Chapter – 2: Conventional Primary batteries: Dry cell; Advanced Primary batteries - Lithium and alkaline

primary batteries
Definition: Battery is an electrochemical device that stores chemical energy for latter release as electricity (direct electric
current at a constant voltage).
Classification: Batteries can be classsified into three main types : (i) Primary and (ii) Secondary Batteries and (iii) Fuel
Cells.
Q. Mention a few differences between Primary and Secondary Batteries
Primary battery Secondary battery
electrochemical cell reaction is electrochemical cell reaction is reversible
irreversible
The reactants cannot be regenerated The reactants can be regenerated by passing direct electric
current in the opposite direction to the discharging
direction
disposable after complete discharge; reusable after complete or partial discharge; can be used
usable for only one cycle through a number of discharging and charging cycles
Cheaper in cost Expensive than primary batteries
Higher charge density Comparatively lesser charge density than primary batteries
e.g. carbon-zinc, alkaline and Lithium e.g. Lead-acid, Ni-Cd, Ni-MH, Lithium-ion rechargable
cells cells

(i) Conventional Primary batteries:

(a) Dry cell: Basic structure
Anode (-ve terminal): made up of zinc with the exposed bottom as
negative (-ve) end.
Electrolyte: manganese (IV) dioxide (MnO2), ammonium chloride
(NH4Cl) and zinc chloride (ZnCl2) added with starch to make a thick-
paste (to maintain the moisture).
Cathode (+ve terminal): made up of a carbon(graphite) rod as positive
(+ve) end, which is immersed in the electrolyte in the center of the cell.
The carbon rod acts as the current collector.
The cell can be represented as Zn (anode)/NH4Cl//MnO2+graphite/Carbon
(cathode)

Electrochemical reaction
Anode half – cell reaction : Oxidation: Zn (s) → Zn2+(aq) + 2e-
Cathode half – cell reaction : it involves many complex reactions.
Step – 1: Reduction: 2MnO2 (s) + H2O (l) + 2e- → Mn2O3 (s) + 2 OH- (aq)
The +4 oxidation state of MnO 2 is reduced to +3 state in Mn2O3.
Step – 2: Acid-base reaction: NH4+ (aq) + OH- (aq) → NH3 (g) + H2O (l)
Acid-base reaction between OH- and NH4+ (from NH4Cl present in the electrolyte) evolves NH3 (g) which disrupts the flow
of electrons.
Step – 3: 2 NH3 (g) + ZnCl2 (s) → [Zn(NH3)2]Cl2 (Complex formation between NH3 gas and Zn2+ present in the electrolyte
as well as from the anode cation).
Therefore, the net cell reaction is: Zn (s) + 2 MnO2 (s) + 2 NH4+ (aq) + 2 Cl- (aq) → Mn2O3 (s) + [Zn(NH3)2]Cl2 (s) + H2O
Cell type: Zn|(ZnCl2),NH4Cl|MnO2,C
Important characterisitics of the dry cell:
The dry cell is a primary cell in which irreversible electrochemical reactions take place. Once discharged, the cell reaction
cannot be reversed by passing direct electric current through the cell. The nominal voltage of the dry cell is 1.5 V.
Advantages of the dry cell:
Dry cell is cheaper to make than the secondary cells; It has much higher charge density than in secondary cells; Better
low-temperature service; Good leak resistance
Disadvantages of the dry cell:
Cannot stand heavy current drain. i.e. when current is drawn rapidly from it, products build up on the electrodes therby
causing drop in the voltage; Since the electrolytic medium is acidic, the zinc metal dissolves slowly, therby affecting the
efficiency and structural stability of the battery; High gassing rate; Requires excellent sealing system due to increased
oxygen sensitivity.
Applications: In flash-lights, calculators, transistor radios, etc.

