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Specifications, Standards and Hype

Batteries may be advertised as Long Life, High Capacity, High Energy, Deep Cycle, Heavy Duty, Fast Charge, Quick Charge, ltra and other, ill defined, parameters and there are fe! industry or legal standards defining e"actly !hat each of these terms means# $dvertising !ords can mean !hatever the seller !ants them to mean# $part from the basic battery design, performance actually depends on ho! the batteries are used and also on the environmental conditions under !hich they are used, but these conditions are rarely, if ever, specified in mass market advertising# For the consumer this can be very confusing or misleading# %he battery industry itself ho!ever does not use such vague terms to specify battery performance and specifications normally include a statement defining or limiting the operating or environmental conditions !ithin !hich the claimed performance can be delivered# %he follo!ing section outlines key parameters used to characterise the cells or batteries and sho!s ho! these parameters may vary !ith the operating conditions#

Discharge Curves
Energy cells have been developed for a !ide range of applications using a variety of different technologies, resulting in a !ide range of available performance characteristics# %he graphs belo! sho! some of the main factors an applications engineer should take into account !hen specifying a battery to match the performance re&uirements of the end product#

Cell Chemistry
%he nominal voltage of a galvanic cell is fi"ed by the electrochemical characteristics of the active chemicals used in the cell, the so called cell chemistry# %he actual voltage appearing at the terminals at any particular time, as !ith any cell, depends on the load current and the internal impedance of the cell and this varies !ith, temperature, the state of charge and !ith the age of the cell# %he graph belo! sho!s typical discharge discharge curves for cells using a range of cell chemistries !hen discharged at '#(C rate# )ote that each cell chemistry has its o!n characteristic nominal voltage and discharge curve# *ome chemistries such as Lithium +on have a fairly flat discharge curve !hile others such as Lead acid have a pronounced slope# %he po!er delivered by cells !ith a sloping discharge curve falls progressively throughout the discharge cycle# %his could give rise to problems for high po!er applications to!ards the end of the cycle# For lo! po!er applications !hich need a stable supply voltage, it may be necessary to incorporate a voltage regulator if the slope is too steep# %his is not usually an option for high po!er applications since the losses in the regulator !ould rob even more po!er from the battery# $ flat discharge curve simplifies the design of the application in !hich the battery is used since the supply voltage stays reasonably constant throughout the discharge cycle# $ sloping curve facilitates the estimation of the *tate of Charge of the battery since the cell voltage can be used as a measure of the remaining charge in the cell# ,odern Lithium +on cells have a very flat discharge curve and other methods must be used to determine the *tate of Charge

%he - a"is sho!s the cell characteristics normalised as a percentage of cell capacity so that the shape of the graph can be sho!n independent of the actual cell capacity# +f the - a"is !as based on discharge time, the length of each discharge curve !ould be proportional to the nominal capacity of the cell#

Temperature Characteristics
Cell performance can change dramatically !ith temperature# $t the lo!er e"treme, in batteries !ith a&ueous electrolytes, the electrolyte itself may free.e setting a lo!er limit on the operating temperature# $t lo! temperatures Lithium batteries suffer from Lithium plating of the anode causing a permanent reduction in capacity# $t the upper e"treme the active chemicals may break do!n destroying the battery# +n bet!een these limits the cell performance generally improves !ith temperature# *ee also %hermal ,anagement and Battery Life for more details#

%he above graph sho!s ho! the performance of Lithium +on batteries deteriorates as the operating temperature decreases# /robably more important is that, for both high and lo! temperatures, the further the operating temperature is from room temperature the more the cycle life is degraded# *ee Lithium Battery Failures#

Self Discharge Characteristics


%he self discharge rate is a measure of ho! &uickly a cell !ill lose its energy !hile sitting on the shelf due to un!anted chemical actions !ithin the cell# %he rate depends on the cell chemistry and the temperature# Cell Chemistry %he follo!ing sho!s the typical shelf life for some primary cells0

1inc Carbon 2Leclanch34 ( to 5 years $lkaline 6 years Lithium 7' years or more Lead $cid 89 to :9 per month )ickel Cadmium 769 to ('9 per month )ickel ,etal Hydride 5'9 per month Lithium (9 to 59 per month

