Chapter-5

Conducting polymers (MScE5 307)
Chapter Four
Conducting Polymers, Application
School of Mechanical Chemical and Materials

Engineering
Materials Science and Engineering Department
Prepared by : Wegene Lelisa
Date : …………………….
1/16/2024 Conducting polymers 1

5.Conducting Polymers, Application
OUTLINE
5.1. Batteries and Energy Devices
5.2.Displays, Including Light-Emitting Diodes (LEDs) and Conductive Film.
5.3. Electrochemomechanical, Chemomechanical, and Related Devices
5.4.Miscellaneous Applications

5.1. Batteries and Energy Devices.
Noted that only DC can be stored in the batteries, AC current can’t be stored.

 In secondary batter( Rechargeable battery ) .

 Reaction can be readily reversed
 Recharging
 Similar to primary cells expect redox reaction can be reversed
 Electrodes undergo the opposite process than discharging.
 Cathode is oxidized and produce electron.
 Anode is electron acceptor or it reduced.

 Lead acid battery

 Charging and discharging process of lithium ion battery.
 Lithium ion battery involves the insertion of lithium ion into the crystalline lattice
of host electrode with out changing its crystal structure.

 During charging :-lithium ion positive

electrode material is ionized and
moves from layer to layer and
inserted into the negative electrode.
 During discharge:- Li ions are

dissociated from the anode and
migrate across the electrolyte and
inserted into the crystal structure of
the host compound of cathode

 Lithium ion battery

 Types of Batteries Incorporating CPs.
 Li Secondary (Rechargeable) Batteries, Li Batteries Using Poly(Acetylene)

(P(Ac)), Li Batteries Using Poly(Pyrrole) (P(Py)) and Poly(Aniline) (P(ANi)).
 CPs, Mostly used for secondary (rechargeable) batteries.
 In Batteries, CPs are mostly used as an anode and cathode materials in Li

batteries (especially secondary (rechargeable) batteries).
 Mostly researched CPs for batteries, poly(aniline) (P(ANi)) and poly(pyrrole)

(P(Py)).
 Other CPs being considered, poly( p-phenylene) (P(PP)), poly(acetylene)
(P(Ac)), and poly(thiophene) (P(T)).


 Advantages of CPs in Batteries
 They are considered primarily for  It make battery a Lightweight

lowdischarge-rate applications, such as in  Low cost
electronic devices, rather than high-rate
 Easily proccesible into odd
applications such as transportation shapes and sizes
systems;  Less corrosive nature
 Besides poor performance under high

 Compatibility with organic
discharge rates, their specific capacities are
liquid and solid electrolytes
too low for transportation systems.


 Battery Parameters and Performance.
 Discharge voltage (or open-circuit voltage, e.g., 1.5 V for a common “D” cell);
 Energy density, usually expressed in mWh/g (milliWatt-hours/gram);
 Specific capacity battery, usually expressed in mAh/g (A = amperes);
 Number of deep discharge cycles obtainable (cyclability or number of cycles);
 Coulombic efficiency (ratio of charge consumed during charging and

discharging), in % and discharge current density.


 Battery Parameters and Performance.
 A battery capable of a high discharge rate is termed “high rate,” usable for
high-power applications such as transportation.
 “low rate discharge battery ,” usable in low power applications such as
consumer electronics. Most CP-based batteries are low rate.
Nickel-Cadmium
Lithium-ion Batteries Lead-Acid Batteries
Batteries
Nickel-Metal Hydride Batteries


 Comparative parameters for various common secondary (rechargeable) batteries and those using
CPs.

 A typical electrode–electrolyte configuration of a battery
 Li anode.
 LiClO4 in propylene carbonate (PC) – Electrolyte.
 P(Py)ClO4 cathode.
 Arrangement of battery =Li/LiClO4 -PC-electrolyte/P(Py)ClO4
 This is lithium ion battery which incorporated CPs.

