Secondary cells

(rechargeable batteries)
KEY KNOWLEDGE
•The common design features and general
operating principles of rechargeable
(secondary) cells, with reference to discharging
as a galvanic cell and recharging as an
electrolytic cell, including the conditions
required for the cell reactions to be reversed
and the electrode polarities in each mode
(details of specific cells not required)
ELECTROCHEMICAL VS ELECTROLYTIC
CELLS
Recharging battery Electrolytic cell)

Discharging battery (Galvanic cell)

https://online.clickview.com.au/libraries/videos/3715154/understanding-el
ectrolysis
Always remember ... (ANY TYPE OF CELL!)
AnOILRIGCat

CATHODE

• The site of REDUCTION 100 % of the time.

• Electrons are “reactants” in half-equation.

ANODE

• The site of OXIDATION 100 % of the time.

• Electrons are “products” in half-equation.
PRIMARY VS SECONDARY CELLS
*Secondary cells are rechargeable batteries.
When discharging (chemicalelectrical) these operate as Galvanic cells.
When recharging (electrical  chemical), they act as an electrolytic cell.
What happens to the polarity of the Anode (Oxidation) and Cathode (Reduction) when
acting as an electrolytic cell? (HINT: Watch electron flow)
*Why was
hydrogen
gas
produced?
HINT: Solid
copper is a
r_________
(check EC
series to
see what
ions were in
the water to
electrons)
 AnOILRIGCat
applies to both
Electrochemical
(Galvanic) and
Electrolytic Cells
(NB Polarity of
Anode & Cathode
different)
Recharging: Equations are reversed. Electrons are FORCED
by a POWER SUPPLY to the side of reduction (cathode). The
CATHODE BECOMES NEGATIVE DURING RECHARGE.
Lead-acid accumulator (car battery)
DISCHARGE:
*Check data book for half equations!

*The products of discharge remain in contact with the electrodes

so the battery can be recharged.
*Can you write the anode, cathode and overall reactions for
recharging?
RECHARGE:
*NB Lead sulfate
gradually falls from
the electrodes over
time, eventually
preventing recharge.
 *Check your data book: Know how to use the
electrochemical series!
A spontaneous reaction (i.e.
(written in Reduction format)
without input of electricity)
will only occur if an oxidant
i.e. electrons feature on the reactant side of the half-equation.
(left) is higher in the series
STRONGER OXIDANT

than a reductant (right)

Cu2+ (aq) + 2e–  Ni
e.g Cu2+(s) + Pb  no + 0.34

 STRONGER REDUCTANTS
(aq) (s)
CO2 (g) + 8H (aq) + 8e
+ –
 CH4 (g) + 2H2O (l) + 0.17
reaction!
S (s) + 2H+ (aq) + 2e–  H2S (g) + 0.14

2H+ (aq) + 2e–  H2 (g) + 0.00

Pb2+ (aq) + 2e–  Pb (s) – 0.13

Sn2+ (aq) + 2e–  Sn (s) – 0.14

Ni2+ (aq) + 2e–  Ni (s) – 0.23

ELECTROLYTIC CELLS CAN FORCE NON-SPONTANEOUS REACTIONS
Small section of the electrochemical series
Potential difference
The electrochemical series can predict the potential
difference (in v______) generated by a galvanic
cell. This is equal to the difference between the
higher half cell E° and the lower half cell E°.
(HIGHER –LOWER)
The cell can only be recharged with the input

greater than the potential difference

generated during discharge.
Electrolytic cells summary (battery recharging)
e
+ ̶ The battery drives the
Battery e reactions.
* The battery PUSHES ELECTRONS
anode onto one electrode
• forces electrons to gather on the electrode
cathode • forces the electrode to be negative
• forces chemical species to use electrons
• forces reduction to occur
* The battery PULLS ELECTRONS
from the other electrode
Electrolytic cell • forces electrons to leave the electrode
• forces the electrode to be positive
• forces chemical species to donate electrons
• forces oxidation to occur
 Summary
• Primary cells cannot be r__________.
• Secondary cells can be recharged by connecting
them to an external source of e_____________.
• The p________ of the discharge reaction must
remain in contact with the e__________ in order
for a cell to recharge.
• The equation for the recharge reaction is the
r________ of the equation for the discharge
reaction.
• The anode (oxidation) is n________ during
discharge but p__________ during recharge.
•
Example (very hard) exam question
https://www.youtube.com/watch?v=E5R4A9q8t6M
Lead acid battery (prac)