Electrochemical

Energy Storage
PROF. FÁTIMA MONTEMOR
ACADEMIC YEAR 2022/2023

Class # 1 IMPORTANCE
 BUT WHAT IS A BATTERY?

Battery is composed of electrochemical cells that can

be organised in series and/or parallel.

When charged, each cell stores energy in the form of

chemical energy and under discharge releases it.
So there is chemistry (electrochemistry) involved.

The core piece is the active electrode material!

FOR PRIMARY BATTERY MANUFACTURING LOOK AT:

https://www.duracell.in/technology/technology-in-the-service-of-battery-power/

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 BUT WHAT IS A BATTERY?
Battery stores energy as chemical energy and releases it under discharge.
Chemical energy is transformed in utile energy

A Battery is an association of electrochemical cells + several passive components

- Pole + Pole
Eth

anode cathode

Current Passive components:

Current
collector Collectors
collector
Terminals
Wiring
Casing
Membrane

Electrochemical reaction Electrochemical reaction

at the anode at the cathode

electrolyte Porous separator

Schematic view of an electrochemical cell
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 BUT WHAT IS A BATTERY?
Battery stores energy as chemical energy and releases it under discharge.

+ Positive terminal

Anode: metal, easy to oxidize,

e.g. Zinc in potassium hydroxide
Separator: prevents short circuit and allows ionic flux
Cathode: species that can be
easily reduced MnOx + C powder

Current collector
Container
Plastic cover SECONDARY BATTERY
Negative terminal LI ION CELL Aluminium collector
-
PRIMARY BATTERY Cathode Li Metal oxide
ALKALINE DRY Separator and electrolyte
BATTERY
Anode - graphite

Copper collector

https://www.learnengineering.org/Lithium-ion-battery/Different-layers-of-chemical-
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compounds-inside-tesla-cell.jpg
 WHAT IS AN ELECTROCHEMICAL CELL ?

(Galvanic Cell – explained by Galvani electrochemist, 1737–1798)

Electron flow
Cell Potential is 0.78 Volts
Electrical
Current
Produces work

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Powering the American Telegraph
pole - pole
Zn2+/Zn
E0 = -0.764 V

Zn metallic anode dissolves and

produces zinc ions and the
electrons

ZnZn2+ + 2e

Cu ions in the electrolyte consume

electrons and reduce to metallic Cu,
Cu2+/Cu
E0 = 0.337 V

Cu2+ + 2e  Cu

1 V Cell = 2 months lifetime

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To increase voltage: Cells connected in series
Positive
Higher voltage
pole Same current Electron
flow

Cell 3
Current

Cell 2 4.5 V 4.5 V 4.5 V

Cell 1

Negative
pole

The same current flows through all the cells

Current is the same as for one cell.

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To increase current: Cells connected in parallel

Positive pole

1.5 V 1.5 V 1.5 V 1.5 V 1.5 V

Cell 1 Cell 2 Cell 3

Negative pole

1.5 V

Parallel connection has the same effect of increasing electrode size

(higher current) but keeps the same potential of one cell!
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+ Current + voltage = Parallel + series Connected Cells

Positive pole

Cell Cell Cell Cell

2 4 2 3

3V 3V 3V
Cell
Cell Cell 1 Cell
1 3 3

Negative pole
v
2 independent series
3 V each 3V 2 series of 3 V
Current = I in parallel
This configuration increases both voltage Current = 2 I
(series) and current (parallel)

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The C – Rate
C-rate is a measure of the rate at which a battery is discharged relatively to its
maximum capacity.
C-Rate = 1 implies that the applied discharge current will discharge the battery
in 1 hour.

The discharge rate of a battery is expressed as C/R, where R is the number of

hours required to completely discharge its nominal capacity.

Examples:
A cell has a nominal capacity of 5 Ah, discharge at the rate of C/10:
It means fully discharge in 10 h. Thus, the current consumption is 0.5 A.

Question:
A cell has a nominal capacity of 5 Ah, discharge at the rate of C/5. How long it
takes to discharge at which current?

Thus, it will be fully discharged in 5 h and the discharge current is 1 A.

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Questions
A cell has a nominal capacity of 2500 mAh, and it is used to load a device that
requires 0,2 A.

How long does it run?:

A cell has a nominal capacity of 5 Ah. It is charged under 1 A.

How long it will take to be charged?