 Li Secondary (Rechargeable) Batteries Principles.
 During discharge (i.e., use), Li

ions migrate from the anode
through the Li ion conducting
electrolyte (liquid or solid) to the
cathode, which is a Li-ion
acceptor.
 During charge, the Li ions are
retransported to the anode and
reduced to Li metal thereon.
 Because of the high place of Li in the

electrochemical series and its low
atomic weight, such batteries have
high discharge voltages, >3 V, and
high energy density.
 Li Secondary (Rechargeable) Batteries Principles.
 A schematic representation of a representative lithium based solid state battery, showing the
direction of ion movement and some of the possible anode, electrolyte, and cathode combinations

 Problems of li ion battery with the simple battery configuration
 Severe corrosion due to the highly reactive Li at the anode. This

overcome by :-
 Substitution of Li metal by Li-intercalates.

Lix -graphite is a common intercalate anode
material, and a LiCoO2 is a common intercalate
cathode material.
 Substitution of Liquid electrolyte by less reactive
solid electrolytes with high conductivity at
ambient temperature
Intercalation principle of lithium-ion batteries
 Acceptability of Li ions at the cathode, another problem, is improved by use

of cathode materials such as V and Mo oxides or sulfides.


 Lithium battery is commercialized as “Li-ion” batteries, sometimes called “Li
rocking-chair batteries“due to the fact that Li ions rock back and forth between
anode and cathode during discharge/charge.
 Li/CP Batteries
 Operation Mechanism of Li/CP battery and advantages of CP
 Anode – Lithium
 Cathode – Cis-P(Ac)
 Electrolyte - 1 M LiClO4 (lithium perchlorate) in propylene

carbonate (PC).


 Li/CP Batteries
 This battery had an initial discharge voltage of 3.7 V and used 6% doped
P(Ac).
 During discharging, de-doping of the CP occurs, while during charging,
doping occurs;
 The reactions at the anode and cathode are:


Electrolytes
 Solid electrolytes
1) PEO/LiClO4 solid electrolytes (PEO – Polyethylene oxide); operates at temp.

>60C
2) poly(acrylonitrile) (PAN)–ethylene carbonate (EC)–salt + PC (Propylene

carbonate) Note: EC and PC are plasticizers.
3) PAN/PMMA/poly(vinylidene difluoride) (PVDF), its composite two-phase
electrolytes where a liquid phase is trapped in a matrix obtained by UV cross-linking or
gelification.


 Problems Associated with Li/CP Batteries.
1) Stability of CPs such as P(Ac), especially in contact with leaking air/moisture or

liquid electrolytes, is a major issue.
2) Spontaneous de-doping when in contact with electrolyte containing counter-

ions inhibits discharge.
3) Poor conductivity of the CP in its de-doped state, e.g., after full charging,
renders it a pseudo electrode and inhibits battery function.
4) Corrosive and reactive effects of liquid electrolytes can be avoided with use of
common solid polymer electrolytes, the latter’s much lowered conductivity severely
inhibits ambient temperature function.


 Problems Associated with Li/CP Batteries.
4) Yet another drawback of CPs is their maximum dopability, for example, ca. 33%
for poly(pyrrole) (P(Py)) or ca. 50% for P(ANi).
 This inhibits their uptake of counterions during charging, in turn lowering their
specific capacity, which is significantly lower than, e.g., that of LiCoO2 or
LixVO2.17, common cathodes in Li-ion batteries.
5) And use of solid electrolytes with CP electrodes greatly diminishes the

diffusion coefficient of the counter-ions involved in CP doping/de-doping,
lowering battery efficiency.
 Indeed, improving physical contact between CP electrode and solid electrolyte
layer is contended to be a major problem in solid-state CP batteries

 Examples of batteries incorporating various CPs as electrode materials.

 Li Batteries Using Poly(Acetylene) (P(Ac)).
 Poly(acetylene) (P(Ac)) batteries, including all-P(Ac) (i.e., non-Li) batteries,
were among the first CP-based secondary batteries fabricated (1981-1984).
 The open circuit potential of a Li/P(Ac) battery is dependent upon the initial
P(Ac) doping level.
 Poor stability of P(Ac) in the presence of O2 or moisture.
 Poor stability of the P(Ac) in the presence of most liquid and solid
electrolytes and poor shelf life due to spontaneous de-doping.


