04/05/2023

Energy Storage Systems

(EE 557)
5/4/2023 7:19 PM

• Muhammad Hammad Uddin

• B.Sc. (UoK)
• B.E. (NED UET)
• M.E. (NEDUET)
• Ph.D. (WPI, Massachusetts, USA) In process

Electrochemical Energy Storage Systems

• Direct storage of electrical energy using capacitors and coils is
extremely efficient
• but it is costly and the storage capacity is very limited.
• Electrochemical-energy storage offers an alternative without these
disadvantages.
• Yet it is less efficient than simple electrical-energy storage
• which is the most efficient form of electricity storage.

1
 04/05/2023

• Batteries and accumulators are forms of electrochemical-energy storage.

• Electrochemical systems use electrodes connected by an ion conducting
electrolyte phase. In general, electrical energy can be extracted from
electrochemical systems.
• In the case of accumulators, electrical energy can be both extracted and
stored.
• Chemical reactions are used to transfer the electric charge.
• Two categories of electrochemical-energy storage are
• low-temperature batteries such as lead, nickel, and lithium batteries,
• high temperature batteries such as sodium-sulfur batteries.
• Two further categories are batteries with external storage such as redox flow
batteries,
• those with internal storage (the majority of batteries).

Basic Physical Principles

• Energy storage in batteries uses charge carriers collected and released by reduction
and oxidation processes.
• Their flow creates an electric current i(t):

• The quantity of released electrons is calculated by using stoichiometry and

reaction equations.
• In the reactions on the anode and cathode sides, ions are converted in each
reaction process.
• As a result, electrons are collected or released.
• To balance the charge, some protons are also collected or released.
• This means that the number of transferred electrons is proportional to the mass of
material on the electrode.
• Faraday’s first law of electrolysis establishes an equivalence between the quantity
of deposited material and the quantity of electric charge.

2
 04/05/2023

• The potential difference is used to calculate the work required to

transport the charge quantity between the cathode and anode per mole
of reactions:
• ∆𝑈 ∆𝜑 𝜑 𝜑
• The electrode potentials are listed in reference books, and depend on
the reduction process of the electrode.
• The potential of a reference hydrogen electrode (RHE) is used as a
convenient reference.

Electrode Potential
• All electrochemical processes involve a transfer of charge between
areas with equivalent physical and chemical characteristics (phases).
• The inner electric potential φ is the quantity of energetic change that
accompanies a change in the phase’s electric charge.
• The inner electric potential is defined by the electric work (Wel)
required to transport a positive charge to a phase from an infinite
distance

• Here z represents the valence and F the Faraday constant.

3
 04/05/2023

• The difference of inner electric potential between two phases in

contact (phase boundary) is called the Galvani potential.
• If the two phases in contact are metallic, then the difference is also
called the Volta potential.
• Because the potentials of various metals vary by temperature,
thermocouples are used to measure the temperature.

Electrode Equilibrium
• When no electric current flows through an electrode, there is equilibrium
between the electrochemical reaction partners.
• A difference in potential in the phases results in a potential difference across
the phase boundary
• The concentrations of materials active in the electrochemical equilibrium
state are called the equilibrium concentrations.
• The potential is called the equilibrium electrode potential.
• If an electrical current is applied or facilitated by creating a power-circuit,
then the electrode is polarized and no longer in electrochemical equilibrium.
• Its potential deviates from the equilibrium value, and the concentrations
change.

4
 04/05/2023

Characteristic material properties

Types of electrochemical-energy storage

10

5
 04/05/2023

Electrolyte
• An important component of galvanic cells is the electrolyte solutions in
which the electrodes are submerged, or with which they are in contact.
• Unlike an electrical conductor, electrolytes are composed of an electrolyte
matrix (usually a solvent with a sufficiently high dielectric constant) and
electrolyte salts, i.e., charged ions disassociated in the solvent.
• This allows the charge carriers to move quite freely, resulting in high
conductivity.
• Electrolyte solutions are always electrically neutral, i.e., they must always
contain an equal number of positive (cations) and negative (anions) ions.
• There are also electrolytes in the form of polymers or gels that function on
the same principle.

