Battery Technology

1
Applications using Batteries

2
Battery
Convert stored chemical energy into electrical
energy
Reaction between chemicals take place
Consisting of electrochemical cells
Contains
Electrodes
Electrolyte

3
Electrodes and Electrolytes
Cathode
Positive terminal
Chemical reduction occurs (gain electrons)
Anode
Negative terminal
Chemical oxidation occurs (lose electrons)
Electrolytes allow:
Separation of ionic transport and electrical transport
Ions to move between electrodes and terminals
Current to flow out of the battery to perform work

4
Battery Overview
Battery has metal or plastic case
Inside case are cathode, anode, electrolytes
Separator creates barrier between cathode
and anode
Current collector brass pin in middle of cell
conducts electricity to outside circuit

5
Primary Cell
One use (non-rechargeable/disposable)
Chemical reaction used, can not be reversed
Used when long periods of storage are
required
Lower discharge rate than secondary
batteries
Use:
smoke detectors, flashlights, remote controls

6
Alkaline Battery
Alkaline batteries name came from the electrolyte in an alkane
Anode: zinc powder form
Cathode: manganese dioxide
Electrolyte: potassium hydroxide

The half-reactions are:

Zn(s) + 2OH(aq) ZnO(s) + H2O(l) + 2e [e = -1.28 V]
2MnO2(s) + H2O(l) + 2e Mn2O3(s) + 2OH(aq) [e = 0.15 V]
Overall reaction:
Zn(s) + 2MnO2(s) ZnO(s) + Mn2O3(s) [e = 1.43 V]
7
Zinc-Carbon Battery
Anode: zinc metal body (Zn)
Cathode: manganese dioxide (MnO2)
Electrolyte: paste of zinc chloride and ammonium chloride dissolved in
water

The half-reactions are:

Zn(s) Zn2+(aq) + 2e- [e = -0.763 V]
2NH4+(aq) + 2MnO2(s) + 2e- Mn2O3(s) + H2O(l) + 2NH3(aq) + 2Cl- [e = 0.50 V]
Overall reaction:
Zn(s) + 2MnO2(s) + 2NH4Cl(aq) Mn2O3(s) + Zn(NH3)2Cl2 (aq) + H2O(l) [e = 1.3 V]

8
 Primary Cell

Alkaline Battery Zinc-Carbon Battery

Zinc powered, basic electrolyte Zinc body, acidic electrolyte
Higher energy density Case is part of the anode
Functioning with a more stable chemistry Zinc casing slowly eaten away by the acidic
Shelf-life: 8 years because of zinc powder electrolyte
Long lifetime both on the shelf and better Cheaper then Alkaline
performance Shelf-life: 1-3 years because of metal body
Can power all devices high and low drains Intended for low-drain devices
Use: Use:
Digital camera, game console, remotes Kid toys, radios, alarm clocks
9
Secondary Cells
Rechargeable batteries
Reaction can be readily reversed
Similar to primary cells except redox
reaction can be reversed
Recharging:
Electrodes undergo the opposite process
than discharging
Cathode is oxidized and produces electrons
Electrons absorbed by anode

10
Nickel-Cadmium Battery
Anode: Cadmium hydroxide, Cd(OH)2
Cathode: Nickel hydroxide, Ni(OH)2
Electrolyte: Potassium hydroxide, KOH

The half-reactions are:

Cd+2OH- Cd(OH)2+2e-
2NiO(OH)+Cd+2e- 2Ni(OH)2+2OH-
Overall reaction:
2NiO(OH) + Cd+2H2O2Ni(OH)2+Cd(OH)2

11
Nickel-Cadmium Battery
Maintain a steady voltage of 1.2v per cell until completely depleted
Have ability to deliver full power output until end of cycle
Have consistent powerful delivery throughout the entire application
Very low internal resistance
Lower voltage per cell

12
Nickel-Cadmium Battery
Advantages:
This chemistry is reliable
Operate in a range of temperatures
Tolerates abuse well and performs well after long periods of storage

Disadvantages:
It is three to five times more expensive than lead-acid
Its materials are toxic and the recycling infrastructure for larger nickel-
cadmium batteries is very limited

13
Lead-Acid Battery
Anode: Porous lead
Cathode: Lead-dioxide
Electrolyte: Sulfuric acid, 6 molar H2SO4

Discharging
(+) electrode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- PbSO4(s) + 2H2O(l)
(-) electrode: Pb(s) + SO42-(aq) PbSO4(s) + 2e-
During charging
(+) electrode: PbSO4(s) + 2H2O(l) PbO2(s) + 4H+(aq) + SO42-(aq) + 2e-
(-) electrode: PbSO4(s) + 2e- Pb(s) + SO42-(aq)

14
Lead-Acid Battery
The lead-acid cells in automobile batteries are wet cells
Deliver short burst of high power, to start the engine
Battery supplies power to the starter and ignition system to start the
engine
Battery acts as a voltage stabilizer in the electrical system
Supplies the extra power necessary when the vehicle's electrical load
exceeds the supply from the charging system

