Electrochemistry

References: Brady/Jespersen/Hyslop, Chemistry, 7E, 2015, John Wiley & Sons, Inc.

Raymond Chang, Chemistry, 10E, 2010, McGraw Hill.

2018/2019
Batteries
• Galvanic cells that generate portable electrical energy
• Usually a collection of several linked in series to get
higher voltages
Ex. Car batteries, usually 6 cells each capable of
producing 2 V; so Net = 12 V
Important properties of battery
Shelf-life
How long do batteries hold
their charge when not in use?
Rate of energy output
High currents
Energy density
Ratio of available energy to
battery volume
Specific energy
Ratio of available energy to
weight Tarascon et al, Nature, 414, 2001

Properties that modern battery designers consider for applications

such as: Cell phones, laptops, digital cameras, cordless tools and
pacemakers
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Two major class of batteries
Primary Cell Secondary Cell
§ Non-rechargeable § Rechargeable
§ Ex. Alkaline dry cell § Pb storage Battery

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Alkaline battery
• Zn/MnO2 battery 1.5 V
• Uses basic or alkaline electrolyte
• Not rechargeable
• Compared to dry cell
• Longer shelf life
• Delivers higher currents
• Less expensive
• Reactions:
Anode Zn(s) + 2OH–(aq) → ZnO(s) + H2O + 2e –
Cathode 2MnO2(s) + H2O + 2e – → Mn2O3(s) + 2OH–(aq)
Net Zn(s) + 2MnO2(s) → ZnO(s) + Mn2O3(s)
Ni-Cd battery

• Rechargeable http://www.rcmodelreviews.com/baffledbybatteries1.shtml

• High energy density

• Release energy quickly
• Rapidly recharged
• Used in portable power tools,
CD players, electric cars
• Disadvantage = Cd toxicity, so
disposal a problem
Reactions (discharge):
Anode: Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e –
Cathode: NiO2(s) + 2H2O + 2e – → Ni(OH)2(s) + 2OH– (aq)
Net: Cd(s) + NiO2(s) → Cd(OH)2(s) + Ni(OH)2(s) 6
Ni-MH battery

• Rechargeable http://www.gpbmindustry.com/en/nimh

• 1.35 V
• Some metals and alloys can absorb H2 gas and effectively
store it, release to redox reaction
• Advantages:
• 50% more power/volume than NiCad
• Useful longer
• Reactions (discharge):
Anode: MH(s) + OH–(aq) → M(s) + H2O + e –
Cathode: NiO(OH)(s) + H2O + e – → Ni(OH)2(s) + OH–(aq)
Net: MH(s) + NiO(OH)(s) → Ni(OH)2(s) + M(s) 7
 Under normal operating conditions, each cell produces 2 V; a total of 12 V from the

Lead-acid battery
six cells is used to power the ignition circuit of the automobile and its other electrical
systems. The lead storage battery can deliver large amounts of current for a short time,
such as the time it takes to start up the engine.
Unlike the Leclanché cell and the mercury battery, the lead storage battery is
rechargeable. Recharging the battery means reversing the normal electrochemical reac-
tion by applying an external voltage at the cathode and the anode. (This kind of process
• Rechargeable is called electrolysis, see p. 866.) The reactions that replenish the original materials are

PbSO4(s) 1 2e2 ¡ Pb(s) 1 SO22

4 (aq )

• ~2.0 V PbSO4(s) 1 2H2O(l) ¡ PbO2(s) 1 4H1(aq ) 1 SO22

4 (aq ) 1 2e

Overall: 2PbSO4(s) 1 2H2O(l) ¡ Pb(s) 1 PbO2(s) 1 4H1(aq ) 1 2SO22

2

4 (aq )

• Each cell has a lead anode and a The overall reaction is exactly the opposite of the normal cell reaction.
Two aspects of the operation of a lead storage battery are worth noting. First,
cathode made of lead dioxide because the electrochemical reaction consumes sulfuric acid, the degree to which the
https://www.bhphotovideo.com/c/product/1009424-REG/profoto_100222_lead_acid_battery_for.html

(PbO2) packed on a metal

Figure 19.9plate Interior section of
a lead storage battery. Under
Anode
Removable cap
Cathode
normal operating conditions, the
–
• Advantages:
concentration of the sulfuric acid
solution is about 38 percent by
mass.

