Czech Technical University in Prague

Faculty of Electrical Engineering

Department of Electroenergetics

Battery Summary

Author:
Minh-Quan Dang

January 12, 2016

Prague

CONTENTS

Contents
1 Introduction of electrochemical sources
1.1 Basis concepts . . . . . . . . . . . . . .
1.2 Classification: . . . . . . . . . . . . . .
1.3 Operation of cell . . . . . . . . . . . .
1.3.1 Discharge . . . . . . . . . . . .
1.3.2 Charge . . . . . . . . . . . . . .
1.4 Factors Affecting Battery performance
1.4.1 Voltage level . . . . . . . . . . .
1.4.2 C-Rate . . . . . . . . . . . . . .
1.4.3 Battery lifetime . . . . . . . . .
1.4.4 Temperature influence . . . . .
1.4.5 Storing position . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

2 Primary cells
2.1 General characteristic . . . . . . . . . . . . . . . . . . . .
2.1.1 Classification . . . . . . . . . . . . . . . . . . . .
2.1.2 Comparision of the performance characteristic . .
2.2 Zinc-Carbon cells . . . . . . . . . . . . . . . . . . . . . .
2.2.1 Principle and Construction . . . . . . . . . . . . .
2.2.2 Characteristics . . . . . . . . . . . . . . . . . . .
2.2.3 Zinc-chloride electrolyte with plastic seals - Heavy
2.3 Alkaline cells . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1 Principle and construction . . . . . . . . . . . . .
2.3.2 Discharge profile . . . . . . . . . . . . . . . . . .
2.4 Lithium primary cells . . . . . . . . . . . . . . . . . . . .
2.4.1 Advantages of Lithium cells . . . . . . . . . . . .
2.4.2 Classification . . . . . . . . . . . . . . . . . . . .
2.4.3 Discharge profile . . . . . . . . . . . . . . . . . .
2.5 Mercury and Silver-Zinc cells . . . . . . . . . . . . . . .
2.5.1 Mercury cell . . . . . . . . . . . . . . . . . . . . .
2.5.2 Silve-Zinc cell . . . . . . . . . . . . . . . . . . . .
2.5.3 Application . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

. . .
. . .
. . .
. . .
. . .
. . .
duty
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .
. . .

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

1
1
2
3
3
3
4
4
4
5
5
5

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

6
6
6
7
7
7
8
8
9
9
10
10
10
10
11
11
11
12
12

3 Accumulators

13

4 Lead-acid batteries
4.1 Principle . . . . . . . . . . . .
4.2 Charging process . . . . . . .
4.3 Discharging process . . . . . .
4.4 Construction . . . . . . . . .
4.5 Production process . . . . . .
4.6 Concepts . . . . . . . . . . . .
4.7 Affection of temperature . . .
4.8 Applications . . . . . . . . . .
4.9 Advantages and disadvantages

15
15
15
16
16
18
18
18
19
20

DANG Minh-Quan

. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
of lead

. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
acid accumulators

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

4.9.1
4.9.2

Advantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5 Nickel based accumulator

5.1 NiZn accumulator . . . . . . . . . . . . . .
5.1.1 Discharging and Charging processes
5.1.2 Characteristics . . . . . . . . . . .
5.2 NiCd accumulator . . . . . . . . . . . . . .
5.2.1 Chemistry . . . . . . . . . . . . .
5.2.2 Construction . . . . . . . . . . . .
5.2.3 Sintered-plate nickel-cadmium . . .
5.2.4 Sealed nickel-cadmium batteries .
5.2.5 Memory effect . . . . . . . . . . . .
5.3 NiMH accumulator . . . . . . . . . . . . .
5.3.1 Chemistry . . . . . . . . . . . . . .
5.3.2 Construction . . . . . . . . . . . .
5.3.3 Performance characteristic . . . . .
5.3.4 Charging characteristic . . . . . . .
5.4 Charging methods for NiMH accumulator
5.4.1 Advantages and disadvantages . . .
5.4.2 Application . . . . . . . . . . . . .
6 Lithium batteries
6.1 Construction .
6.2 LiCoO2 cells . .
6.3 LiM n2 O4 cells .
6.4 LiF eP O4 cells .
6.5 Lix T iy O4 cells .
6.6 Li-polimer type

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

7 Battery charging
7.1 Objectives . . . . . . . . . .
7.2 Charging conditions . . . . .
7.3 Charging procedure . . . . .
7.4 Charging process for Pb Acc
7.5 Charging Methods . . . . .
7.6 Time of charging . . . . . .

