Lecture: Lead-acid batteries

ECEN 4517/5517

How batteries work

Conduction mechanisms Development of voltage at plates Charging, discharging, and state of charge

Key equations and models

The Nernst equation: voltage vs. ion concentration Battery model Battery capacity and Peukert s law

Energy efciency, battery life, and charge proles

Coulomb efciency, voltage drops, and round-trip efciency Battery life vs. depth of discharge Charging strategies and battery charge controllers

ECEN 4517

Lead-acid battery: construction

Pb

PbO2

Negative electrode: Porous lead

H 2O H2SO4

Positive electrode: Lead-dioxide

Electrolyte: Sulfuric acid, 6 molar

How it works Characteristics and models Charge controllers

ECEN 4517

Electrical conduction mechanisms

Lead and lead-dioxide are good electrical conductors. The conduction mechanism is via electrons jumping between atoms. The electrolyte contains aqueous ions (H+ and SO4-2). The conduction mechanism within the electrolyte is via migration of ions via diffusion or drift.

Pb H+ H+ SO4
-2

H+ H+ SO4-2

PbO2

H 2O

Q: What are the physical mechanisms of conduction in the complete path from one terminal, through an electrode, into the electrolyte, onto the other electrode, and out the other terminal?
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Conduction mechanism at the surface of the electrode

Oxidation-reduction (Redox) reaction transfers charge from ions in solution to conducting electrons in the electrode At the surface of the lead (negative) electrode:
Charged sulfate ion approaches uncharged lead atom on surface of electrode
Lead electrode Pb0 Pb0 Pb0 Pb Pb
0 0

Lead atom becomes ionized and forms ionic bond with sulfate ion. Two electrons are released into lead electrode
Lead electrode Pb0 Pb0 Pb0 Pb
+2 0

Sulfuric acid electrolyte H+ SO4-2 SO4-2 H+ H+ H 2O H+

Sulfuric acid electrolyte H+ SO4-2 SO4-2 H+ H+ H 2O H+

Pb

Pb0 Pb
0

Pb0 Pb
0

ECEN 4517

The chemical reaction (half reaction) at the lead electrode

Pb + SO42
solid aqueous

PbSO4 + 2e
solid in conductor

Lead electrode

Pb0 Pb0 Pb Pb
0

Sulfuric acid electrolyte H+ SO4

-2

H+

This reaction releases net energy

+2 0

SO4-2 H+ H+ H 2O

E0

= 0.356 eV

Pb

the Gibbs free energy, under standard conditions (T = 298K, concentration = 1 molar)

Pb0 Pb
0

Units: Energy = (charge)(voltage) Energy in eV = (charge of electron)(1 V)

So the charge of the aqueous sulfate ion is transferred to two conducting electrons within the lead electrode, and energy is released.

ECEN 4517

Conduction mechanism at the surface of the positive electrode

Charged sulfate and hydrogen ions approach lead-dioxide molecule (net uncharged) on surface of electrode
Sulfuric acid electrolyte H+ H+ SO4-2 SO4
-2

Lead atom changes ionization and forms ionic bond with sulfate ion. Two water molecules are released into solution
Sulfuric acid electrolyte O2 Pb+4 O2 SO4-2 H 2O
+2 SO4-2 Pb

O2 Pb+4 O2 O2 Pb+4 O
2

Leaddioxide electrode

Leaddioxide electrode

H 2O H 2O

H+ H 2O H+

O2 Pb+4 O2

O2 Pb+4 O2

Lead changes oxidation state from +4 to +2 Two electrons are removed from conduction band in electrode
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The chemical reaction (half reaction) at the lead-dioxide electrode

PbO2 + SO42 + 4H+ + 2e
solid aqueous aqueous in conductor H+ H+ SO4-2 SO4
-2

Sulfuric acid electrolyte

O2 Pb+4 O2 O2 Pb+4 O
2

Leaddioxide electrode

PbSO4 + 2H2O
solid liquid

This reaction releases net energy

H+ H 2O H+

E0 = 1.685 eV
Net charge of two electrons is transferred from the electrode into the electrolyte Both half reactions cause the electrodes to become coated with lead sulfate (a poor conductor) and reduce the concentration of the acid electrolyte
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O2 Pb+4 O2

How the battery develops voltage

Consider the following experiment: New electrodes are placed inside electrolyte, with no external electrical circuit connected The reactions start to occur
Pb
H 2O Pb
0

PbO2
SO4-2 H+
-2

They use up aqueous ions near electrodes Diffusion within electrolyte replenishes ions near electrodes

O2 H+ H+ Pb O O SO4-2 H+
+4

Pb0 Pb Pb Pb Pb Pb
0 +2 0 0 0

H+ SO4
-2

2 2

SO4

-2

SO4 H+

Pb+4 O2 O2 Pb
+4

H+ H 2O H 2O

H+

O2

Excess electrons are created in lead electrode, and electron decit is created in lead-dioxide electrode Electric eld is generated at electrode surfaces. This electric eld opposes the ow of ions.