(ii) Advanced Primary batteries:

(a) Alkaline battery: It is an improved form of the dry cell in which the NH4Cl is replaced by KOH as the electrolyte.
Basic structure : Anode (-ve terminal): made up of zinc powder (increased surface area for increased rate of reaction
and hence more electron flow). The outer surface of the cell is made up of zinc with the exposed bottom as the negative (-
ve) end of the battery.
Electrolyte: Potassium hydroxide (KOH, electrolyte) mixed at 35 to 50 wt.-% with the zinc powder and a small quantity
of a gelling material to get a thick paste.
A metal pin or a sheet is inserted into the anode mixture provide contact to the anode electrode.
Cathode (+ve terminal): made up of a carbon(graphite) rod as positive (+ve) end, which is immersed in the electrolyte in
the center of the cell and mainly surrounded by electrolytically produced manganese (IV) dioxide (MnO2) (higher purity
than naturally available MnO2) and carbon powder (for increased conductivity).
The natural manganese (IV) dioxide (MnO2) used as a electrolyte in dry cells is cheaper in cost and present in the form of
mineral “insutite”. Its efficiency will also be less than the electrolytically or chemically produced MnO 2 used in alkaline
cells. This is reason for higher performance of the alakine cells compared to the dry cells.
Separator: The anode and cathode materials are separted using a non-woven layer of cellulose or a synthetic polymer.
The role of the separator is to avoid the mixing of anode and cathode materials; to conduct ions and to remain stable in the
highly alkaline electrolyte solution.
For additional safety, the alkaline cells has a safety valve which opens when the internal pressure of the cell exceeds a
particular limiting value.
Electrochemical reaction
Anode half – cell reaction : Oxidation: Zn (s) + 2OH− (aq) → Zn(OH)2 (s) + 2e−
Cathode half – cell reaction : Reduction: 2MnO2 (s) + H2O (l) + 2e− → Mn2O3 (s) + 2OH− (aq)
Therefore, the net cell reaction is: Zn (s) + 2 MnO2 (s) + H2O (l) → Mn2O3 (s) + Zn(OH)2 (s)
Cell type: Zn,ZnO|KOH(paste)|MnO2,C
Important characterisitics of the alkaline cell:
The nominal voltage of the alkaline battery cell is 1.5 V.The fully discharged cell has a remaining voltage in the range of
0.8 to 1.0 V. To prevent gassing of the cell at the end of its life, excess MnO2 is taken than that required to react with all
the zinc powder present in the cell.
Advantages of the alkaline cell:
Zinc does not dissiolve as readily in the basic medium; longer shelf life than zinc-carbon battery since there is no acid
corrosion of zinc; Charge density of an alkaline battery is larger than similar sized zinc-carbon cell because the MnO2 in
the electrolyte is purer and denser; space taken up by internal components such as current collectors is less; can provide
between 3 to 5 times more operating time than zinc – carbon battery; the space taken up by other cell components
(separator, current collectors) is minimized.
Disadvantages of the alkaline cell:
The efficiency of the alkaline cell decreases with decreasing temperature unlike dry cells. Over time, alkaline batteries are
prone to leaking KOH, a caustic agent that can cause respiratory, eye and skin irritation; The leaking crystalline growths
of KOH may oxidize the copper traces in the circuit, therby leading to permanent circuitary damage.
Applications: In camera flash, calculators, watches, etc.