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

20
20

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

21
21
21
21
22
22
22
23
26
28
28
28
28
30
30
31
32
32

.
.
.
.
.
.

33
33
33
33
34
34
34

.
.
.
.
.
.

35
35
35
35
36
36
36

1 INTRODUCTION OF ELECTROCHEMICAL SOURCES

Introduction of electrochemical sources

1.1

Basis concepts

A battery is a device that converts the chemical energy from its active materials
directly into electric energy by means of an electrochemical oxidation-reduction (redox)
reaction. Batteries are capable of having high energy conversion efficiencies.
A battery contains one or more cells which is connected in parallel, series or both
to archive desired output voltage and capacity.
The cell consist of three major components:
The anode (negative electrode) gives up electrons and is oxidized during redox
reaction.
The cathode (positive electrode) accepts electrons and is reduced during redox
reaction.
The electrolyte (ionic conductor) provides the medium for transfer ions between
anode and cathode.
The separator is used to separate the anode and cathode mechanically. It is
permeable to electrolyte.
The most desired combination of anode and cathode materials will have such
qualities:
1. Light
2. High cell voltage
3. High cell capacity

In practical, the anode is selected with those properties:

1. Efficiency as a reducing agent
2. High coulombic output (Ah/g)
3. Good conductivity
4. Stability
5. Ease to fabrication
6. Low cost

The cathode is selected as:

1. Efficient oxidizing agent
2. Stable when contact with electrolyte
3. High working voltage

DANG Minh-Quan

1 INTRODUCTION OF ELECTROCHEMICAL SOURCES

The electrolyte is selected as:

1. Good ionic conductivity but not be electronically conductive.
2. Nonreactivity with the electrode materials
3. Durable against temperature
4. Safety in handling
5. Low cost

Cell configurations typically are cylindrical, button, flat and prismatic.

Figure 1: Components of a cell [?]

1.2

Classification:

Primary cell are dischaged once and discarded.

Advantage: Good shelf life, high energy density, low-moderate self discharge rate,
no maintenance.
Application: portable electric and electronic devices.
Secondary cells can be recharged electrically. They are storage devices for electric
energy. Advantage: high power density, high discharge rate, flat discharge curves,
good low-temperature performance. But energy densities are lower than primary
cells. Application: energy-storage devices, as primary function.

DANG Minh-Quan

1 INTRODUCTION OF ELECTROCHEMICAL SOURCES

1.3
1.3.1

Operation of cell
Discharge

When the cell is connected to the external load, electrons flow from anode to cathode
and in the electrolyte positive ions and negative ions flow toward anode and cathode
respectively to close the circuit.

Figure 2: Electrochemical operation of a cell (discharge)[?]

1.3.2

Charge

During charging process the current flow in opposite direction and the electrons flow
from positive electrode to negative electrode. Anode becomes cathode and reverse.

Figure 3: Electrochemical operation of a cell (charge)[?]

DANG Minh-Quan

1 INTRODUCTION OF ELECTROCHEMICAL SOURCES

1.4
1.4.1

Factors Affecting Battery performance

Voltage level

1. Open-circuit voltage is the voltage under a no-load condition close to theoretical voltage.
2. Closed-circuit voltage is the voltage under a load condition.
3. Nominal voltage is typical operating voltage.
4. Working voltage is actual operating voltage under load and lower than opencicuit voltage.
5. Mid-point voltage is the central voltage during the discharge of the cell .
6. Cutoff voltage is voltage at the end of discharge.

Figure 4: Voltage level of cell

When the cell is discharged its voltage is lower than OCV because the losses IR
(the product of the discharging current and internal resistance) and polarization of the
active materials at both electrodes. [?, sec. 3.2.1]
The specific energy that is delivered by battery in practical lower than theoretical
case because:
1. The average voltage during the discharge is lower than the theoretical voltage.
2. The battery is not discharged to zero therefore all the Ah capacity is not utilized.
1.4.2

C-Rate

A method for indicating the discharge, as well as the charge current of battery.
I = M Cn
DANG Minh-Quan

1 INTRODUCTION OF ELECTROCHEMICAL SOURCES

where
I
C
n
M

=
=
=
=

discharge current, A
rated capacity of the battery, in ampere hours (Ah)
time, in hours
multiple of C

The capacity of a battery decreases with increasing discharge current.