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Questions
A cell has a nominal capacity of 2500 mAh, and it is used to load a device that
requires 0,2 A.

How long does it run?: t = 2.5 Ah/0.2 A

t = 12.5 h

A cell has a nominal capacity of 5 Ah. It is charged under 1 A.

How long it will take to be charged?
t = 5 Ah/1A
t=5h

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 1st generation = (Zinc-Carbon) Batteries
The major primary battery! (-) electrode = Zn;
Used for more than 100 years (+) electrode manganese oxide

Electrolyte = ammonium chloride

Cheap

Satisfactory Electrochemical Parameters

Convenient Storage Life

Convenient Utilization

Strong Voltage Decrease (Final Voltage is 50-70% of Initial)

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Source: Bagotsky, V. S., Skundin, A. M., Volfkovich, Y. M., Electrochemical Power Sources: Batteries, Fuel Cells, and Supercapacitors, Wiley, 2015
Zn-C battery development: the massive commercialization
The Zn-C battery is produced in many sizes and geometries

Features:
• Production above 1010 units
• True workhorses
• Cost: 1/20 of a Lead Battery or 1/50 of a Ni battery
Configuration of a commerical • Capacities from 0.05 Ah to 500 Ah
battery • Typically the cell voltage decreases with current and
time, but recovers at open circuit.

Industrial Electrochemistry, Ed. Derek Pletcher, Pub Springer, 1984 22

 The 1st generation: Zn-C BATTERIES

Positive Cap
Ni plated
steel
Metal jacket

Paper
separator
Electrolyte

Cathode
MnO2 on C
rod
Anode Zn

There is risk of H2 release; Corrosion of the Zn anode: The effect

was mitigated by using Hg (eliminated in 1990’s).
Today zinc alloys are used to minimise the effect.

EC - DG environment, Battery Cpacity determination and labelling, report

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September 2008
The 2nd generation Alkaline Manganese - Zinc Batteries

(-) electrode = Zn; (+) electrode MnO2

Aqueous Electrolyte = Potassium hydroxide = KOH 27- 40%

Early 1960’s – Introduction of the alkaline Zn/MnO2 battery.

Uses alkaline electrolyte – reduced risk of H2 release and corrosion damage
Identical voltage to Zn-C, but constant over longer time
IDEAL BATTERY

Alkaline- KOH
VOLTAGE

Closed inside a STEEL can

Zinc carbon
NH4Cl
Uses Zn powder as anode
More MnO2 powder - cathode

TIME

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 Compared to Zn-C, the alkaline batteries:

Contain Powdered Zn Less quantity of

more MnO2 electrode alkaline electrolyte

Rechargeable Alkaline Mn-Zn

batteries are also available but
limited to few cycles.

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Primary Alkaline Manganese-Zinc Batteries

Positive
terminal
Steel can
Separator

Anode

Cathode
Collector

Vent

Support
ring
Negative
terminal

EC - DG environment, Battery Cpacity determination and labelling, report September 2008 27

Some definitions
Capacity (Ah) Energy (Wh) Power

C  I .t Wh = AhV
V
2

E = C V P
I = discharge current R
Battery capacity varies
A battery typically has
with discharge rate. Supercapacitors have low
high specific energy but
Discharge at higher rates: specific energy but can
low specific power (load
capacity will be lower deliver high specific power.
capability)
than the nominal capacity.

Specific energy (Wh/kg) is Batteries are used in Specific power (W/kg)

dependent on the battery applications that require depends upon internal
capacity energy on a long run resistance

Sources: http://batteryuniversity.com/learn/article/battery_definitions (consulted on the 29th July) 28

Holm et. Al. (), A Comparison of Energy Storage Technologies as Energy Buffer in Renewable Energy Sources with respect to Power Capability
Exercise:
One alkaline battery, with 1.5 V, is used to provide energy to an electronic
device. The total energy supplied is 36E3 J.

If the flowing current is 2 A for how long the battery will run?

Note: 1 Wh = 3600 J; E = C.V; C = I.t

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Exercise:
One alkaline battery, with 1.5 V, is used to provide energy to an electronic device.
The total energy supplied is 36000 J.

If the flowing current is 2 A for how long the battery will run?

Note: 1 Wh = 3600 J; E = C.V ; C = I.t

Solution:

1 Wh = 3600 J
10 Wh = 36000 J

E = 10 Wh
E = C. V
C = 6,66 Ah

C = I.t

t=3,33 h

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