature
User requirements

Battery properties

Stress factors

Cross matrix to correlate the most

Operating
regime

Voltage important impacts of stress

factors on the aging
Partial cycling mechanisms of cells and other
battery failure mechanisms

Time at low SoC

Figure 5 Diagram showing schematically the interaction among operating conditions, stress factors, aging processes, and lifetime for
a lead–acid battery. SoC, state-of-charge.

components. Impurities may be introduced by production Lead–acid batteries for forklift trucks used in refrigerated
processes, leaching processes, or may be present in fuel warehouses have a longer lifetime than those used in other
supplies (e.g., sulfur in fuel cells) or electrolyte top-up. applications and the lifetime of starter batteries in vehicles
correlates with the average yearly temperature of the state
in which the vehicle is used (see Figure 4).
Temperature
Low temperature, particularly during rest periods or
The rate of all chemical reactions increases with in- during storage prior to use, therefore increases the lifetime.
creasing temperature, as a rule by a factor of two for each Power sources with high operating temperatures, e.g.,
10 K temperature increase. As a result, the rate of all self- solid oxide fuel cell systems or NaNiCl2 batteries, have
discharge reactions and chemical degradation processes to be heated up before use and, depending on appli-
doubles as well. In high-temperature conditions therefore, cation, are allowed to cool down when the system is not
the lifetime decreases. This is shown not only in many in use. The different thermal expansion coefficients of
datasheets of manufacturers but also in a field result. the materials and temperature gradients during the
 Batteries and Fuel Cells | Lifetime 557

Table 1 Qualitative description of the relationships among some stress factors encountered in the use of lead–acid batteries for
renewable energy applications and aging processes
Aging processes Corrosion of the Hard/irreversible Shedding (loss of Water loss/drying out Active mass
positive grid sulfation material) degradation
(reduction of
surface)
Stress factors
Long time at low Indirect through A strong positive No direct impact None None
states of charge low acid correlation: longer
concentration time at a low SoC
and low accelerates hard/
potentials irreversible
sulfation
Ah throughput No impact No direct impact Impact through No direct impact Loss of active
mechanical material
stress surface, larger
crystals
Charge factor A strong indirect Negative correlation, Strong impact Strong impact No direct impact
impact because impact through through gassing
a high charge regimes with high
factor and an charge factors,
extensive which decrease the
charge is risk of sulfation
associated with
a high charging
voltage (high
polarization of
electrode)
Time between full Strong negative Strong positive Negative Negative correlation No direct impact
charge correlation: correlation: correlation,
shorter time frequent full increasing with
increases recharge decreasing time
corrosion decreases hard/
irreversible
sulfation
Temperature Strong impact, High temperature No direct impact Increasing with Low impact; high
positive helps to fully increasing temperature
correlation recharge the temperature degrades
battery (more negative
sulfate can be electrode
recharged). On the expanders
other hand, high
temperature leads
to more hard
sulfate at a low
SoC
A positive correlation means that the aging process is accelerated if the stress factor increases.