1.4.3

Battery lifetime

With Primary cells, the lifetime ends when the capacity of the cells drop by selfdischarging to 80% to 50% of declared capacity.
With Accumulator, is the number of discharge-charge cycles that the battery can
experience before it fails to meet specific performance criteria (80% of nomical C)
The actual lifetime of the battery is affected by many other factor such as the rate
and depth of D-C cycles, temperature and humidity.[?]
1.4.4

Temperature influence

Operating (discharging) temperature (10 40o C) has a significant effect on

batterys life and voltage characteristics. At lower temperature it reduced the chemical
activity and increase the internal resistance of the battery. Low operating temperature
results a reduction of capacity as well as increase in the slope of the discharge curve.
In the other hand, high operating temperature increase the chemical activity and may
cause problem with self-discharge.

Figure 5: Effect of temperature on battery capacity.[?]

Storing temperature is the temperature range in which the cell does not operate
but make sure no damage nor change of the properties during its operation.
1.4.5

Storing position

For liquid state electrolyte cell the positions of the cell is needed to be consider.
Wrong position can leads to deterioration of the cells.
DANG Minh-Quan

2 PRIMARY CELLS

Primary cells

2.1

General characteristic

In practical, the internal voltage of a cell is not constant and the internal resistance
is not zero. Even under no load condition the cell discharge it self and lost their
capacity by time.
Major advantages of the primary battery are that it is convenient, simple, and easy
to use, requires little, if any, maintenance, and can be sized and shaped to fit the
application. Other general advantages are good shelf life, reasonable energy and power
density, reliability, and acceptable cost.
2.1.1

Classification

Base on type of electrolyte:

1. Acid electrolyte (Zinc-carbon)
2. Alkaline electrolyte (Zinc-MnO2)
3. Special (Zn-HgO,Zn-Ag2O)
Base on material of electrodes:

Figure 6: Major characteristics and application of primary batteries[?]

DANG Minh-Quan

2 PRIMARY CELLS

2.1.2

Comparision of the performance characteristic

Voltage and discharge profile: For zinc anode batteries usually have a discharge
voltage 1.5 to 0.9 V, lithium anode will give about 3V. The conventional zinc-carbon,
alkaline cell have sloping profiles. Other cells have less or flat voltage profiles.

Figure 7: Discharge profiles of primary battery

2.2
2.2.1

Zinc-Carbon cells
Principle and Construction

Cathode: Graphite (carbon) rod (current collector) + Manganese dioxide (MnO2)

(Bobbin)
Anode: Zinc alloy can (Zn) contains Pb, Cd [?, sec. 9.5.1]
Electrolyte: Ammonium + 20% of ZnCl2
Overall reaction
Zn(s) + 2M nO2 (s) + 2N H4 Cl(aq) M n2 O3 (s) + Zn(N H3 )2 Cl2 (aq) + H2 O(l)
We can see that carbon is not a part of the reaction but use to improve conductivity
and retain moisture.

DANG Minh-Quan

2 PRIMARY CELLS

Figure 8: Zinic-Carbon cylindrical construction [?]

2.2.2

Characteristics

Storage time maximum 2 years

2.2.3

Zinc-chloride electrolyte with plastic seals - Heavy duty

This concept use only ZnCl2 electrolyte and the anode is pure Zn without Hg
and Cd make it more environmental friendly. This concept is suitable for higher load
current and also has 2-3 times longer lifetime than basic concepts. [?]

Figure 9: A comparision of typical discharge curves between conventional Zn-C and

ZnCl2 battery [?]

DANG Minh-Quan

2 PRIMARY CELLS

2.3
2.3.1

Alkaline cells
Principle and construction

Cathode:
Manganese dioxide (MnO2) - Graphit mixture cathode
Silver oxide (Ag2O) - button batteries
Oxygen (O2) - button batteries, coin jackets.
Anode: Powder zinc alloy
Electrolyte potassium hydroxide (KOH)
Anode collector steel nail
Overal reaction
Zn(s) + 2M nO2 ZnO(s) + M n2 O3 (s) [eo = 1.43V ]
We can see that electrolyte is not a part of the reaction. The lifetime of the alkaline
battery is 3-5 times longer than Zn-C.