 At a discharge current density of 0.1 mA/cm2 , a coulombic efficiency of 86%
is obtained, while at 5.0 mA/cm2 , a coulombic efficiency of less than 27% is
obtained.
 Increasing the doping level of the P(Ac), in-fact decreases the coulombic
efficiency.
 An optimal doping level of ca. 2%, coulombic efficiency steadily decreases,

going, e.g., from
 ca. 86% at 2% doping
 To Ca 60% at 7% doping to
 ca. 35% at 19% doping


 Li Batteries Using Poly(Pyrrole) (P(Py)), Poly(Aniline) (P(ANi)), and Poly(Thiophenes)
 A cylindrical AA-dimension rechargeable battery developed using a

 P(ANi)-TiO2 composite as cathode
 Zn outer container as anode,
 Cellulose acetate as the separator.
 polyvinyl sulfate and carboxy methyl cellulose as the

solid polymer electrolytes (SPE).
 This battery displayed acceptable performance: open-circuit voltage (OCV) of

1.4 V, current of 250 mA to 1.0 A, 50 recharge cycles, power density of 350
Ah/kg, and power efficiency of 70%.

 Polyaniline in Li batteries
 P(ANi) nanofibers and nanotubes using a spray technique by wetting a

template with a CP solution.
 These nanofibers and nanotubes showed good electrochemical performance

when used as the cathode electrode material in lithium batteries.
 The discharge capacity value of the doped P(ANi) nanotubes/nanofibers

reached 75.7 mAh/g and retained 72.3 mAh/g it is 95.5% of the highest
discharge capacity) in the 80th cycle.


 Polyaniline in Li batteries
 The values are higher than the commercially doped polyaniline powders, about
54.2 mAh/g.
 The specific discharge energy of the nanostructures was claimed to reach 227
Wh/Kg.
 The nanotube electrodes were claimed to exhibit longer charge and discharge
plateaus as compared to those for electrodes composed of commercial powders

 Li/P(Py) batteries
 It have been studied for all sorts of variables, such as the
a) porosity/morphology of the P(Py),
b) synthesis method, and
c) dopant type/concentration.
 It was found that the porosity of P(Py), and battery efficiency due to improved
counterion diffusion, is higher in the order PF6 - > triflate > perchlorate >
tetrafluoroborate.


 Li/P(Py) batteries
 P(Py) chemically polymerized with ferric perchlorate showed improved
charge/discharge characteristics as compared to that polymerized using Cu
tetra fluoroborate.
 One of the improved properties of Li/P(Py) batteries, as compared, e.g., to
Li/P(Ac) batteries, is the improved storage (shelf) life.
 (a, b) Comparative charge/discharge curves for similarly constructed (a) Li/P(Ac)

and (b) Li (P(Py))
 Organic Photovoltaic/Solar cells
 Formation of pn homojunction in a single semiconductor material through doping

is key for photocurrent generation in inorganic solar cells (SCs).
Inorganic solar cell Homo pn junction
 A donor/acceptor heterojunction is generally utilized in organic SCs in order to

split coulombically bound exciton forming in organic semiconductors.

 Hetero junction Organic PVC  In organic homo Pn junction.

 One solar cell

give 0.5 eV.

 Advantage of Organic solar cells over with their inorganic counterpart.
(i) It has good conversion efficiency.
(ii) It is ease of process able,
(iii) It can be mass produced by printing techniques on flexible

substrates at room temperature.
(iv) The absorption coefficient of photoactive organic semiconductors
is very high.
 The strongly bound electron–hole pair as primary photoexcitation in organic

semiconductors, a singlet exciton, has a lifetime below 1 ns;
 The corresponding diffusion length being limited to a few nanometres. Exciton
diffusion length is limited.

 To overcome the electron/hole diffusion limitations, reducing the length of

exciton diffusion before reaching an Donor/acceptor.
 This achieved by forming bulk heterojunction solar cells mixing the two
materials, donor and acceptor.
Kotane, L. M. (2019). Efficiency and opto-electrical studies of solution processed bulk heterojunction organic photovoltaic devices,
Faculty of Science, University of the Witwatersrand, Johannesburg.