11

Overview of common electrolytes

12

6
 04/05/2023

Cell Designs
• Batteries and cells differ in design.
• Since batteries can either be sealed or vented, one criterion is how the
energy storage is separated from the environment.
• The terms for these two designs vary by battery type.
• Depending on their design, cells are called prismatic cells (preferable to the
term rectangular), round cells (cylindrical), or pouch cells (cell units
wrapped in foil).
• The design partly determines the heat exchange capacity.
• Cells can be combined in modules and batteries or used as single cells (for
example, in frames, trays, etc.).
• In recent years, a number of requirements have been introduced that can
only be met by very compact, high-energy density batteries.

13

Energy Storage Parameters

• The most important parameters for energy storage are the voltage curve
and the energy content.
• The voltage curve is determined by the difference between the electrode
potentials, and therefore by the kind of electrodes used.
• Charging and discharging process voltage limits must be determined
separately for each individual system.
• The energy storage’s energy content is determined by the quantity of
material used (Faraday’s law) and the voltage curve during discharging.
• With batteries, the measure used is called A h capacity.
• here, capacity means the charge quantity that can be stored in a battery.

14

7
 04/05/2023

Battery systems and their application areas

15

• An important criterion in practice is also the power that can be

extracted from the battery
• This depends on the cell design, and is typically limited by the
manufacturer as required.
• Because of electrochemical processes, this quantity is dynamically
determined by the battery’s state (for example, SOC).

16

8
 04/05/2023

• A cell has an internal resistance determined by the battery’s resistance

and external conditions.
• This is calculated using pulse measurements (voltage changes during
discharging or charging with adequate pulse height)
• or impedance measurements (overlapping low level signals from
alternating current electricity or voltage, frequency-dependent or at a
fixed measuring frequency).
• To compare batteries, the parameters are related to weight (specific
energy, specific power) or volume (energy or power density).
• Comparison is often difficult, because it depends on whether the
comparison is on the cell, battery, or system level, and which
components are taken into account.

17

Overview of Common Battery Systems

18

9
 04/05/2023

Cont.

19

Lead-Acid Batteries
• The lead sulfuric acid system was invented 150 years ago, and is still
one of the best-known electrochemical systems.
• In its first form, it consisted of sheets of lead rolled together
• Lead batteries with low water consumption (low-maintenance
batteries) have been manufactured in America since 1935 with
electrode grids made out of lead-calcium alloys instead of lead-
antimony alloys.
• At the end of the 1950s, ‘dry-cell batteries’ using gelled electrolyte
were developed for the commercial market by the company
Sonnenschein
• Today, the lead battery is the most commonly used form of storage for
applications outside the consumer sector

20

10
 04/05/2023

Design
• A lead battery cell is composed of the following electrochemical chains
connected in series:

• Each of these electrochemical chains consists of an electrode of the

second kind, forming a half-cell
• The electrodes are in turn composed of a collector (for example a grid)
and the active mass.
• The electrode collector is made of a lead alloy.
• The active mass of the positive electrode is made of lead-dioxide.
• The active mass of the negative electrode is made of porous sponge lead

21

• Both electrodes are completely submerged in the electrolyte (diluted

sulfuric acid).
• To increase mechanical stability and avoid short-circuits, a separator is
placed between the electrodes.
• Higher capacities can be achieved by connecting the chains in parallel
and expanding the electrodes.

22

11
 04/05/2023

Battery design (exploded view)

23

Basic Reactions, Equilibrium and Cell Voltage

• By separating the two half-cells, the central chemical reactions can be
isolated:

• The cell reaction of the complete cell is a synproportionation from

elementary non-valent lead and tetravalent lead to the level of bivalent
• lead.
• This is the result of adding the individual reactions in the half-cells.