Figure 10: Schematic view of typical alkaline cell construction [?]

DANG Minh-Quan

2 PRIMARY CELLS

2.3.2

Discharge profile

Continual dischage

Figure 11: Continual discharge profile of Alkaline battery-LR6, Zn-C battery-R6S and
ZnCl2 battery-R6G [?]

2.4
2.4.1

Lithium primary cells

Advantages of Lithium cells

1. High voltage : about 4V compared to 1.5V of other then reduce number of cells
in 1 battery.
2. High specific energy and energy density: 870Wh/kg is 2-5 times more than zinc
anode batteries. [?]
3. Operation over a wide temperature range: -40 to 70 oC
4. Good power density
5. Flat discharge characteristic
6. Superior shelf life: up to 10 years
2.4.2

Classification

Based on type of electrolyte and cathode material:

DANG Minh-Quan

10

2 PRIMARY CELLS

Figure 12: Classification of Lithium Primary batteries[?]

2.4.3

Discharge profile

Figure 13: Typical discharge curves of lithium[?]

2.5
2.5.1

Mercury and Silver-Zinc cells

Mercury cell

Cathode: HgO
Anode: Zn
Operation voltage: 1.35V and low dependence on discharging process

DANG Minh-Quan

11

2 PRIMARY CELLS

2.5.2

Silve-Zinc cell

Cathode Ag2O
Anode Zn
Operation voltage: 1.55V and low dependence on discharging process
2.5.3

Application

On small loads (A, mA) like watches, hearing aids usually button jackets

DANG Minh-Quan

12

3 ACCUMULATORS

Accumulators

Accumulator is an energy storage device. It accepts energy, stores and releases

energy when necessary. Accumulator can be classified by electrodes materials or electrolytes material. By electrodes materials, there are three types popular namely Lead
(Pb), Nickel (Ni) and Lithium (Li). By electrolytes material, we can divide accumulator into acid and alkaline. Lead accumulator could have both acid and alkaline
electrolyte. The Ni and Li accumulator has only alkaline electrolyte.

Figure 14: Discharge profiles of conventional secondary battery systems and rechargeable lithium-ion battery at approximately C/5 discharge rate.

DANG Minh-Quan

13

3 ACCUMULATORS

Figure 15: Major Characteristics and Applications of Secondary Batteries

DANG Minh-Quan

14

4 LEAD-ACID BATTERIES

4
4.1

Lead-acid batteries
Principle

The lead accumulator is invented by Gaston Plante in 1859 and it is the first
rechargeable battery for commercial use. The principle of lead accumulator can be
explained as follow.
At the anode, Pb plate is oxidized by HSO4- from the electrolyte loss electrons.
If load connected the anode to the cathode from PbO2, the reduction action occurs
create H20 and finish the discharge process. The fully discharge will create identical
lead sulfate (PbSO4) plates and H20.
During the charging process, the PbSO4 is reconverted to lead and sulfuric acid.
Electricity flows though the water in electrolyte. The water is dissociated into H+ and
O2- by electrolyze. Some of this ion will recombine to H2 and O2 leads to leakage of
the water from the accumulator which is needed to refill.
Overal reaction:
P b + P bO2 + 2H2 SO4 2P bSO4 + 2H2 O
Both the charging and discharging processes required some attention about the
discharge voltage limit and charging voltage limit. When the nominal voltage of
accumulator is 12V, the charging voltage should not over 14.4V to avoid
gases creation. The accumulator also should not be discharged under 10.5V to avoid
crystal PbSO4 growth on the electrodes. Nominal cell voltage is 2V.

4.2

Charging process

Basic charging characteristic includes two phases. The first phase the accumulator
is charged by constant current, the Imax is limited by accumulator or the charger. The
1st phase end when the gases voltage(14.4V) is reached. The second phase typically
by constant voltage (14.4V) until current drops to 5% Imax. The accumulator had
charged to 95% nominal capacity at the same time. After finishing the last phase,
current is set back to 30% Imax and voltage will rises above (14.4V) leads to gases
creation. Charging ends when acheve V = 2.67V/cell that means accuumlator had
charged to 99%.