%ypical self discharge rates for common rechargeable cells are as follo!s0

Temperature Effects %he rate of un!anted chemical reactions !hich cause internal current leakage bet!een the positive and negative electrodes of the cell, like all chemical reactions, increases !ith temperature thus increasing the battery self discharge rate# *ee also Battery Life # %he graph belo! sho!s typical self discharge rates for a Lithium +on battery#

Internal Impedance
%he internal impedance of a cell determines its current carrying capability# $ lo! internal resistance allo!s high currents# Battery Equivalent Circuit %he diagram on the right sho!s the e&uivalent circuit for an energy cell#

Rm is the resistance of the metallic path through the cell including the terminals, electrodes and inter;connections# Ra is the resistance of the electrochemical path including the electrolyte and the separator# C is the capacitance of the parallel plates !hich form the electrodes of the cell# Ri is the non;linear contact resistance bet!een the plate or electrode and the electrolyte#

%ypical internal resistance is in the order of milliohms# Effects of Internal Impedance <hen current flo!s through the cell there is an += voltage drop across the internal resistance of the cell !hich decreases the terminal voltage of the cell during discharge and increases the voltage needed to charge the cell thus reducing its effective capacity as !ell as decreasing its charge>discharge efficiency# Higher discharge rates give rise to higher internal voltage drops !hich e"plains the lo!er voltage discharge curves at high C rates# *ee ?Discharge =ates? belo!# %he internal impedance is affected by the physical characteristics of the electrolyte, the smaller the granular si.e of the electrolyte material the lo!er the impedance# %he grain si.e is controlled by the cell manufacturer in a milling process# *piral construction of the electrodes is often used to ma"imise the surface area and thus reduce internal impedance# %his reduces heat generation and permits faster charge and discharge rates# %he internal resistance of a galvanic cell is temperature dependent, decreasing as the temperature rises due to the increase in electron mobility# %he graph belo! is a typical e"ample#

%hus the cell may be very inefficient at lo! temperatures but the efficiency improves at higher temperatures due to the lo!er internal impedance, but also to the increased rate of the chemical reactions# Ho!ever the lo!er internal resistance unfortunately also causes the self discharge rate to increase# Furthermore, cycle life deteriorates at high temperatures# *ome form of heating and cooling may be re&uired to maintain the cell !ithin a restricted temperature range to achieve the optimum performance in high po!er applications# %he internal resistance of most cell chemistries also tends to increase significantly to!ards the end of the discharge cycle as the active chemicals are converted to their discharged state and hence are effectively used up# %his is principally responsible for the rapid drop off in cell voltage at the end of the discharge cycle# +n addition the @oule heating effect of the +(= losses in the internal resistance of the cell !ill cause the temperature of the cell to rise# %he voltage drop and the +(= losses may not be significant for a 7''' m$h cell po!ering a mobile phone but for a 7'' cell ('' $h automotive battery they can be substantial# %ypical internal resistance for a 7'''m$ Lithium mobile phone battery is around 7'' to (''mAhm and around 7mAhm for a (''$h Lithium cell used in an automotive battery# *ee e"ample# Aperating at the C rate the voltage drop per cell !ill be about '#( volts in both cases, 2slightly less for the mobile phone4# %he + (= loss in the mobile phone !ill be bet!een '#7 and '#( <atts# +n the automotive battery ho!ever the voltage drop across the !hole battery !ill be (' Bolts and +(= po!er loss dissipated as heat !ithin the battery !ill be 8' <atts per cell or 8C< for the !hole battery# %his is in addition to the heat generated by the electrochemical reactions in the cells# $s a cell ages, the resistance of the electrolyte tends to increase# $ging also causes the surface of the electrodes to deteriorate and the contact resistance builds up and at the same the effective area of the plates decreases reducing its capacitance# $ll of these effects increase the internal impedance of the cell adversely affecting its ability to perform# Comparing the actual impedance of a cell !ith its impedance !hen it !as ne! can be used to give a measure or representation of the age of a cell or its effective capacity# *uch measurements are much more convenient than actually discharging the cell and can be taken !ithout destroying the cell under test# *ee ?+mpedance and Conductance %esting? %he internal resistance also influences the effective capacity of a cell# %he higher the internal resistance, the higher the losses !hile charging and discharging, especially at higher currents# %his means that for high discharge rates the lo!er the available capacity of the cell# Conversely, if it is discharged over a prolonged period, the $mpHour capacity is higher# %his is important because some manufacturers specify the capacity of their batteries at very lo! discharge rates !hich makes them look a lot better than they really are#

