Batteries

Lead/acid batteries
• The lead acid battery is the most used secondary battery in the world.
• used for motor vehicles for engine Starting, vehicle Lighting and
engine Ignition, however it has many other applications (such as
communications devices, emergency lighting systems and power
tools) due to its cheapness and good performance.
• It was first developed in 1860 by Raymond Gaston Planté.
• Strips of lead foil with coarse cloth in between were rolled into a
spiral and immersed in a 10% solution of sulphuric acid. The cell was
further developed by initially coating the lead with oxides, then by
forming plates of lead oxide by coating an oxide paste onto grids.
• The electrodes were also changed to a tubular design.
 Characteristics in brief
• Voltage: 2 V

Discharge characteristics: Generally quite curved, particularly at

higher discharge rate. Best performance with intermittent discharge.

Service Life: Several years

• Chemistry
• The lead acid battery uses lead as the anode and lead dioxide as the cathode, with an acid
electrolyte.
• The following half-cell reactions take place inside the cell during discharge:
• At the anode: Pb + HSO4– → PbSO4 + H+ + 2e–
• At the cathode: PbO2 + 3H+ + HSO4– + 2e– → PbSO4 + 2H2O
• Overall: Pb + PbO2 +2H2SO4 → 2PbSO4 + 2H2O
• During the charging process, the reactions at each electrode are reversed; the anode becomes
the cathode and the cathode becomes the anode.
• Gassing
• During charging, given the high voltage, water is dissociated at the two electrodes, and gaseous
hydrogen and oxygen products are readily formed leading to the loss of the electrolyte and a
potentially explosive situation. Sealed batteries are made safer by allowing the gases to
recombine within the cell.
• Sulphation
• Under certain circumstances the lead sulphate products at both the electrodes achieve an
irreversible state, making the recharging process very difficult.
 Construction
• The simplest cell would consist of one cathode
plate, one anode plate and a separator
between them.
• In practice, most cells contain up to 30 plates
with separators between.
• The separators are usually cellulose, PVC,
rubber, microporous polyethylene or non-
woven polypropylene.
• The plates are stacked and welded together.
The tabs that are fixed to the plates are cast,
then punched on between the layers and
welded together.
• The plates are suspended inside the case,
 Types of Lead-Acid Batteries
Types Description
Sealed, or First appeared in the mid-1970s. Engineers deemed the term
maintenance free “sealed lead–acid” a misnomer because lead–acid batteries
cannot be totally sealed. To control venting during stressful
charge and rapid discharge, valves have been added to allow the
release of gases if pressure builds up
Starter Designed to crank an engine with a momentary high-power
load lasting a second or so. For its size, the battery delivers high
currents, but it cannot be deep-cycled.
Deep-cycle Built to provide continuous power for wheelchairs, golf carts,
and forklifts, among others. This battery is built for maximum
capacity and a reasonably high cycle count.
Starter Batteries
The starter battery is designed to crank an engine with a
momentary high-power load lasting a second or so.
For its size, the battery is able to deliver high current but it
cannot be deep-cycled
Starter batteries have a very low internal resistance that is achieved
by adding extra plates for maximum surface area .The plates are
thin and the lead is applied in a sponge-like form that has the
appearance of fine foam, expanding the surface area further.

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
 Deep-cycle Battery
The deep-cycle battery is built to provide continuous
power for wheelchairs, golf cars, forklifts and more.
This battery is built for maximum capacity and a
reasonably high cycle count. This is achieved by making
the lead plates thick
The deep-cycle battery has thick plates for improved cycling abilities.
The deep-cycle battery generally allows about 300 cycles

A starter battery cannot be swapped with a deep-cycle battery or vice versa.

While an inventive senior may be tempted to install a starter battery instead of the
more expensive deep-cycle on his wheelchair to save money, the starter battery
would not last because the thin sponge-like plates would quickly dissolve with
repeated deep cycling.
 Cycle performance of starter and
deep-cycle batteries.
Depth of Discharge Starter Battery Deep-Cycle Battery