24

12
 04/05/2023

Cell discharging reaction

25

Individual chemical reaction steps (for a negative electrode, in

this instance)

26

13
 04/05/2023

Acid density, Cell Voltage and molality, OCV

27

Mole Balance and Storage Capacity

• In the complete reaction in Eq. 7.34, a mole conversion occurs with 642 g of
reactants using two moles of electrons. This is equivalent to a charge
quantity of 53.6 A h.
• The ideal energy content requires a moderate discharging voltage of 1.92

28

14
 04/05/2023

• But the ideal energy content can never actually be achieved:

• Because the actual system must include active components (grid, head
lead, pole, battery housing, separators, water to dilute the sulfuric acid).
• Because in an actual system the active components cannot be fully
charged (mass efficiency, acid consumption).
• The actual energy content of a lead battery is therefore between 25 and
40Wh/kg.
• A lead battery’s extractable quantity of charge under real conditions is
called its capacity
• The nominal capacity can be measured by discharging the battery under
standard conditions

29

Charge content

30

15
 04/05/2023

Over voltages in a lead accumulator

• Lists the most important factors contributing to polarization in a cell.

31

Discharging characteristics with discharging

32

16
 04/05/2023

Circuit Diagram

33

Aging mechanisms in lead batteries

34

17
 04/05/2023

Aging mechanisms in lead batteries

35

Assignment
Discuss an Energy Storage Technology in details with Explanation and
working principles.
Every one has to select a single topic, First you have to select any
technology.
The report has to be submitted via Turnitin so no plagiarism above 20 %
is allowed.
To propose an efficient new energy storage technology to be employed
in Pakistan with its economic feasibility.
The assignment should be in IEEE Format.
The submission deadline is 10th July 2023

Please ask question if you have

36

18
 04/05/2023

Nickel Batteries
• Jungner and Edison invented an alkaline battery using a nickel
oxyhydroxide/nickel hydroxide electrode.
• These advances paved theway for nickel cadmium and nickel-iron batteries.
• Unlike lead accumulators, these batteries have a low-rated voltage of only
1.3V.
• Although a low-rated voltage has drawbacks, an advantage is that
practically no aging and corrosion processes occur in alkaline electrolytes.
• As a result, the cells have a very long service and cycle life.
• These cells are also extremely reliable, even when used improperly (abuse
tolerance).
• The addition of steel housing made these batteries even more robust.
• Due to their high, nearly constant electrolyte concentration, these cells are
also suited for use at very low-temperatures.

37

Overview of nickel batteries

38

19
 04/05/2023

Summary
• Nickel batteries were developed to meet the need for electrochemical 
storage with a higher‐energy density and greater reliability than 
conventional lead batteries.
• Nickel batteries have a low‐rated voltage of only around 1.3V.
• Practically no aging and corrosion processes occur in alkaline 
electrolytes. 
• As a result, these cells have a long service life.
• Nickel batteries are suited for use at low temperatures.

39

Nickel-Cadmium Batteries
• Nickel-cadmium accumulators are alkaline batteries.
• Energy is stored by converting nickel hydroxide into nickel
oxyhydroxide at the positive electrode,
• where the nickel undergoes a formal change of metal valence state
from +2 to +3.
• During charging, at the negative electrode the cadmium-hydroxide
(cadmium with a valence of +2) is converted to metallic cadmium
(valence 0).
• The reactants and reaction products are in a solid aggregate state that
is typically insoluble in the alkaline electrolyte, which is a potassium
hydroxide solution.

40

20
 04/05/2023

• The rated cell voltage is around 1.3V.

• The composition of the electrodes and the electrolyte, as well as the
design of the electrodes and cells, vary by application.
• The theoretical energy content of a Ni/Cd system is about 210Wh/kg.

41

Cells
• The cell’s passive components (metal leads, etc.) are typically made of
nickel or nickel-plated steel.
• For the cell housing, in addition to plastics such as polyolefins (PP,
PE), polyamide, and polyethersulfone, steel is also used.
• The cell design can either be vented (degassing vent) or sealed
(overpressure valve/safety valve/rupture disk, partly hermetic cells).