ECEN 4517

Battery voltage at zero current

Energy barriers at electrode surface

Vbatt

Ibatt

Pb H+ H+ SO4
-2

H+ H+ SO4-2

PbO2

The chemical reactions at the electrode surfaces introduce electrons into the Pb electrode, and create a deficit of electrons in the PbO2 electrode These charges change the voltages of the electrodes The system reaches equilibrium when the energy required to deposit or remove an electron equals the energy generated by the reaction Total voltage (at T = 298K and 1 molar acid electrolyte) is Vbatt = 0.356 + 1.685 = 2.041 V

H 2O
Diffusion Drift Diffusion Drift

Eo/qe = 1.685 V Eo/qe = 0.356 V

ECEN 4517

Discharging
R +

Vbatt < 2.041 V

Ibatt

Connection of an electrical load allows electrons to flow from negative to positive terminals This reduces the charge and the voltages at the electrodes The chemical reactions are able to proceed, generating new electrons and generating the power that is converted to electrical form to drive the external electrical load

Pb H+ H+ SO4
-2

H+ H+ SO4
-2

PbO2

H 2O PbSO4 v
Diffusion Drift Diffusion Drift

< 1.685 V < 0.356 V

As the battery is discharged, the electrodes become coated with lead sulfate and the acid electrolyte becomes weaker
10

ECEN 4517

Charging
External source of electrical power

Vbatt > 2.041 V

Ibatt

Connection of an electrical power source forces electrons to flow from positive to negative terminals This increases the charge and the voltages at the electrodes The chemical reactions are driven in the reverse direction, converting electrical energy into stored chemical energy

Pb H+ H+ SO4
-2

H+ H+ SO4-2

PbO2

H 2O PbSO4 v
Diffusion Drift Diffusion Drift

> 1.685 V > 0.356 V

As the battery is charged, the lead sulfate coating on the electrodes is removed, and the acid electrolyte becomes stronger
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ECEN 4517

Battery state of charge (SOC)

Fully Charged Completely Discharged

State of charge: Depth of discharge: Electrolyte concentration: Electrolyte specic gravity: No-load voltage:
(specic battery types may vary)

100% 0% ~6 molar ~1.3 12.7 V

0% 100% ~2 molar ~1.1 11.7 V

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Battery voltage vs. electrolyte concentration

The Nernst equation relates the chemical reaction energy to electrolyte energy:
E = E0 + (kT/qe) ln [(electrolyte concentration)/(1 molar)]
(idealized)

with
E = energy at a given concentration E0 = energy at standard 1 molar concentration kT/qe = 26 mV at 298 K

Implications:
At fully charged state (6 molar), the cell voltage is a little higher than E0 /qe As the cell is discharged, the voltage decreases
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Voltage vs. electrolyte concentration

Fully charged

Usab

le ra

nge

Time to recycle

Voltage of lead-acid electrochemical cell vs. electrolyte concentration, as predicted by Nernst equation
R. S. Treptow, The lead-acid battery: its voltage in theory and practice, J. Chem. Educ., vol. 79 no. 3, Mar. 2002

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Mechanisms that affect terminal voltage

1. 2. 3. Equilibrium voltage changes with electrolyte concentration (as described above Nernst equation) With current ow, there are resistive drops in electrodes, especially in surface lead-sulfate With current ow, there is an electrolyte concentration gradient near the electrodes. Hence lower concentration at electrode surface; Nernst equation then predicts lower voltage Additional surface chemistry issues: activation energies of surface chemistry, energy needed for movement of reacting species through electrodes Physical resistance to movement of ions through electrodes

4.

5.