100% 12–15 cycles 150–200 cycles

50% 100–120 cycles 400–500 cycles

1,000 and more

30% 130–150 cycles cycles

There are combination starter/deep-cycle batteries available for trucks, buses, public
safety and military vehicles, but these units are big and heavy. As a simple guideline, the
heavier the battery is, the more lead it contains, and the longer it will last
Simple Guidelines for Charging Lead Acid
Batteries
• Charge in a well-ventilated area. Hydrogen gas generated during charging is explosive.
• Choose the appropriate charge program for flooded, gel and AGM batteries. Check
manufacturer’s specifications on recommended voltage thresholds.
• Recharge lead acid batteries after each use to prevent sulfation. Do not store on low
charge.
• The plates of flooded batteries must always be fully submerged in electrolyte. Fill the
battery with distilled or de-ionized water to cover the plates if low. Never add electrolyte.
• Fill water level to designated level after charging. Overfilling when the battery is on low
charge can cause acid spillage during charging.
• The formation of gas bubbles in a flooded lead acid indicates that the battery is reaching
full state-of-charge. (Hydrogen appears on negative plate and oxygen on positive plate).
• Lower the float charge voltage if the ambient temperature is higher than 29°C (85°F)..
• Do not allow a lead acid to freeze. An empty battery freezes sooner than one that is fully
charged. Never charge a frozen battery.
• Avoid charging at temperatures above 49°C (120°F).
 Uses of Lead–Acid Batteries
Type of Lead–Acid Type of Lead–Acid Battery Uses
Battery Uses
Sealed lead–acid (SLA) Small UPS, emergency lighting, and wheelchairs.
Because of its low price, dependable service, and low
maintenance requirement, the SLA remains the
preferred choice for health care in hospitals and
retirement homes.
Valve-regulated lead–acid Power backup for cellular repeater towers, internet
(VRLA)- Gel electrolyte hubs, banks, hospitals, airports, and others

Absorbent glass mat (AGM)- Starter battery for motorcycles, start–stop function for
glass mat micro-hybrid cars, as well as marine vehicles and RVs
that need some cycling.
 Advantages and Disadvantages of
Lead–Acid Batteries
Advantages Disadvantages

• Low-cost and simple manufacture Low specific energy; poor weight-to-energy

• Low cost per watt-hour ratio
• High specific power, capable of Slow charging: Fully saturated charge takes
high discharge currents 14–16 hours Need for storage in charged
• Good performance at low and high condition to prevent sulfation
temperatures Limited cycle life; repeated deep-cycling
• No block-wise or cell-wise BMS reduces battery life
required Watering requirement for flooded type
Transportation restrictions for flooded type
Adverse environmental impact
 Alkaline/manganese oxide batteries

• This primary battery system has a higher capacity than the

zinc/carbon cell.
• It has a very good performance at high discharge rates and
continuous discharge and at low temperatures.
• The first modern alkaline cell was developed in the 1960s and by 1970
it was produced all over the world.
• Currently over 15 billion alkaline cells are used worldwide each year.
Alkaline batteries are used in many household items such as MP3 players,
CD players, digital cameras, toys, flashlights, and radios.
 Chemistry
• The active materials used are the same as in the Leclanché cell – zinc and manganese dioxide.
However the electrolyte is potassium hydroxide, which is very conductive, resulting in low internal
impedance for the cell.
• This time the zinc anode does not form the container; it is in the form of a powder instead, giving
a large surface area.
• The following half-cell reactions take place inside the cell:
• At the anode: Zn + 2OH– → Zn(OH)2 + 2e–
Zn(OH)2 + 2OH– → [Zn(OH)4]2–
• At the cathode: 2MnO2 + H2O + 2e– → Mn2O3 + 2OH–
For full discharge: MnO2 + 2H2O + 2e– → Mn(OH)2 + 2OH–
• Overall: Zn + 2MnO2 → ZnO + Mn2O3
For full discharge: Zn + MnO2 + 2H2O → Mn(OH)2+ Zn(OH)2
• It is not possible to describe the cathodic reaction on discharge in a simple unambiguous way,
despite a lot of research. In fact the discharge curve has two fairly distinct sections corresponding
to change in the oxidation state of Mn from +4 to +3 and then to +2 during the reduction of MnO 2.
The reality is more complicated than described in the two reactions shown above.
The manganese dioxide cathode is external to the zinc
anode, giving better diffusion properties, and lower
internal resistance.