42

21
 04/05/2023

Fiber nickel-cadmium (FNC) cell design

43

Charging efficiency curve

44

22
 04/05/2023

Electrolyte
• These cells use an alkaline electrolyte. This electrolyte is a potassium
hydroxide solution (KOH).
• Concentrations of 20% with a lye density of 1.19 g/cm3 are common.
Potash lye is a highly corrosive liquid.
• Contact with the skin results in severe chemical burns and should be
• strictly avoided.
• Protective gear (protective eyewear and gloves) is required when
working with open cells.

45

Technologies for Alkaline Cells

• Nickel-cadmium batteries are manufactured in a variety of designs.
The most important technologies used here include
• pocket-plate electrodes,
• sinter electrodes,
• fiber structure electrodes,
• and foam electrodes.
• These electrodes differ widely in terms of their composition and
characteristics.
• Tubular pocket technology first developed by Edison is no longer used
because it is too costly.

46

23
 04/05/2023

Required capacity compared with current load capacity and technology used

47

Nickel-cadmium cell charging characteristics

48

24
 04/05/2023

a FNC-A-industrial cell, b gastight FNC-RECOM cell

FNC cell for a range of applications

49

Summary
• Nickel-cadmium batteries have a very long service and cycle life,
• a high-current capacity, and can be operated over a wide temperature-
range.
• Nickel-cadmium batteries are relatively tolerant to operational
conditions, such as deep-discharging and overcharging.
• Unlike other battery technologies, nickel cadmium batteries can be
stored in practically any SOC without causing irreversible changes or
damage.

50

25
 04/05/2023

Nickel Metal Hydride Batteries

• Nickel metal hydride batteries are, in many ways, similar to gas-tight
nickel-cadmium batteries.
• These similarities include their voltage, long service life, and
reliability.
• The positive electrode, separation method, and electrolyte are also
basically the same.
• The most important difference is the negative electrode.
• This is where the hydrogen stored in the alloy is converted.
• In simple terms, the cell reaction is a hydrogen shuttle mechanism that
results in a very compact cell.

51

Chemical Reactions

52

26
 04/05/2023

Summary
• Nickel metal hydride batteries were designed for high-performance
applications.
• These batteries are widely used in consumer electronics and to store energy
in hybrid cars.
• In simple terms, the cell reaction is a hydrogen shuttle mechanism.
• This allows the cells to be very compact.
• The advantages of nickel metal hydride batteries are the significantly higher
energy and power densities, the avoidance of toxic cadmium, and the low
final charging voltage for a full charge.
• Nickel metal hydride battery cells contain practically no soluble electrode
components.
• As a result, the risk of dendritic short-circuits is minimal.
• This also means the cells have a very long cycle life.

53

25 kWh NiMH hybrid drive battery system for buses

54

27
 04/05/2023

NiMH industrial cell characteristics

55

Lithium Ion Battery

• Lithium ion batteries use a range of different cell chemistries. In
lithium ion batteries,
• during discharge the negative electrode functions as a source of
lithium ions (Li ions), and the positive electrode as a sink.
• The electrolyte separates the transport of Li ions from the transport of
electrons.
• If metallic lithium is used for the negative electrode, then the cell
voltage results from the difference between the electrochemical
potential of the positive electrode material and the lithium (negative
electrode).
• The Li ions resulting from the reaction are transported through the
electrolyte to the positive electrode. The electrons flow through the
exterior power-circuit to supply electrical energy.

56

28
 04/05/2023

• Lithium batteries, therefore, fall into two categories;

• systems with metallic lithium and systems without.
• Lithium ion cells are systems where the Li ions can be embedded in
the positive and negative electrode materials (as solids).
• This means that metallic lithium is not used for the negative electrode
in lithium ion cells.
• Lithium batteries first appeared in the early 1970s.
• Since then, a range of different electrode materials have been
developed and tested.
• The diversity of materials used for the electrodes and electrolyte in the
lithium system makes it quite unlike the lead-acid system,

57

Operating Principle, Chemical Reactions, and Active Materials

• Energy storage in rechargeable lithium ion cells is based on the
reversible insertion and removal of Li ions in active materials by
electrochemical redox reactions.
• The insertion of Li ions in the host grid is called intercalation.The
active materials are also called intercalation compounds, and the
electrodes are called intercalation electrodes.
• The term insertation is also sometimes used in this context.
Intercalation can occur at the positive or negative electrode.

