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ECEN 4517/5517
ECEN 4517
Pb
PbO2
ECEN 4517
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?
ECEN 4517
3
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
Pb
Pb0 Pb
0
Pb0 Pb
0
ECEN 4517
PbSO4 + 2e
solid in conductor
Lead electrode
Pb0 Pb0 Pb Pb
0
H+
+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
ECEN 4517
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
ECEN 4517
6
O2 Pb+4 O2 O2 Pb+4 O
2
Leaddioxide electrode
PbSO4 + 2H2O
solid liquid
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
ECEN 4517
7
O2 Pb+4 O2
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
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
ECEN 4517
Discharging
R +
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
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
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
As the battery is charged, the lead sulfate coating on the electrodes is removed, and the acid electrolyte becomes stronger
11
ECEN 4517
State of charge: Depth of discharge: Electrolyte concentration: Electrolyte specic gravity: No-load voltage:
(specic battery types may vary)
ECEN 4517
12
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
ECEN 4517
13
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
ECEN 4517
14
4.
5.
ECEN 4517
15
V(SOC)
V(SOC) +
Rdischarge(SOC)
0% 100%
SOC
ECEN 4517
16
Ours are
Sealed, valve regulated, absorbent glass mat Rated 56 A-hr at 2.33A (24 hr) discharge rate
ECEN 4517
17
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
ECEN 4517
19
Example
Our lab batteries k = 1.15 C = 36 A Cp = 63 A-hr Prediction of Peukert equation is plotted at left
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
Coulomb efciency = (discharge A-hrs)/(charge A-hrs) Voltage efciency = (discharge voltage)/(charge voltage)
Rdischarge(SOC) Rcharge(SOC) Ideal diodes Vbatt Ibatt + V(SOC) +
ECEN 4517
21
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%
ECEN 4517
22
Battery life
ECEN 4517
23
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
ECEN 4517
24
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)
The three-step charge profile used by the chargers in our power lab
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
ECEN 4517
27
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