Cathode
For an alkaline cell electrochemically produced
MnO2 must be used. The ore rhodochrosite (MnCO3)
is dissolved in sulphuric acid, and electrolysis is
carried out under carefully controlled conditions
using titanium, lead alloys or carbon for the
electrode onto which the oxide is deposited. This
gives the highest possible purity, typically 92 ±
0.3%.
The cathode itself also contains around 10%
graphite – more for more powerful batteries. A
typical composition would be:
70% MnO2 (of which 10% is water);
~10%graphite;
1-2%acetyleneblack;
Balance: binding agents and electrolyte. Separators
These cells usually use “macro porous” separators.
These are made from woven or felted materials.
• Zinc Anode
• The zinc must be very pure (99.85 – 99.90%) and is produced by electroplating or
distilling. Very small amounts of lead are sometimes added to help prevent corrosion
(usually ~0.05%) The zinc is powdered by discharging a small stream of molten zinc
into a jet of air “atomising” it. The powder contains particles between 0.0075 and 0.8
mm.
• There are two methods of formation of the anodes from the powder:
• Gelled anodes: These contain around 76% Zn, 7% mercury, 6% sodium carboxymethyl
cellulose and 11% KOH solution. It is extruded into the cell, as the viscosity is high. In
very small cells, NaOH is added to reduce creepage around the seal area. However this
mixture is not ideal: it does not fully utilise the zinc at high current densities. Two-
phase anodes have therefore been developed, consisting of a clear gel phase and a
more compact zinc-powder gel phase, which enables 90% zinc usage.
• Porous anodes: The zinc powder is wetted with mercury and cold pressed, welding the
particles together. The porosity can be controlled by materials such as NH4Cl or plastic
binders if required, which can be removed later. These anodes can carry very high
currents.
Adv & Disadv
 Nickel–Cadmium (Ni–Cd) Battery
• A nickel-cadmium battery (Ni-Cd) is a rechargeable battery used for
portable computers, drills, camcorders, and other small battery-
operated devices requiring an even power discharge
Chemical Equations
 Advantages and Disadvantages of
Advantages
Nickel–Cadmium Batteries
Disadvantages

• Rugged, high cycle count with proper maintenance • Relatively low specific energy compared with newer
• Only battery that can be ultra-fast-charged with • systems
little stress • Memory effect; needs periodic full discharge and
• Good load performance; forgiving if abused can be
• Long shelf life; can be stored in a discharged state, • rejuvenated
• needing priming before use • Cadmium is a toxic metal; cannot be disposed of in
• Simple storage and transportation; not subject to • landfills
regulatory control • High self-discharge; needs recharging after storage
• Good low-temperature performance • Low cell voltage of 1.20 V requires many cells to
• Economical pricing: Ni–Cd has the lowest cost per achieve
cycle • high voltage
• Availability in a wide range of sizes and performance
• Options
 Li-ion Battery
• lightest of all metals, has the greatest electrochemical potential and
provides the largest specific energy per weight.
• mobile phones, laptops, cameras and many other consumer products.
• Li-ion cells use carbon as the anode
• LiCoO2 or LiMn2O4 as the cathode
 Construction

• In order to overcome the problems associated with the high reactivity

of lithium, the anode material is not purely the metal, it is a non-
metallic compound, e.g. carbon, which can store and exchange
lithium ions.
• A lithium ion-accepting material, for example CoO2, is then used as
the cathode material, and lithium ions are exchanged back and forth
between the two during discharging and charging. These are called
intercalation electrodes.
 Working
This type of battery is known as a “rocking chair battery” as the
ions simply “rock” back and forth between the two electrodes.
Cathode materials

• LiCoO2, LiNiO2 and LiMn2O4. Of these, LiCoO2 has the best

performance but is very high in cost, is toxic and has a
limited lithium content range over which it is stable.
• LiNiO2 is more stable, however the nickel ions can disorder.
LiMn2O4 is generally the best value for money, and is also
better for the environment