58

29
 04/05/2023

Basic design and operation of a lithium ion cell. Lithium ions are reversibly
intercalated in the active material of the positive and negative electrodes. The
external circuit carries the flow of electrons. The positive and negative electrodes
are separated by the electrolyte (ion conductor)

59

• The positive and negative electrodes are connected by an ion-conducting

electrolyte.
• The separator serves as an electrical insulator, preventing direct contact
between the two electrodes (electrical short-circuit).
• The electrodes are electrically connected to the consumer by an external
circuit.
• During charging and discharging, the electrochemical reactions occur at the
electrode active materials.
• The following equations describe the chemical reactions in simplified form.
where x is between zero and one.
When metallic lithium is used, the Li ions are 
separated at the anode.

60

30
 04/05/2023

• During discharging, the processes at the electrodes occur in reverse.

• This allows the exterior power-circuit to supply electrical energy.
• The Li ions are deintercalated at the negative electrode.
• After being transported to the positive electrode, they are intercalated
in the active material there.
• As a result, the electrons from the negative electrode are fed into the
exterior power-circuit.
• The positive electrode active material is reduced.
• The negative electrode active material is oxidized.

61

Cell Voltage
• To achieve the highest cell voltage possible, the positive electrode active
material’s redox pair must have the highest possible standard potential in
comparison to the negative electrode.
• High-capacity results from maximizing the number of Li ions that can be
introduced in the material.
• The following criteria determine an active material’s effectiveness in a
lithium ion cell:
• High-specific energy density (inWh/kg)
• Reversible and fast-acting intercalation reaction
• Good electric and ionic conductivity
• Thermal stability
• Structural stability with Li ion intercalation
• Electrochemical stability
• Another factor is mechanical stress caused by volume change in the active material
during Li ion intercalation and deintercalation.

62

31
 04/05/2023

Redox potentials and maximum usable specific capacity for several

applicable active materials

63

Charge discharge curves for various activematerial systems with 

LiMn2O (LMO), LiFePO4 (LFP), Li(Ni,Co,Al)O2 (NCA), Li(Ni,Mn,Co)O2 
(NMC), carbon (C), and Li4Ti5O12 (LTO)

64

32
 04/05/2023

Graph of electrode potential at 
the positive (Vpos.) and negative 
(Vneg.) electrode during discharge 
using LiFePO4/graphite as an 
example system.
The difference (the dotted line) 
determines the cell voltage 
discharge curve. 
The potential range within which 
the electrolytes used in lithium ion 
cells are electrochemically stable 
are also indicated

65

Physical characteristics of frequently used non-aqueous solvents (EC – ethylene-

carbonate, PC – propylene carbonate, DMC – dimethyl-carbonate, DEC – diethyl-
carbonate, EMC – ethylmethyl-carbonate,
LiPF6 – lithium hexafluorophosphate)

66

33
 04/05/2023

Summary
• Energy storage in rechargeable lithium ion batteries is based on the reversible
insertion and removal of Li ions in active materials
• by electrochemical redox reactions.
• This is called intercalation.
• A variety of compounds can be used as active materials in the positive and
negative electrodes.
• As a result, lithium ion cells vary in terms of their cell voltage and specific
capacity.
• In modern large-format cells, layered oxides (such as Li(Ni,Mn,Co)O2), spinel
structures (such as LiMn2O4), or transition metal phosphates/olivine structures
(such as LiFePO4) are typically used in the positive electrode.
• Graphite's and amorphous carbons are frequently used in the negative electrode.
• Typical figures for the practically usable specific capacity of the (positive) active
materials range from110 to 190A h/kg; typical cell voltages range from 2.3–3.9V.

67

Reference
• Sterner, Michael, and Ingo Stadler, eds. Handbook of energy
storage: Demand, technologies, integration. Chapter 7
Electrochemical Energy Storage Systems Springer, 2019.

68

34