Discharge Rates
%he discharge curves for a Lithium +on cell belo! sho! that the effective capacity of the cell is reduced if the cell is discharged at very high rates 2or conversely increased !ith lo! discharge rates4# %his is called the capacity offset and the effect is common to most cell chemistries#

Battery !oad Battery discharge performance depends on the load the battery has to supply# +f the discharge takes place over a long period of several hours as !ith some high rate applications such as electric vehicles, the effective capacity of the battery can be as much as double the specified capacity at the C rate# %his can be most important !hen dimensioning an e"pensive battery for high po!er use# %he capacity of lo! po!er, consumer electronics batteries is normally specified for discharge at the C rate !hereas the *$E uses the discharge over a period of (' hours 2'#'6C4 as the standard condition for measuring the $mphour capacity of automotive batteries# %he graph belo! sho!s that the effective capacity of a deep discharge lead acid battery is almost doubled as the discharge rate is reduced from 7#'C to '#'6C# For discharge times less than one hour 2High C rates4 the effective capacity falls off dramatically# %he effectiveness of charging is similarly influenced by the rate of charge# $n e"planation of the reasons for this is given in the section on Charging %imes #

%here are t!o conclusions to be dra!n from this graph0

Care should be e"ercised !hen comparing battery capacity specifications to ensure that comparable discharge rates are used# +n an automotive application, if high current rates are used regularly for hard acceleration or for hill climbing, the range of the vehicle !ill be reduced#

Duty Cycle Duty cycles are different for each application# EB and HEB appications impose particular, variable loads on the battery# *ee Load %esting e"ample# *tationary batteries used in distributed grid energy storage applications may have very large *AC changes and many cycles per day# +t is important to kno! ho! much energy is used per cycle and to design for the ma"imum energy throughput and po!er delivery, not the average# "otes# For information

$ typical small electric car !ill use bet!een 76' to (6' <atthours of energy per mile !ith normal driving# %hus, for a range of 7'' miles at ('' <atthours per mile, a battery capacity of (' C<h !ill be re&uired# Hybrid electric vehicle use smaller batteries but they may be re&uired to operate at very high discharge rates of up to 8'C# +f the vehicle uses regenerative braking the battery must also accept very high charging rates to be effective# *ee the section about Capacitors for an e"ample of ho! this re&uirement can be accommodated#

$eu%ert Equation %he /eukert e&uation is a convenient !ay of characterising cell behaviour and of &uantifying the capacity offset in mathematical terms# %his is an empirical formula !hich appro"imates ho! the available capacity of a battery changes according to the rate of discharge# C D + n % !here ?C? is the theoretical capacity of the battery e"pressed in amp hours, ?+? is the current, ?%? is time, and ?n? is the /eukert )umber, a constant for the given battery# %he e&uation sho!s that at higher currents, there is less available energy in the battery# %he /eukert )umber is directly related to the internal resistance of the battery# Higher currents mean more losses and less available capacity# %he value of the /eukert number indicates ho! !ell a battery performs under continuous heavy currents# $ value close to 7 indicates that the battery performs !ellE the higher the number, the more capacity is lost !hen the battery is discharged at high currents# %he /eukert number of a battery is determined empirically# For Lead acid batteries the number is typically bet!een 7#5 and 7#8

%he graph above sho!s that the effective battery capacity is reduced at very high continuous discharge rates# Ho!ever !ith intermittent use the battery has time to recover during &uiescent periods !hen the temperature !ill also return to!ards the ambient level# Because of this potential for recovery, the capacity reduction is less and the operating efficiency is greater if the battery is used intermittently as sho!n by the dotted line# %his is the reverse of the behaviour of an internal combustion engine !hich operates most efficiently !ith continuous steady loads# +n this respect electric po!er is a better solution for delivery vehicles !hich are subFect to continuous interruptions#

Ragone $lots
%he =agone plot is useful for characterising the trade;off bet!een effective capacity and po!er handling# )ote that the =agone plots are usually based on logarithmic scales# %he graph belo! sho!s the superior gravimetric energy density of Lithium +on cells# )ote also that Lithium ion cells !ith Lithium %itanate anodes 2$ltairnano4 deliver a very high po!er density but a ruduced energy density#