Electrolyte
Since lithium reacts violently with water, and the cell voltage is
so high that water would decompose, a non-aqueous
electrolyte must be used. A typical electrolyte is LiPF6 dissolved
in an ethylene carbonate and dimethyl carbonate mixture.
Anode material
The anode material is carbon based, usually with composition
Li0.5C6. This lithium content is lower than would be ideal,
however higher capacity carbons pose safety issues
• The cathode is metal oxide
• the anode consists of porous carbon.
• During discharge, the ions flow from the anode to the cathode
through the electrolyte and separator;
• charge reverses the direction and the ions flow from the cathode to
the anode
• When the cell charges and discharges, ions shuttle between cathode
(positive electrode) and anode (negative electrode). On discharge, the
anode undergoes oxidation, or loss of electrons, and the cathode sees
a reduction, or a gain of electrons. Charge reverses the movement.
A battery should have a flat voltage curve
in the usable discharge range. The
modern graphite anode does this better
than the early coke version. Courtesy of
Cadex
Advantages Limitations
High specific energy and high load Requires protection circuit to prevent
capabilities with Power Cells thermal runaway if stressed
Long cycle and extend shelf-life; Degrades at high temperature and when
maintenance-free stored at high voltage
High capacity, low internal resistance, No rapid charge possible at freezing
good coulombic efficiency temperatures (<0°C, <32°F)
Simple charge algorithm and reasonably Transportation regulations required
short charge times when shipping in larger quantities
Low self-discharge (less than half that of
NiCd and NiMH)
 Flow Batteries
• The sodium–sulfur battery (NaS) is a new technology that has been
given much attention in recent years.
• Its higher specific power density makes it more competitive.
However, its safety is a big concern because this battery is normally
operated at temperatures as high as 350 ◦ C with highly combustible
sodium as its active ingredient.
• The RFB represents a new electrochemical energy storage method
and has many attractive features, such as independent design of the
power and energy capacity, high efficiency, and long cycle life.
• The RFB is well suited for a variety of applications
 https://www.youtube.com/watch?v=t9zwgL7UpDA&t=415s
Types
• the VRB;
• the sodium polysulfide/bromine, zinc/bromine, and iron/chromium
flow batteries; the soluble lead-acid battery; and the zinc/nickel flow
battery
Animation video

https://www.youtube.com/watch?v=TSsqCazP1V0&t=161s
 DEFINITION
A flow battery is a rechargeable
fuel cell in which an electrolyte
containing one or more dissolved
electroactive elements flows
through an electrochemical cell
that reversibly converts chemical
energy directly to electricity.
REDOX
TYPES HYBRID

MEMBRANE LESS
 DIFFERENCE BETWEEN
NORMAL BATTERY AND
FLOW BATTERY
NORMAL BATTERY FLOW BATTERY
• Solid state battery. • Liquid state battery.
• Higher energy density. • Lower density.
• Easily scalable. • Highly scalable.
• Limited cycle. • Longer cycle life.
• Minimal maintenance. • Occasional maintenance.
 WORKIN
A flow battery produces
G chemical
energy by mixing two chemical
constituents that are dissolved in
liquids contained within the device
with a membrane separating them.
Ion exchange occurs via the
membrane, accompanied by the
passage of an electric current, while
both liquids circulate at their own
DESCRIPTION

ANOLYTE
CATHOLYTE
- β-Cyclodextrin
(catalyst)
CATHOLYTE
ANOLYTE
- For a balanced charge
environment
- Electron
- Electron

- Membrane

Yellow
ELECTROLYTE
Blue
 Fundamental equations of
a flow battery
Oxidation Half-Cell
(Anode):
- Oxidation Reaction: V²⁺(in solution)→ V³ ⁺ + e ⁻

Reduction Half-Cell (Cathode):

- Reduction Reaction: V⁴⁺ + e⁻ → V³⁺

Overall Cell Reaction: V²⁺ + V⁴⁺ → 2V³⁺

 charging
 One of the electrodes undergoes
an oxidation reaction, releasing
electrons, while the other electrode
undergoes a reduction reaction,
accepting those electrons. This is
the process of chemical energy
storage.
 The overall reaction stores energy
in the form of chemical potential
energy within the electrolyte
Discharging
solutions.
 The stored chemical energy is released as the reactions at the electrodes
reverse. Electrons flow from the electrode with excess electrons (reduction
reaction) to the electrode with a deficit of electrons (oxidation reaction).
 This flow of electrons creates an electrical current that can be used to power
electrical devices or be fed into the grid.
HISTORY OF BATTERY
 COMPONENTS
 ELECTRODE USED : Carbon and Graphite felt
 ELECTROLYTE USED : Vanadium-Saturated
electrolyte (mixture of vanadium sulfate and
sulfuric acid)
 MEMBRANE USED : Perfluorosulfonic acid
polymers
 ADVANTAGES
 Modularity allows quick upgrades
Energy can be stored in liquid form
 Can fully charge/discharge with little electrode

Can be "instantly recharged" if desired by

pumping in fresh fluid
 Less expensive materials: $300/kW vs $1000/kW for
Li-ion
 Decoupling of power and storage
 DISADVANTAGES
 Specific capacity is -10 x less than standard
batteries due to
 solubility limits 1000 Generally low voltages
(<1.5VVSSVT Li-ion
 Pumps required to circulate electrolyte
 Technology not as developed as standard
Batteries
 More weight, because size is proportional to
energy.
 Experimental example for size

Storage Capacity is 0.796 Storage Capacity is 6.33

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• e

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