DANG Minh-Quan

15

4 LEAD-ACID BATTERIES

Figure 16: Charging characteristic of Lead-acid accumulator [?]

4.3

Discharging process

Depend on the load, accumulator could be discharged within hours, minutes or even
seconds. Therefore, we need to avoid short circuit to protect the accumlator.

Figure 17: Discharging characteristic of lead acid accumulator [?]

4.4

Construction

The construction of Lead-acid battery is shown on the figure.

The grid structure (plate) is made from the lead alloy because the pure lead is too
soft and not support itself. The commonly additives are antimony (Sb), calcium (Ca),
tin (Zn) and selenium (Se). Each kind of additive will provide structure additional
mechanical or electrical properties. Another structure of grid can be used like rods or
tubular plate.
The separator is made from porous fiberglass cloth or PVC perforated film. Electrolyte is sulfuric acid about 1.24g/cm3 (traction, stationary) and 1.28 g/cm3 (starter
and motor). The cover is polypropylene (PP), polyethylene (PE) or ebonite.

DANG Minh-Quan

16

4 LEAD-ACID BATTERIES

Figure 18: Typical construction of Lead acid accumulator

Figure 19: Grid construction of electrodes

Figure 20: Flat plate and tubular plate structure

DANG Minh-Quan

17

4 LEAD-ACID BATTERIES

4.5

Production process

The production process of Pb plate including two steps:

1. Grid forming and pasting: first the grid is casted by molten Pb and stretched to
get Pb band.
2. After the pasting process will paste the PbO layer on the grid surface. The plate
will be dried in and oxidizing atmosphere to achieve cathode PbO2 and in the
reducing atmosphere to archive anode Pb.

4.6

Concepts

The lead accumulator is designed with two concepts is flooded concept and sealed
concept.
The flooded concept is accumulator without cover, the water leakage could be
add easily but repeatedly.
The sealed concept or maintenance free concept allow reduce maintenance requirement of accumulator when it is assured that the amount of the electrolyte is
sufficient during whole warranty period. This concept is developed into several other
concepts as follow:
1. Valve regulated lead acid (VRLA) is the sealed concept with valve for safely
escaping of H2 and O2 during charging.
2. Absorbed glass matte (AGM) holds the electrolyte in a specially designed glass
mat.
3. GEL concept has electrode with gel state could be used at any orientation.

4.7

Affection of temperature

Figure 21: Affect of temperature on cells capacity

DANG Minh-Quan

18

4 LEAD-ACID BATTERIES

As we can see that low temperature decrease the cells capacity dramatically.

Figure 22: Affect of temperature on cells lifetime

The high temperature will shorten the accumulators lifetime.

Figure 23: Affect of temperature on self discharge rate

High temperature will increase the self discharge rate.

4.8

Applications

Lead accumulator is dependable and cheap. Their application coud be found on

autobattery with high starting current, traction battery with deep-cycle (max capacity,
high cycle count), stationary battery.

DANG Minh-Quan

19

4 LEAD-ACID BATTERIES

(a) Stater battery

(b) Deep cycle battery

Figure 24: Construction of stater battery and deep cycle battery [?]
The starter battery has many thin plates in parallel to achieve low resistance with
high surface area. The starter battery does not allow deep cycling.
The deep-cycle battery has thick plates for improved cycling abilities. The deepcycle battery generally allows about 300 cycles.

4.9
4.9.1

Advantages and disadvantages of lead acid accumulators

Advantages

1. Inexpensive and simple to manufacture; low cost per watt-hour

2. Low self-discharge; lowest among rechargeable batteries
3. High specific power, capable of high discharge currents
4. Good low and high temperature performance
5. Electrically efficiency - 70% charge-discharge energy
4.9.2

Disadvantages

1. Low specific energy; poor weight-to-energy ratio

2. Slow charge; fully saturated charge takes 14-16 hours
3. Must be stored in charged condition to prevent sulfation
4. Limited cycle life (50-500 cycles); repeated deep-cycling reduces battery life
5. Flooded version requires watering
6. Transportation restrictions on the flooded type
7. Not environmentally friendly

DANG Minh-Quan

20

5 NICKEL BASED ACCUMULATOR

Nickel based accumulator

The family of alkaline aqueous system based on nickel positive electrodes that include nickel-Zinc, Nickel-cadmium, nickel-metal hydride. The common features of these
family are:
1. High cycle life under wide variety of charge and discharge rates.
2. High nominal voltage (1.65V)

5.1
5.1.1

NiZn accumulator
Discharging and Charging processes

The NiZn accumulator cannot be discharged under 1.3V.