Energy and $o&er Density ' Ragone $lot

*ource $ltairnano %he =agone plot belo! compares the performance of a range of electrochemical devices# +t sho!s that ultracapacitors 2supercapacitors4 can deliver very high po!er but the storage capacity is very limited# An the other hand Fuel Cells can store large amounts of energy but have a relatively lo! po!er output#

Ragone $lot of Electrochemical Devices

%he sloping lines on the =agone plots indicate the relative time to get the charge in or out of the device# $t one e"treme, po!er can be pumped into, or e"tracted from, capacitors in microseconds# %his makes them ideal for capturing regenerative braking energy in EB applications# $t the other e"treme, fuel cells have a very poor dynamic performance taking hours to generate and deliver their energy# %his limits their application in EB applications !here they are often used in conFunction !ith batteries or capacitors to overcome this problem# Lithium batteries are some!here in bet!een and provide a reasonable compromise bet!een the t!o# *ee also $lternative Energy *torage Comparisons#

$ulse $erformance
%he ability to deliver high current pulses is a re&uirement of many batteries# %he current carrying capacity of a cell depends on the effective surface area of the electrodes# 2*ee Energy>/o!er %rade;Affs4# %he current limit is ho!ever set by the rate at !hich the chemical reactions occur !ithin the cell# %he chemical reaction or ?charge transfer? takes place on the surface of the electrodes and the initial rate can be &uite high as the chemicals close to the electrodes are transformed# Ance this has occurred ho!ever, the reaction rate becomes limited by the rate at !hich the active chemicals on the electrode surface can be replenished by diffusion through the electrolyte in a process kno!n as ?mass transfer?# %he same principle applies to the charging process and is e"plained in more detail in the section on Charging %imes# %he pulse current can therefore be substantially higher than the C rate !hich characterises the continuous current performance#

Cycle !ife
%his is one of the key cell performance parameters and gives an indication of the e"pected !orking lifetime of the cell#

%he cycle life is defined as the number of cycles a cell can perform before its capacity drops to G'9 of its initial specified capacity# Each charge ; discharge cycle, and the associated transformation cycle of the active chemicals it brings about, is accompanied by a slo! deterioration of the chemicals in the cell !hich !ill be almost imperceptible to the user# %his deterioration may be the result of unavoidable, un!anted chemical actions in the cell or crystal or dendrite gro!th changing the morphology of the particles making up the electrodes# Both of these events may have the effect of reducing the volume of the active chemicals in the cell, and hence its capacity, or of increasing the cellHs internal impedance# )ote that the cell does not die suddenly at the end of the specified cycle life but continues its slo! deterioration so that it continues to function normally e"cept that its capacity !ill be significantly less than it !as !hen it !as ne!#

%he cycle life as defined is a useful !ay of comparing batteries under controlled conditions, ho!ever it may not give the best indication of battery life under actual operating conditions# Cells are seldom operated under successive, complete charge ; discharge cycles, they are much more likely to be subFect to partial discharges of varying depth before complete recharging# *ince smaller amounts of energy are involved in partial discharges, the battery can sustain a much greater number of shallo! cycles# *uch usage cycles are typical for Hybrid Electric Behicle applications !ith regenerative braking# *ee ho! cycle life varies !ith depth of discharge in Battery Life# Cycle life also depends on temperature, both operating and storage temperature# *ee more details in the section on Lithium Battery Failures# $ more representative measure of battery life is the !ifetime Energy Throughput# %his is the total amount of energy in <atthours !hich can be put into and taken out of a battery over all the cycles in its lifetime before its capacity reduces to G'9 of its initial capacity !hen ne!# +t depends on the cell chemistry and the operating conditions# nfortunately this measure is not yet in common use by cell manufacturers and has not yet been adopted as a battery industry standard# ntil it comes into general use it !ill not be possible to use it to compare the performance of cells from different manufacturers in this !ay but, !hen available, at least it provides a more useful guide to applications engineers for estimating the useful life of batteries used in their designs# *ee also Estimating Battery Lifetimes

Deep Discharge
Cycle life decreases !ith increased Depth of Discharge 2DAD4 2*ee Battery Life4 and many cell chemistries !ill not tolerate deep discharge and cells may be permanently damaged if fully discharged# *pecial cell constructions and chemical mi"es are re&uired to ma"imise the potential DAD of deep cycle batteries#

Charging Characteristics
Charging curves and recommended charging methods are included in a separate section on Charging

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