heating processes are potentially very damaging. The
number of thermal cycles for these systems is still very
limited and may determine the end of lifetime.
All of the above effects lead to (1) decrease in the
amount of available active material, (2) decrease in the
effective area for charge/discharge, (3) higher ohmic
resistances, and (4) poor current distribution.
Short Circuits
If the membrane of a fuel cell develops pinholes, then
these may act as short circuits between adjacent cells
resulting in decreased efficiency, increased temperature,
and an increase in the size of the hole. Ultimately the
cell is destroyed. Similar effects are associated
with dendrite formation in batteries charged at high
overpotentials.
Some power sources have failure modes that are dif-
ficult to detect and lead to a sudden failure of the power
source. An example is corrosion of the group bar and
interconnectors in lead–acid batteries. The corrosion
attack is very difficult to detect during operation, par-
ticularly during float charging. Once a component breaks
as a result of corrosion, the battery does not conduct
electricity and, if the component breaks in an unfortunate
place, the battery may explode.
558 Batteries and Fuel Cells | Lifetime
Combination of Aging Effects
All aging processes take place in parallel and affect each
other. The end of lifetime of an electrochemical power
source is therefore the result of the complex interactions
between the aging processes.
Figure 5 and Table 1 show the interactions among
operating conditions, stress factors, and aging processes for
a lead–acid battery, and include a feedback loop that so-
phisticated energy management systems could use. It
should be noted particularly that it may be beneficial for an
aged battery to be operated differently than a new battery,
with an operating regime specially adapted to its age.
Table 1 shows stress factors for lead–acid batteries
and their impact on different aging processes. The impact
of temperature on aging processes is particularly note-
worthy. A high temperature is usually detrimental, but a
high temperature toward the end of charging will im-
prove the charge efficiency because lead sulfate dissolves
more quickly, making it more easily accessible to charg-
ing. Overcharging and active mass deterioration from
gassing and high charging voltage is then reduced. In
contrast, high temperature at medium or low SoC at rest
is detrimental because it accelerates Ostwald ripening.
Summary
The lifetime of an electrochemical power source depends
on the operating conditions of the application and the
interaction of different aging processes. Often the end of
lifetime is the result of a number of different aging pro-
cesses, which together reduce the performance capability.
As the rate of degradation is usually slow and predictable,
there is no clear end of lifetime and the criterion for end of
lifetime has to be defined application specific.
Nomenclature
Symbols and Units
Cact capacity of the battery under
reference discharge and charge
conditions
Cfresh capacity of the new battery under
reference discharge and charge
conditions
Cthreshold minimum capacity acceptable for the
application
V1 voltage of the battery at a specified
point in the first discharge
half-cycle
Vfresh minimum voltage of a battery in a
new and good condition during the
starting process
Vmin minimum voltage during the starting
process
Vn voltage of the battery at a specified
point in the nth discharge
half-cycle
Vthreshold minimum voltage acceptable for the
application
Abbreviations and Acronyms
AM active mass
ICE internal combustion engine
PEMFC proton-exchange membrane fuel
cell
SLI starting, lighting, ignition
SoC state-of-charge
SoF state-of-function
SoH state-of-health
See also: Electrochemical Theory: Corrosion.
Further Reading
Demettre D, Mattera F, Malbranche P, and Métain S (2000) Qualibat –
investigations for a quicker assessment of lifetime and other key
characteristics of photovoltaic batteries. Publishable Final Report of
the Project Funded in Part by the European Union, JOR3-CT97-
0161.
Meissner E and Richter G (2005) The challenge to the automotive
battery industry; the battery has to become an increasingly
integrated component within the vehicle electric power system.
Journal of Power Sources 144: 438--460.
Sauer DU (2003) Optimierung des Einsatzes von Blei-Säure-
Akkumulatoren in Photovoltaik-Hybrid-Systemen unter spezieller
Berücksichtigung der Batteriealterung. Dissertation, University of
Ulm, Germany, June.
Sauer DU and Wenzl H (2008) Comparison of different approaches
for lifetime prediction of electrochemical systems – using lead–
acid batteries as example. Journal of Power Sources 176(2):
534--546.
Sinyama K, Magari Y, Akita H, et al. (2005) Investigations into
the deterioration in storage characteristics of nickel–metal
hydride batteries during cycling. Journal of Power Sources 143:
265–269.
Vetter J, Novak P, Veit C, et al. (2005) Ageing mechanisms in lithium-
ion batteries. Journal of Power Sources 147: 269--281.
Wenzl H, Baring-Gould I, Kaiser R, et al. (2005) Life prediction of
batteries for selecting the technically most suitable and cost
effective battery. Journal of Power Sources 144(2): 373--384.
Wright RB and Motloch CG (2001) Calendar-life studies of advanced
technology development program Gen 1 lithium ion batteries. Report
by US Department of Energy DOE/ID-10844.
Yokokawa H, Tu H, Iwanschitz B, and Mai A (2008) Fundamental
mechanisms limiting solid oxide fuel cell durability. Journal of Power
Sources 182: 400--412.
Zamel N and Li X (2006) Life cycle comparison of fuel cell vehicles and
internal combustion engine vehicles for Canada and the United
States. Journal of Power Sources 167: 1241--1253.