Thank to low internal resistance, it can provide high discharge currents.
Charging time of NiZn is short (2.5-3 hours)
Overall reaction:
2H2 O + Zn + 2N iOOH Zn(OH)2 + 2N i(OH)2
5.1.2

Characteristics

Figure 25: The Range of Characteristics of Nickel-Zinc Batteries

DANG Minh-Quan

21

5 NICKEL BASED ACCUMULATOR

Figure 26: The voltage-capacity curves for a 1.9 Ah sub C cell and associated temperature rise
We can see from the figure that large the discharge rate higher the temperature
and lower the operating voltage.

5.2
5.2.1

NiCd accumulator
Chemistry

The overall reaction:

2N iOOH + 2H2 O + Cd 2N i(OH)2 + Cd(OH)2
5.2.2

Construction

Cathode: NiOOH, CoOOH, Graphite (80/2/18)

Anode: CdOOH, Fe, Ni, Graphite (78/18/1/3)
Electrolyte is potassium hydroxide (KOH) is not a part of reaction.
Separator: Porous fiberglass cloth
Electrodes:
Plates with submerged electrodes (stationary)
Coiled electrodes in cylindrical jacket.

DANG Minh-Quan

22

5 NICKEL BASED ACCUMULATOR

5.2.3

Sintered-plate nickel-cadmium

Figure 27: Cross section of vented sintered-plate nickel-cadmium cell.

Application: UPS, railcars, mining and military, auto battery.
Charging methods:
1. Constain-potential recharging (current limited),
2. Constant-Current, Voltage-Controlled
Notice that there will be gassing during the charging process so cells must have vents
and plugs for electrolyte refilling.
Operation temperature: -40-65oC
Cells capacity: 1-500 Ah
Cost: 5-8x Pb

Figure 28: Typical discharge curves at various C rates, 25oC of NiCd cell

DANG Minh-Quan

23

5 NICKEL BASED ACCUMULATOR

Figure 29: Typical discharge curves at various temperatures 1 C rate of NiCd cell

Figure 30: Self discharge of NiCd cell

Figure 31: Life cycle of NiCd cell respected to DOD

DANG Minh-Quan

24

5 NICKEL BASED ACCUMULATOR

Figure 32: Influence of teperature onf capacity of NiCd cell

Advantages:
1. Flat discharge profile
2. Higher energy density (50% greater than pocket plate)
3. Superior high-rate and low-temperature performance
4. Excellent long-term storage
5. Can be fully discharge and remain in a discharged state
Disadvantage:
1. Higher cost
2. Memory effect (voltage depression)
3. Temperature controlled charging system required to enhance life

DANG Minh-Quan

25

5 NICKEL BASED ACCUMULATOR

5.2.4

Sealed nickel-cadmium batteries

Figure 33: Construction of sealed nickel cadmium cylindrical

This construction minimum thickness of electrodes and separators. It has excellent
mechanical resistance of electrode system provide it ability to withstands high charging
and discharging currents. However it make difficulty for disposing gases during charging
and problem with contacting.
Performance characteristic:
The voltage increases slowly but steadily at the C/10 charge rate to a steady-state
condition, decays slightly during the 1 h rest, and is relatively flat during the 1 h
discharge to 1.0 V. The voltage recovers rapidly over the next hour, while at rest, to
near 1.2 V.

Figure 34
DANG Minh-Quan

26

5 NICKEL BASED ACCUMULATOR

Charging characteristic:
Sealed nickel-cadmium batteries are usually charged by means of the constantcurrent method. The 0.1C rate can be used and the battery is charged for 12 to 16 h
(140%). At this rate, the battery can withstand overcharging without harm, although
most sealed nickel-cadmium batteries can be safely charged at the C/100 to C/3 rate.
At higher charge rates, care must be taken not to overcharge the battery excessively
or develop high battery temperatures and pressures.