• Good low and high +

temperature performance H2SO 4 electrolyte

• Low self-discharge; lowest

among rechargeable batteries Negative plates (lead grills
filled with spongy lead)

Reactions (discharge): Positive plates (lead grills

Anode: Pb(s) + SO42–(aq) → PbSO4(s) + 2e –

filled with PbO2)

Cathode: PbO2(s) + 4H+(aq) + SO42–(aq) + 2e – → PbSO4(s) + 2H2O (l)

Net: Pb(s) + PbO2(s) + 4H+(aq) + SO42–(aq) → 2PbSO4(s) + 2H2O (l)

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Lead-acid battery
Recharging the battery means reversing the normal
electrochemical reaction by applying an external voltage at the
cathode and the anode (this kind of process called
ELECTROLYSIS-next part)
Reactions (re-charge):
PbSO4(s) + 2e – → Pb(s) + SO42–(aq) WHICH ELECTRODE?
PbSO4(s) + 2H2O (l) → PbO2(s) + 4H+(aq) + SO42–(aq) + 2e – WHICH?
Net: 2PbSO4(s) + 2H2O (l) → Pb(s) + PbO2(s) + 4H+(aq) + SO42–(aq)

Food for thought

In lead-acid battery, the degree of discharge can be checked by
measuring density of the electrolyte. Density of fluid in a
“healthy” fully charged battery should be equal or greater than
1.2 g/mL. What will you expect to the density of electrolyte if
you over-discharged?
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 the battery to function properly, the electrolyte must be fully conduct-

Li ion batteries (LIB)

the ions move much more slowly in a viscous medium, so the resistance
creases, leading to a decrease in the power output of the battery. If an
ead battery” is warmed to near room temperature on a frigid day, it
bility to deliver normal power.

• Rechargeable
m-Ion Battery high specific energy (due to
low mass)
shows a schematic diagram of a lithium-ion battery. The anode is
onducting carbonaceous material, usually graphite, which has tiny
• High energy density (very negative E °)
structure that can hold both Li atoms and Li1 ions. The cathode is
ansition metal oxide such as CoO2, which can also hold Li1 ions.
• Li ion battery is based on transport of
+ of the metal, nonaqueous electrolyte (organic solvent
e high reactivity
d salt) must be used. During the discharge of the battery, the half-cell
Li+ ions
oxidation):+ Li(s) ¡ Li1 1 e2
• Li ions can slip between layers of atoms
reduction): Li1 1 CoO2 1 e2 ¡ LiCoO2 (s)
in solids
Overall: Li (s) 1such asLiCoO
CoO ¡ graphite
(s) or
E 5LiCoO
23.4 V 2 2 cell

(Process called intercalation)

Figure 19.10 A lithium-ion
battery. Lithium atoms are
Charging: LiCoO + C → Li CoO2 + LixC6
embedded in the graphite, which
serves as2 the anode,
6 and CoO1–x
2
e– e–
Discharge: Li CoO + Li C → Li1–x+yCoO2 + Lix–yC6
is the cathode. During operation,
Li1–x
1
2 through the
ions migrate x 6
nonaqueous electrolyte from the
Anode Cathode
anode to the cathode while

Advantages:
electrons flow externally from
the anode to the cathode to
complete the circuit.
Li +

Li in CoO
• High specific energy and high load
capabilities with Power Cells
2
graphite
Nonaqueous electrolyte

• Long cycle and extend shelf-life;

Li Li + + e – Li + + CoO2 + e – LiCoO
2 maintenance-free 10
Li ion batteries (LIB)
Name LCO LNO NCA NMC LMO LFP LTO
Items Lithium Lithium Lithium Nickel Lithium Nickel Lithium Lithium Lithium
Cobalt Nickel Cobalt Aluminium Manganese Manganese Iron Titanate
Oxide Oxide Oxide Cobalt Oxide Spinel Phosphate
Cathode LiCoO2 LiNiO2 Li(Ni0.85Co0.1Al0.05)O2 Li(Ni0.33Mn0.33Co0.33)O2 LiMn2 O4 LiFePO4 LMO or
NCA
Anode Graphite Graphite Graphite Graphite Graphite Graphite Li4 Ti5 O12

Cell 3.7-3.9 V 3.6 V 3.65 V 3.8-4.0 V 4.0 V 3.3 V 2.3-2.5 V

Voltage
Energy 150 150 130 Wh/kg 170 Wh/kg 120 Wh/kg 130 85
density Wh/kg Wh/kg Wh/kg Wh/kg

Power + O + O + + ++

Safety - O O O + ++ ++

Lifetime - O + O O + +++

cost -- + O O + + O

www.rechargebatteries.org
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Fuel Cell
• Galvanic cells in which reactants are continuously supplied
with reagents
• Able to operate as long as supply of reactants is maintained
• Attractive power source for long-term generation of electricity
• Major advantages:
• Clean burning
• No electrode loss
• Easily replenished
• Highly efficient
• Low T to high T application

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Fuel Cell

The Electrochemical Society Interface • Spring 2006, 41-44

The classification determines the electrochemical reactions and also

operating temperatures of each type of fuel cells. This characteristics affect
the application for which these cells are suitable (e.g. portable devices or
stationary use)
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