 For example of donor-acceptor blends - polyphenylenevinylene (PPV) was

used as light absorbing material (p-type), whereas, the charge generation was
assisted by blending it with the fullerene C60 (n-type/electron acceptor).
 The charge separation in this system was only femtoseconds.
 C60 is not solvent process able, and it’s derivative PCBM ([6,6]-phenyl-C61
butyric acid methyl ester) is processable.

 An important optimization parameter is the phase separation and its spatial

dimensions:
(i) Too large phases limit the photocurrent due to the low exciton diffusion
length, whereas.
(ii) (ii) A too fine-grained intermixing hinders the charge (electron-hole)
extraction
 Phase separation is optimized by selecting solvents with a higher boiling point,

allowing for a slower drying time and thus better self-organization. To get an
efficiency of 1 to 2.5%.
 Poly(3-hexyl thiophene) (P3HT) in conjunction with PCBM due to better phase

separation can get efficiency from 0.4 to 3.5%.

 Copolymer–fullerene blends led to a conversion efficiency of beyond 8%.
 The performance of polymer solar cells can be improved by charge carrier

generation and reducing recombination.
 Usage of conducting polymers in solar cells and photovoltaics,
PTB7=Poly(thieno[3,4 - b ] - thiophene /benzodithiophene )
Typical organic solar cell

 Blended MEH-PPV with C60 and its derivatives are the first CP-based solar cell
of this type with a high conversion efficiency.


 Types of Organic photovoltaic cell,there three types
photovoltaic solar cells .
1.Small- molecule based OPC.
 Donor :-Highly conjugated systems (CPs) used:-

Eg.Phthalocyanines ,polyacenes ,and squarenes
 Acceptor :-Perylene dyes and fullerenes
2.Polymer based OPC

 Donor :long chain CPs molecular systems ;e.g
P3HT,MDMO-PPV
 Acceptor :-Fullerene derivatives;PC60BM,PC70BM
P3HT

3.Dye sensitized OPC
 Donor:-Small –molecules absorber dyes

 Acceptor :ZnO,TiO2
 Electrolyte to regenerate dye

 One of the great discovery in conducting polymer application was the use of
poly(phenylene vinylene) (P(PV)) as an emissive layer in light-emitting diodes
(LEDs).
 Irrespective of the drawbacks in CPs compared to it’s inorganic counterpart but

still it has been researched extensively, especially in flat-panel displays for
computer and electronic uses.
 Organic-based LEDs
 Organic-based LEDs, i.e., OLEDs, are not new.
 Those based on such materials as anthracene, naphthalene, and pyrene,
with Ag, liquid, alkali metal, or even ITO electrodes, have been known for
several decades.
 An OLED (organic light-emitting diode) is a type of LED (light-emitting diode),

where the emissive electroluminescent layer is a film of organic compound
which emits light in response to an electric current(electric field).

 Working principle of OLED.

 A voltage is applied across the anode and
cathode
 Current flows from cathode to anode through
the organic layers
 Electrons flow to emissive layer from the
cathode
 Electrons are removed from conductive layer
and leaving holes
 Holes jump into emissive layer
 Electron and hole combine and light emitted at
emissive layer.
anthracene
 PEDOT:PSS - poly(3,4-
ethylenedioxythiophene) polystyrene
sulfonate
 It is one of the efficient hole injecting layer

 Organic LEDs based on perylene-doped poly(vinyl carbazole) (P(VCz))
 Schematic of a typical OLED display,

e.g., as used in TVs.
 The substrate can be flexible, e.g.,
plastic, or rigid, e.g., glass or metal.
 With a voltage applied across the
OLED, current flows from the cathode
to the anode.
 This adds electrons to the emissive
layer and creates holes at the anode.
 At the layers’ boundary, electrons and
holes combine to give off light.
 Electron and hole injection and transport layers can be added to further modulate
electron movement.
 Single crystals(pn jumction LED) might need high voltage, typically 10-20 V
but frequently as much as 50–100 V.
 Efficiencies in these LEDs, were detrimental to their practical and commercial
implementation.
 Whereas the advantages of using CPs in LED.
1) Requiring low voltages, of the order of 2– 5 V DC.