Figure 35: Typical pressure, temperature, and voltage relationships on NiCd sealed.
NOTICE: The voltage profile of sealed type is different from the vented type. The
end-voltage for sealed type is lower. The negative plate does not reach as high a state
of charge as does in the vented construction because of oxygen recombination reaction.

Figure 36: Charge voltage for sealed and vented comparison

Advantages and disadvantages

DANG Minh-Quan

27

5 NICKEL BASED ACCUMULATOR

Figure 37: Major Advantages and Disadvantages of Sealed NiCd battery

5.2.5

Memory effect

The tendency of a battery to adjust its electrical properties to a certain duty cycle
to which it has been subjected for an extended period of time. The effect results from
charging following repetitive shallow discharges where some portion of the active materials in the cell is not used or discharged, such as in a typical engine-start use. This
effect is noticed when the previously undischarged material is eventually discharged.
The terminal voltage during the latter part of that full discharge may be lower by approximately 120 mV (hence, voltage depression). The total capacity is not reduced,
however, if the discharge is continued to the lower voltages, as, for example, to the
knee of the curve.
This effect is completely reversible by a maintenance cycle consisting of a thorough
discharge followed by a full and complete charge-overcharge.

Figure 38: Memory effect

5.3
5.3.1

NiMH accumulator
Chemistry

The overall reaction:

M H + N iOOH M + N i(OH)2 E0 = 1.35V
5.3.2

Construction

NiMH cells are produced almost exclusively in the coil design (cylindrical and prismatic).
DANG Minh-Quan

28

5 NICKEL BASED ACCUMULATOR

Figure 39: Cylindrical Configuration of NiMH battery

Figure 40: NiMH button configuration

DANG Minh-Quan

29

5 NICKEL BASED ACCUMULATOR

Figure 41: NiMH Small Prismatic Configuration

5.3.3

Performance characteristic

Number of cycle at DOD 80% min. 500

Operating Temperature: 0-60oC.
Cells cannot be discharged under 0.9V or leaving in discharged state.
The discharge characteristics of sealed NiMH batteries are very similar to those
of sealed nickel cadmium batteries. The open-circuit voltage of the batteries of both
systems ranges from 1.25 to 1.35 V, the nominal voltage is 1.2 V, and the typical end
voltage is 1.0 V.
5.3.4

Charging characteristic

Charging characteristic of NiMH battery is similar to NiCd but it is impossible to

use simple version of charger of NiCd for NiMH. Reason is because NiMH battery is
more sensitive to overcharge (thermal effect).

DANG Minh-Quan

30

5 NICKEL BASED ACCUMULATOR

5.4

Charging methods for NiMH accumulator

Figure 42: Comparison of charge termination methods

Techniques for Charge Control:
1. Timed Charge. Battery is charged for a predetermined amount of time. This
method use small current and used as a final step of charging to ensure a complete
recharge.
2. Voltage Drop (V ). The voltage during charge is monitored and charge terminated when the voltage begins to drop. However the peak voltage of NiMH
cell is not very prominent and absent in small current (0.3C). The voltage sensor must be sensitive enough to recognize voltage drop and noise and voltage
fluctuation.
3. Voltage Plateau (0 V ) terminate charge when the voltage peaks and the
slope is zero rather than waiting for the voltage to drop. The risk of overcharge
is reduced as compared to the (V ) method.
4. Temperature Cutoff (TCO). monitor the temperature rise of the battery and
terminate charge when the battery has reached a temperature that indicates the
beginning of overcharge. It is difficult to determine this point precisely. Therefore
this method is used as a safety method.
5. Delta Temperature Cutoff (T ). This technique measures the battery temperature rise above the ambient temperature during charging and terminates
charge when this rise exceeds a predetermined value.
6. Rate of Temperature Increase (T /t). the change in temperature with
time is monitored and charge is terminated when a predetermined incremental
temperature rise is reached.

DANG Minh-Quan

31

5 NICKEL BASED ACCUMULATOR

5.4.1

Advantages and disadvantages

Advantages:
1. Higer capcity compare with NiCd
2. No Cd content
3. No memory effect
4. Low internal resistance
Disadvantage:
1. More climatic and mechanical sensitive
2. Higher self-discharge rate than NiCd
3. Higher internal impedance (no high charging/discharging current)
5.4.2

Application

Small appication, portable equipment, light traction.