(b) Lithium-MnO2 batteries: are disposable (primary) type, low maintenance batteries. .
Basic structure :
Anode (-ve terminal): uses Lithium as the anode;
Electrolyte: containing Lithium perchlorate in a mixed organic solvent such as propylene carbonate and 1,2-
dimethoxyethane;
Cathode (+ve terminal): Carbon in contact with MnO2 (IV oxidation state)
Electrochemical reaction
Anode half – cell reaction : Oxidation: xLi → xLi+ + e−
Cathode half – cell reaction : Reduction: MnIVO2 + xLi+ + e− → LixMnIIIO2
Therefore, the net cell reaction is: xLi + MnIVO2 → LixMnIIIO2
Cell type: Li|Li+(nonaqueous)|KOH(paste)|MnO2,Mn(OH)3,C
Important characterisitics of the lithium cell:
Lithium is a light weight metal, has low density and high reduction potential suitable for storing electrical energy for a
long time.
Advantages of the lithium cell:
High energy density; provide very high current; long shelf-life; although they are more costly, lithium cells require low
maintenance, less self-discharge rate compared to Ni-Cd cells.
Disadvantages of the lithium cell:
Require protection circuit to maintain voltage and current within safer limits; transport of lithium batteries by air is
restricted; expensive to manufacture; about 40% higher in cost than Ni-Cd battery; lithium metal scrapped from the
batteries can be illegally used as a reducing agent in methamphetamine (used as drugs) labs.
Applications:
Used in auto-wind, auto-focus camera; in portable consumer electronic devices, artificial pacemakers and other
implantable electronic medical devices; as backup batteries in computers and communication equipment, and in remote
car locks (with a common variety being the 3 volt "coin" type manganese variety); lithium batteries can easily support the
brief, heavy current demands of devices such as digital cameras, and they maintain a higher voltage for a longer period
than alkaline cells; self-discharge is less than half compared to Ni-Cd batteries, thereby making lithium ion well suited for
fuel gauge applications.
(c) Lithium-I2 batteries: are disposable (primary) type, solid-state type batteries using a dry solid polymer as the
electrolyte (like a plastic film) that does not conduct electricity but allows the exchange of ions.
Basic structure : The cell may be represented as Li / LiI (s) /I2 (in polymer).
Anode (-ve terminal): Lithium;
Solid Electrolyte: Lithium Iodide or poly-2-vinylpyridiene (P2VP) as solid organic charge transfer complex
Cathode (+ve terminal): Iodine
Electrochemical reaction
Anode half – cell reaction : Oxidation: Li (s) → Li+ + e−
Cathode half – cell reaction : Reduction: ½ I2 (s) + e− → I-
Therefore, the net cell reaction is: Li (s) + ½ I2 (s) → Li+ + I-
Cell type: Li|LiI(s)|I2(in polymer)
Important characterisitics of the lithium cell:
Lithium is a light weight metal, has low density and high reduction potential suitable for storing electrical energy for a
long time; The voltage given by this battery is 2.8 volts; shelf-life is about 10 years.
Advantages of the lithium cell:
Although they are more costly, lithium cells require low maintenance, provide much longer life upto 15 years, thereby
minimizing battery replacement; Can deliver high pulse currents; Wide application temperature range; lithium cells can
produce voltages more than twice the voltage of an ordinary zinc-carbon battery or alkaline cell; The higher voltage
reduces the number of cells in a battery pack by a factor of at least 2; less self-discharge rate compared to Ni-Cd batteries;
Does not generate gas even under short circuit; Operation over a wide temperature range (-40 to 70oC).
Disadvantages of the lithium cell:
Lithium batteries can provide extremely high currents and can discharge very rapidly which can result in overheating of
the battery, rupture, and even explosion. Hence, lithium batteries incorporate overcurrent or thermal protection or vents in
order to prevent explosion; Because of the above risks, transport of lithium batteries by air is restricted; low energy
density; expensive to manufacture; lithium metal scrapped from the batteries can be illegally used as a reducing agent in
methamphetamine (used as drugs) labs.
Applications:
used in portable consumer electronic devices, artificial pacemakers and other implantable electronic medical devices; as
backup batteries in computers and communication equipment, and in remote car locks (with a common variety being the 3
volt "coin" type manganese variety); lithium batteries can easily support the brief, heavy current demands of devices such
as digital cameras, and they maintain a higher voltage for a longer period than alkaline cells; self-discharge is less than
half compared to Ni-Cd batteries, thereby making lithium ion well suited for fuel gauge applications.