2) They are processible in their undoped state in polymer form into odd
shapes/sizes and films.
3) They are relatively inexpensive and exhibit comparatively higher quantum
efficiencies.
4) Their emission colors are possibly “tunable,” through structural changes in
the CP backbone, combination of multiple CPs, or several other methods,
throughout the visible and even NIR region

 Principles of CP-Based LEDs
Simple design of one of the first CP-LEDs (left) and variant thereof
 Normally, one electrode needs to be semitransparent, e.g., ITO/glass, so that

the electroluminescence is visible.

 The function of CP-LEDs is intimately associated with properties such as

electroluminescence (EL), upon which the LED’s function is based.
 Photoluminescence (PL), and photo-induced absorption (PIA) are the other

intrinsic properties of LEDs.
 These material properties should be characterized first before constructing any

complete LED.
 CP property highly useful for designing an LED is its equilibrium redox

potential or “work function,” obtainable from electrochemical data such as
voltammetry.

 An LED functions on the principle of double charge injection.
 That is, through the medium of an applied electric field, holes are
“injected” at one electrode (into the valence band of the active LED
material) and electrons at the other (into its conduction band).
 Then transported through the body of the active LED material, i.e., the CP,
where they combine or “capture” each other, forming excitons (usually mid-
gap states)
 Certain of these excitons, usually the singlets, decay radiatively, emitting light at a
wavelength characteristic of the CP’s bandgap.

 The thermodynamic work function of the contact electrode thus must match that
of the CP (in terms of its overall redox potential or more specifically its.
(i) ionization potential (IP) or ionization

energy (IE) for hole injection.
ii) electron affinity (EA) for electron

injection)
 In this a way to facilitate hole or electron injection.


 Energy diagram of a semiconductor with flat
bands to the surface.
 Band edges (CBM/LUMO and VBM/HOMO),

vacuum level EVAC, work function WF, energy
gap EG , ionization energy IE and electron
affinity EA are defined.

 Working Principles of OLEDs
 External voltage source of typically a few volts is applied to the device
 Then two types of charge carriers are injected from the opposite
electrodes, that is, electrons from the cathode and holes from the anode,
and drift toward each other.
 Which radiatively recombine to form strongly bound electron–hole pairs

(excitons) in the emission layer.

 The whole process can be separated into four fundamental steps
1) Injection of electrons and holes at the electrodes.
2) Transport of charge carriers through the organic layers.
3) Formation of bound electron–hole pairs (excitons).
4) Radiative exciton decay and emission of light.


1) Injection of electrons
and holes at the
electrodes
2) Transport of charge
carriers through the
organic layers
3) Formation of bound
electron– hole pairs
(excitons)
4) Radiative exciton decay
and emission of light
 Schematic energy diagram of a three-layer OLED illustrating the basic processes

of electroluminescence.

 Since the anode and cathode have different WF, BI – built in voltage exists in
the device, which has to be overcome by an external voltage V before current
can flow through the device.
 Most CPs studied have low IPs, and thus hole injection is not a problem for them.
 Even transparent ITO/glass appears to be an acceptable electrode for hole

injection.
 However, since the EA of CPs is generally also quite low, electron injection into
them has been found to be more problematic.


 Very low work function metals,
such as Ca, were required to
be used for acceptable electron
injection.
 Metals such as Al have higher a work

function than Ca, resulting in much
lowered device efficiency. The primary
mode of electron injection in such
devices is thought to be tunnelling.


 Varieties of CPs Used
 P(PV) was the first CP used in LEDs, due to its easy processibility in defect-free
form.
 In theory, any CP exhibiting singlet exciton formation on charge injection could

be used in an LED.
 In practice, processing difficulties in the fabrication of a device.
 The presence of impurities which quench excitonic states, has limited practical
implementation to a few CP classes.


 Varieties of CPs Used
 These classes CPs that used for OLED include:
 P(PV) and its derivatives

 Poly(3-alkyl thiophenes) [P(3-octyl-T)]
 The relatively new CP structures embodied in
poly(pyridine) and poly(pyridylvinylene)
 Poly( p-phenylene) (P(P)).
 Poly(bithiophene) derivatives
 Poly(thienylene vinylene) derivatives


 Fabrication and assembly of a typical CP-LED, having the configuration ITO-
glass/P(PV)/(Al or Ca or Au).
1. P(PV) is deposited on ITO-glass substrates via a precursor polymer route.