15
Lead-Acid Battery
Advantages:
Batteries of all shapes and sizes, available in
Maintenance-free products and mass-produced
Best value for power and energy per kilowatt-hour
Have the longest life cycle and a large environmental advantage
Ninety-seven percent of the lead is recycled and reused in new batteries

Disadvantages:
Lead is heavier compared to alternative elements
Certain efficiencies in current conductors and other advances continue to
improve on the power density of a lead-acid battery's design

16
Lithium-Ion Battery
Anode: Graphite
Cathode: Lithium manganese dioxide
Electrolyte: mixture of lithium salts

Lithium ion battery half cell reactions

CoO2 + Li+ + e- LiCoO2 E = 1V
Li+ + C6+ e- LiC6 E ~ -3V
Overall reaction during discharge
CoO2 + LiC6 LiCoO2 + C6
Eoc = E+ - E- = 1 - (-3.01) = 4V

17
Lithium-Ion Battery
Ideal material
Low density, lithium is light
High reduction potential
Largest energy density for weight
Li-based cells are most compact ways of storing electrical energy
Lower in energy density than lithium metal, lithium-ion is safe
Energy density is twice of the standard nickel-cadmium
No memory and no scheduled cycling is required to prolong battery
life

18
Lithium-Ion Battery
Advantages:
It has a high specific energy (number of hours of operation for a given weight)
Huge success for mobile applications such as phones and notebook
computers

Disadvantages:
Cost differential
Not as apparent with small batteries (phones and computers)
Automotive batteries are larger, cost becomes more significant
Cell temperature is monitored to prevent temperature extremes
No established system for recycling large lithium-ion batteries

19
Ionic Conductivity and Solid
Electrolytes I: The Basics

Chemistry 754
Solid State Chemistry
Lecture #26
June 2, 2003

Chem 754 - Solid State Chemistry

 References
A.R. West Solid State Chemistry and its
Applications, Chapter 13, Wiley (1984)
C.N.R Rao and J. Gopalakrishnan New Directions
in Solid State Chemistry, pp. 409-416, Cambridge
(1997)
A. Manthiram & J. Kim Low Temperature Synthesis
of Insertion Oxides for Lithium Batteries, Chem.
Mater. 10, 2895-2909 (1998).
J.C. Boivin & G. Mairesse Recent Material
Developments in Fast Oxide Ion Conductors, Chem.
Mater. 10, 2870-2888 (1998).
Craig Fisher (Japan Fine Ceramic Institute)
http://www.spice.or.jp/~fisher/sofc.html

Chem 754 - Solid State Chemistry

 Solid Electrolytes
Electrolyte - A substance that conducts electricity through the
movement of ions.

Most electrolytes are solutions or molten salts, but some electrolytes are solids and
some of those are crystalline solids. Different names are given to such materials:
Solid Electrolyte
Fast Ion Conductor
Superionic Conductor

Over the next two lectures we will be looking at materials which behave as solid
electrolytes, their properties and applications.

Chem 754 - Solid State Chemistry

 Ionic vs. Electronic Conductivity
Lets begin by comparing the properties of ionic
conductors with the conventional electronic conductivity
of metals.
Metals
Conductivity Range = 10 S/cm < s < 105 S/cm
Electrons carry the current
Conductivity Increases linearly as temperature decreases
(phonon scattering decreases as T )

Solid Electrolytes
Conductivity Range = 10-3 S/cm < s < 10 S/cm
Ions carry the current
Conductivity decreases exponentially as temperature
decreases (activated transport)

Chem 754 - Solid State Chemistry

 Defects
In order for an ion to move through a crystal it must hop from an
occupied site to a vacant site. Thus ionic conductivity can only
occur if defects are present. The two simplest types of point
defects are Schottky and Frenkel defects.

Schottky Defect Frenkel Defect

(i.e. NaCl) (i.e. AgCl)
Na+ + Cl- Vna + VCl Ag+ VAg+ Ag+interstitial

Chem 754 - Solid State Chemistry

 Ion Migration (Schottky Defects)
Consider the movement of Na+ ions in NaCl via vacancies
originating from Schottky defects. Note that the Na+ ion must
squeeze through the lattice, inducing significant local
distortion/relaxation. This is one factor that limits the mobility
of ions. A second factor that contributes is the relatively high
probability that the ion will jump back to its original position,
leading to no net ionic migration.