DANG Minh-Quan

32

6 LITHIUM BATTERIES

Lithium batteries

6.1

Construction

Anode materials: LiCoO2 , LiM n2 O4 , LiF eP O4 , Lix T iy O4

Cathode materials: Composite of Lithium and graphite or amorphous carbon,
metallic Li.
Electrolyte: LiBF4

Figure 43: Schematic diagram of a wound cylindrical Li battery

6.2

LiCoO2 cells

Nominal - 3.6 - 3.7V

End-charging - 4.2V/cell
End-discharging - 3V/cell
Standard charging current 0.3-0.5CA
Max discharging current 2 to 5CA
Service-life: 80 DOD- 1000cy, 70 DOD - 2000cy.
Self-discharging: 2% / month
Operating temperature -20 - 75oC

6.3

LiM n2 O4 cells

Nominal - 3.6 - 3.7V

End-charging - 4.35V/cell
End-discharging - 2.2V/cell
Standard charging current 0.3-1CA
DANG Minh-Quan

33

6 LITHIUM BATTERIES

Max discharging current 5CA

Service-life: 80 DOD- 300cy, 70 DOD - 500cy.
Self-discharging: 3% / month
Operating temperature -25 - 75oC

6.4

LiF eP O4 cells

Nominal - 3.2 - 3.3V

End-charging - 4.25V/cell
End-discharging - 2.5V/cell
Standard charging current 0.3-3CA
Max discharging current 3CA
Service-life: 80 DOD- 2000cy, 70 DOD - 3000cy.
Self-discharging: 3% / month
Operating temperature -25 - 75oC

6.5

Lix T iy O4 cells

Anode Li4 T i5 O12

Cathode LiM n2 O4 , LiCoO2
Nano-structure of LiTi increase the active surface so the energy density of LiTi
batteries is large.
Nominal - 1.5-4.2V
Service-life 7000-8000 in DOD
Charging time 2-8h
Operation temperature: -40-80 oC

6.6

Li-polimer type

Anode material: LiCoO2

Cathode material: Composite material from Li and C or metal Li
Electrolyte: P EO + LiP F6 + SiO2
Construction: prismatic cells and packs
Charging current 2CA
Discharge current 40CA
Operating temperature -10 to 60oC
Capacity: 0.2 to 5 Ah/cell

DANG Minh-Quan

34

7 BATTERY CHARGING

Battery charging

7.1

Objectives

Recharging is the process of replacing energy that has been discharged from the
battery.The main criteria for effective charging are to:
Recharge the battery to its full capacity
Limit the extent of overcharge
Avoid high temperatures and excessive temperature fluctuations
Charging procedures is chosen base ton type of battery.

7.2

Charging conditions

1. Operational charge : charge when cells voltage is lower than the final discharge
voltage.
2. Initial charge: performed by the manufacturer. 2-3 charge/discharge cycles to
get full capacity. Necessary in case of dry cell.
3. Regenerative charge: when a large number of CD cycles was performed. Using
large current to refresh the cell.
4. Rescue of deeply discharged cells: when the cell is discharged lower than min.
discharge voltage.

7.3

Charging procedure

Generally the charging procedure includes 2 phases:

1. Constant current: the constant current is given by Imax of battery or charger.
This phase ends when gassing voltage is achieve (Pb) or max. charging voltage.
2. Constant voltage: the voltage hold at previous value and current decreases until
5% Imax then the battery is charge to 95% CA

Figure 44: General charging process

DANG Minh-Quan

35

7 BATTERY CHARGING

7.4

Charging process for Pb Acc

After 2 general steps the third step is set current to 30% Imax the charging process
finish when U = 2.67 V/cell (99%)

Figure 45: Charging proces of Pb acc

7.5

Charging Methods

1. One step charging - constant current + time predetermined for small capacity
NiMH, NiCd
2. Natural charging - without regulator element - rising voltage will terminates
current.

7.6

Time of charging

1. Standard charging recommended by the manufacturer in tech sheet. for 15 Ah

and more 6-20h
2. Quick charge 2-5h heat problem, mechanical stress and may deform electrode.
3. Rapid charge 0.5-2h Fast but shorten service life and not fully charged

DANG Minh-Quan

36