(2) - (5) can be modeled electrically as resistances

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A basic battery model

Basic model Dependence of model parameters on battery state of charge (SOC)
Rdischarge(SOC) Rcharge(SOC) Ideal diodes Vbatt Ibatt +
Rcharge(SOC)

V(SOC)

V(SOC) +

Rdischarge(SOC)
0% 100%

SOC

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Types of lead-acid batteries

1. Car battery
SLI - starter lighting ignition Designed to provide short burst of high current
Maybe 500 A to crank engine

Cannot handle deep discharge applications

Typical lifetime of 500 cycles at 20% depth of discharge

2. Deep discharge battery

We have these in power lab carts More rugged construction
Bigger, thicker electrodes Calcium (and others) alloy: stronger plates while maintaining low leakage current More space below electrodes for accumulation of debris before plates are shorted

Ours are
Sealed, valve regulated, absorbent glass mat Rated 56 A-hr at 2.33A (24 hr) discharge rate
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Types of lead-acid batteries

3. Golf cart or forklift batteries
Similar to #2 Bigger, very rugged Low cost established industry Antimony alloy
Strong big electrodes But more leakage current than #2

Can last 10-20 years

Manufacturers specifications for our power lab batteries:

Nominal capacity: A-hrs @ 25C to 1.75 V/cell 1 hr 36 A-hr

ECEN 4517

2 hr 45 A-hr

4 hr 46 A-hr
18

8 hr 49 A-hr

24 hr 56 A-hr

Battery capacity
The quantity C is defined as the current that discharges the battery in 1 hour, so that the battery capacity can be said to be C Ampere-hours (units confusion) If we discharge the battery more slowly, say at a current of C/10, then we might expect that the battery would run longer (10 hours) before becoming discharged. In practice, the relationship between battery capacity and discharge current is not linear, and less energy is recovered at faster discharge rates. Peukerts Law relates battery capacity to discharge rate: Cp = Ik t where Cp is the amp-hour capacity at a 1 A discharge rate I is the discharge current in Amperes t is the discharge time, in hours k is the Peukert coefficient, typically 1.1 to 1.3
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Example

Our lab batteries k = 1.15 C = 36 A Cp = 63 A-hr Prediction of Peukert equation is plotted at left

What the manufacturers data sheet specified:

Nominal capacity: A-hrs @ 25C to 1.75 V/cell 1 hr 36 A-hr 2 hr 45 A-hr

20

4 hr 46 A-hr

8 hr 49 A-hr

24 hr 56 A-hr

ECEN 4517

Energy efciency
Efciency = ED/EC VC I C T C VDIDTD

EC = Total energy during charging = vbatt (-ibatt) dt ED = Total energy during discharging = vbatt ibatt dt

Energy efficiency =

VD VC

I DT D = voltage efficiency coulomb efficiency I CT C

Coulomb efciency = (discharge A-hrs)/(charge A-hrs) Voltage efciency = (discharge voltage)/(charge voltage)
Rdischarge(SOC) Rcharge(SOC) Ideal diodes Vbatt Ibatt + V(SOC) +

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Energy efciency
Energy is lost during charging when reactions other than reversal of sulfation occur
At beginning of charge cycle, coulomb efciency is near 100% Near end of charge cycle, electrolysis of water reduces coulomb efciency. Can improve this efciency by reducing charge rate (taper charging) Typical net coulomb efciency: 90% Approximate voltage efciency: (2V)/(2.3V) = 87%

Energy efciency = (87%)(90%) = 78% Commonly quoted estimate: 75%

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Battery life

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Charge management
Over-discharge leads to sulfation and the battery is ruined. The reaction becomes irreversible when the size of the lead-sulfate formations become too large Overcharging causes other undesirable reactions to occur
Electrolysis of water and generation of hydrogen gas Electrolysis of other compounds in electrodes and electrolyte, which can generate poisonous gasses Bulging and deformation of cases of sealed batteries

Battery charge management to extend life of battery:

Limit depth of discharge When charged but not used, employ oat mode to prevent leakage currents from discharging battery Pulsing to break up chunks of lead sulfate Trickle charging to equalize charges of series-connected cells

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Charge prole
A typical good charge prole: Bulk charging at maximum power
Terminate when battery is 80% charged (when a voltage set point is reached)

Charging at constant voltage

The current will decrease This reduces gassing and improves charge efciency Absorption or taper charging

Trickle charging / oat mode

Equalizes the charge on series-connected cells without signicant gassing Prevents discharging of battery by leakage currents Occasional pulsing helps reverse sulfation of electrodes
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The three-step charge profile used by the chargers in our power lab

Charge and oat voltages

Good chargers can:
Program charge/oat voltages to needs of specic battery type Temperature-compensate the voltage set points Maintain battery in fully charged state (oat mode) when in storage Avoid overcharging battery (charge voltage set point) Taper back charging current to improve charge efciency and reduce outgassing
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Battery charge controller

Charge controller Inverter AC loads

PV array

Prevent sulfation of battery Low SOC disconnect Float or trickle charge mode Control charge profile Multi-mode charging, set points Nightime disconnect of PV panel
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Direct energy transfer Charge battery by direct connection to PV array MPPT Connect dc-dc converter between PV array and battery; control this converter with a maximum power point tracker