Na Cl
Cl Na E

Cl

Na Cl

To get across the unit cell into the vacancy the Na+ ion must hop through the
center of the cube where it squeezes by 4 Cl- and 2 Na+. The energy of this
transition state will determine the ease
Chemof754
migration.
- Solid State Chemistry
 Ion Migration (Frenkel Defects)
The Frenkel defects in AgCl can migrate via two mechanisms.
Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag1
Ag1
Cl Ag2 Cl Cl Ag2 Cl

Ag Cl Ag Ag Cl Ag

Direct Interstitial Jump

Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag2
Ag1
Cl Ag2 Cl Cl Ag1 Cl

Ag Cl Ag Ag Cl Ag

Interstitialcy Mechanism
Chem 754 - Solid State Chemistry
 Applications of Ionic Conductors
There are numerous practical applications, all based on
electochemical cells, where ionic conductivity is needed and it
is advantageous/necessary to use solids for all components.
Batteries e- Useful
Fuel Cells Power
Gas Sensors
Electrolyte

Anode Cathode
In such cells ionic conductors are needed for either the
electrodes, the electrolyte or both.
Electrolyte (Material needs to be an electrical insulator to
prevent short circuit)
Electrode (Mixed ionic and electronic conductivity is
needed to avoid open circuit)
Chem 754 - Solid State Chemistry
Schematic of a Solid Oxide Fuel Cell

Taken from http://www.spice.or.jp/~fisher/sofc.html

Chem 754 - Solid State Chemistry
Schematic of Rechargable Li Battery

Taken from A. Manthiram &

J. Kim Low Temperature
Synthesis of Insertion
Oxides for Lithium
Batteries, Chem. Mater.
10, 2895-2909 (1998).

Chem 754 - Solid State Chemistry

 Solid Electrolyte Materials
Ag+ Ion Conductors
AgI & RbAg4I5
Na+ Ion Conductors
Sodium b-Alumina (i.e. NaAl11O17, Na2Al16O25)
NASICON (Na3Zr2PSi2O12)
Li+ Ion Conductors
LiCoO2, LiNiO2
LiMnO2
O2- Ion Conductors
Cubic stabilized ZrO2 (YxZr1-xO2-x/2, CaxZr1-xO2-x)
d-Bi2O3
Defect Perovskites (Ba2In2O5, La1-xCaxMnO3-y, )
F- Ion Conductors
PbF2 & AF2 (A = Ba, Sr, Ca) Chem 754 - Solid State Chemistry
 a-AgI & RbAg4I5
Stabilized ZrO2 is
have ionic
not a good ionic
conductivities
conductor at low
comparable to
temperature.
conc. H2SO4

Chem 754 - Solid State Chemistry

Taken from Solid State Chemistry and its Applications by Anthony West
General Characteristics: Solid Electrolytes
1. A large number of the ions of one species should be mobile. This
requires a large number of empty sites, either vacancies or
accessible interstitial sites.
Empty sites are needed for ions to move through the lattice.
2. The empty and occupied sites should have similar potential
energies with a low activation energy barrier for jumping between
neighboring sites.
High activation energy decreases carrier mobility, very stable
sites (deep potential energy wells) lead to carrier localization.
3. The structure should have solid framework, preferable 3D,
permeated by open channels.
The migrating ion lattice should be molten, so that a solid
framework of the other ions is needed in order to prevent the
entire material from melting.
4. The framework ions (usually anions) should be highly polarizable.
Such ions can deform to stabilize transition state geometries
of the migrating ion through covalent Chem
interactions.
754 - Solid State Chemistry
 Molten Sublattice (1/2 Melting)
In the best ionic conductors one ion becomes so mobile that for all intensive purposes
those ions are in a molten state. This behavior can be seen in part from the entropies
of the observed phase transitions, where the Ag (and F respectively) sublattice melts
prematurely.

(poor ionic conductor) b-AgI a-AgI (excellent ionic conductor)

T = 146 C, DS = 14.5 J/mol-K
a-AgI molten AgI
DS = 11.3 J/mol-K
Compare with the an entropy of melting of 24 J/mol-K for NaCl.

solid PbF2 molten PbF2

DS = 16.4 J/mol-K
Compare with the an entropy of melting of 35 J/mol-K for MgF2

Chem 754 - Solid State Chemistry

Ag+ Ion Conductors
b-AgI
Stable below 146 C
Wurtzite Structure (tetrahedral
coordination)
s = 0.001 S/cm 0.0001 S/cm
a-AgI
Stable above 146 C
BCC Arrangement of I-, molten/
disordered Ag+
s ~ 1 S/cm, EA=0.05 eV
Conductivity decreases on melting
RbAg4I5
Highest known conductivity at room
temperature
BCC Arrangement of I-,
molten/disordered Ag+
s ~ 0.25 S/cm (25 C), EA=0.07 eV

Chem 754 - Solid State Chemistry

 Na+ Ion Conductors
NaAl7O11 (Na2O.nAl2O3)
FCC like packing of oxygen
Every fifth layer of the O2- ions
are missing, Na+ ions present.
These layers are sandwiched
between spinel blocks.
2D ionic conductor

Na3Zr2PSi2O12 (NASICON)
Framework of corner sharing
ZrO6 octhahedra and PO4/SiO4
tetrahedra
Na+ ions occupy trigonal prismatic
and octahedral sites, of the Na+
sites are empty
EA ~ 0.3 eV Chem 754 - Solid State Chemistry