 The tetrahydro-thiophenium precursor is spin coated onto the ITO
substrate.
 Then converted to P(PV) via heating at 220 C for ca. 10 h in
vacume.Final P(PV) thickness in the region of 100–250 nm
.obtained
 Metal, electron-injecting electrode, contacts (Ca, Al, Au) of several
mm2 area are then formed by vacuum evaporative deposition.

 Fabricated configuration of ITO-

glass/P(PV)/(Al or Ca or Au).
tetrahydro-thiophenium

Conductive Films:-READING ASSIGNMENT

5.3. Electrochemomechanical, Chemomechanical, and Related Devices.

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Conducting polymers (MScE5 307)

School of Mechanical Chemical and Materials

Prepared by : Wegene Lelisa

1/16/2024 Conducting polymers 1

5.1. Batteries and Energy Devices

5.2.Displays, Including Light-Emitting Diodes (LEDs) and Conductive Film.

5.3. Electrochemomechanical, Chemomechanical, and Related Devices

1/16/2024 Conducting polymers 2

5.1. Batteries and Energy Devices.

1/16/2024 Conducting polymers 3

5.1. Batteries and Energy Devices.

 In secondary batter( Rechargeable battery ) .

 Similar to primary cells expect redox reaction can be reversed

 Electrodes undergo the opposite process than discharging.

 Cathode is oxidized and produce electron.

 Anode is electron acceptor or it reduced.

1/16/2024 Conducting polymers 4

1/16/2024 Conducting polymers 5

 Charging and discharging process of lithium ion battery.

1/16/2024 Conducting polymers 6

 During charging :-lithium ion positive

 During discharge:- Li ions are

1/16/2024 Conducting polymers 7

1/16/2024 Conducting polymers 8

 Types of Batteries Incorporating CPs.

 Li Secondary (Rechargeable) Batteries, Li Batteries Using Poly(Acetylene)

 CPs, Mostly used for secondary (rechargeable) batteries.

 In Batteries, CPs are mostly used as an anode and cathode materials in Li

 Mostly researched CPs for batteries, poly(aniline) (P(ANi)) and poly(pyrrole)

1/16/2024 Conducting polymers 9

5.1. Batteries and Energy Devices.

 They are considered primarily for  It make battery a Lightweight

 Besides poor performance under high

1/16/2024 Conducting polymers 10

5.1. Batteries and Energy Devices.

 Energy density, usually expressed in mWh/g (milliWatt-hours/gram);

 Specific capacity battery, usually expressed in mAh/g (A = amperes);

 Number of deep discharge cycles obtainable (cyclability or number of cycles);

 Coulombic efficiency (ratio of charge consumed during charging and

1/16/2024 Conducting polymers 11

5.1. Batteries and Energy Devices.

Nickel-Metal Hydride Batteries

1/16/2024 Conducting polymers 12

5.1. Batteries and Energy Devices.

1/16/2024 Conducting polymers 13

5.1. Batteries and Energy Devices.

 A typical electrode–electrolyte configuration of a battery

 Arrangement of battery =Li/LiClO4 -PC-electrolyte/P(Py)ClO4

 This is lithium ion battery which incorporated CPs.

1/16/2024 Conducting polymers 14

5.1. Batteries and Energy Devices.

 Li Secondary (Rechargeable) Batteries Principles.

 During discharge (i.e., use), Li

 Because of the high place of Li in the

5.1. Batteries and Energy Devices.

 Li Secondary (Rechargeable) Batteries Principles.

1/16/2024 Conducting polymers 16

5.1. Batteries and Energy Devices.

 Problems of li ion battery with the simple battery configuration

 Severe corrosion due to the highly reactive Li at the anode. This

 Substitution of Li metal by Li-intercalates.

 Acceptability of Li ions at the cathode, another problem, is improved by use

1/16/2024 Conducting polymers 17

5.1. Batteries and Energy Devices.