Introduction to the field of

polymer ionics:

Definitions and historical development
Prof. Dr. Agnieszka Pawlicka
Summary
1. Introduction to the field of polymer ionics

1.1. Definition of polymers and conductivity
1.2. Definition of polyelectrolytes, polymer electrolytes,
polymeric gels
1.3. Historical development
1.4. Current state of art in the field of polymer
electrolytes
Poly(ethylene oxide) systems, grafted, crosslinked,
plasticized and composite systems;
1.5. Advantages and disadvantages of different
systems
What are polymers ?
Polymers are composts formed by an almost regular repetition of units (atomic
groups) connected by chemical bonds which to form linear long chains or
branched, or three-dimensional net (polymerization) .
Monomer
What is a polymer?

What is a conduction?
Conduction is the movement of electrically charged particles through a
transmission medium (electrical conductor).

The movement of charge constitutes an electric current.

The charge transport may result as a response to an electric field, or as
a result of a concentration gradient in carrier density, that is, by
diffusion.

The physical parameters governing this transport depend upon the
material.
Electrical conduction
Heat conduction or thermal conduction is the spontaneous transfer of
thermal energy through matter, from a region of higher temperature to a region
of lower temperature, and hence acts to even out temperature differences.
Topics to cover
Metals, semiconductors, and insulators.
Band structure & electron conduction.
Electrical conductivity in metals.
Semiconducting materials.
Conducting polymers.
Ionic conduction & polymer electrolytes.
Electrical Conductivity in Materials
Metals: good conductors with electrical conductivity on the order of 10
7

-1
m
-1
(10
5
S/cm)
Metallic bonding leads to a sea of electrons that are free to move around.

Insulators: electrical conductivity ~ 10
-10
to 10
-20

-1
m
-1
.
Ionic or strong covalent bonds where valence electrons are tightly bound
(localized).

Semiconductors: electrical conductivity ~ 10
-6
to 10
4

-1
m
-1
.
Covalent (or predominantly covalent) bonds that are relatively weak
(valence electrons are not as tightly bound as in insulators).

Types of conductivity
electronic conduction: motion of electrons and/or holes (in most solid
materials).
ionic conduction: motion of charged atoms and/or molecules.
Metals, Semiconductors and Insulators
Electrical Conduction
Free electrons
needed for
electrical
conduction
(applied electric
field is sufficient to
generate large
number of free
electrons).
METALS
SEMICONDUCTORS OR INSULATORS
Due to the band
gap, much more
energy input is
necessary to create
charge carriers
(electrons in
conduction band or
holes in valence
band).
Fermi level
Fermi level" is the term used to describe the top of
the collection of electron energy levels at absolute
zero temperature.
This concept comes from Fermi-Dirac statistics.
Electrons are fermions and by the Pauli exclusion
principle cannot exist in identical energy states. So
at absolute zero they pack into the lowest available
energy states and build up a "Fermi sea" of electron
energy states.
The Fermi level is the surface of that sea at absolute
zero where no electrons will have enough energy to
rise above the surface. The concept of the Fermi
energy is a crucially important concept for the
understanding of the electrical and thermal
properties of solids.
Both ordinary electrical and thermal processes
involve energies of a small fraction of an electron
volt. But the Fermi energies of metals are on the
order of electron volts.
This implies that the vast majority of the electrons
cannot receive energy from those processes
because there are no available energy states for
them to go to within a fraction of an electron volt of
their present energy. Limited to a tiny depth of
energy, these interactions are limited to "ripples on
the Fermi sea".

Although the Fermi function has a finite value in the gap, there is no
electron population at those energies (that's what you mean by a
gap). The population depends upon the product of the Fermi function
and the electron density of states. So in the gap there are no
electrons because the density of states is zero. In the conduction
band at 0K, there are no electrons even though there are plenty of
available states, but the Fermi function is zero. At high temperatures,
both the density of states and the Fermi function have finite values in
the conduction band, so there is a finite conducting population.

The Fermi function f(E) gives the
probability that a given available
electron energy state will be
occupied at a given temperature.
The Fermi function comes from
Fermi-Dirac statistics and has the
form
Electrical conduction in
Semiconductors
Bonding and band gap
Structure m.p. (K) E
g
(eV)
C (Diamond) Diamond 3773 5.5
Si Diamond 1683 1.1
Ge Diamond 1210 0.7
Need to create free electrons (or holes) for electrical
conduction.
The smaller the band gap, the less energy is
required to create charge carriers.
Conductivity of intrinsic (undoped) semiconductors:
|
|
.
|

\
|

kT
E
g
exp o
Conductivity increases with T.
What is a conducting polymer?

Conjugated polymers: long conjugated systems;
Energy states related with structural defects
Defects are caused by alterations in the molecular geometry and in the charges distribution.
What are conducting polymers ?
Quasi-particles doping
Delocalization
OBS: The carriers not are electrons neither holes
localized in the interior of bands but are charged
defects, localized long the polymeric chain.
Conjugated Polymers:
Organic semiconductors with t-bonds delocalizing along the polymer chain
Conjugated Polymers
Synthetic Metals
go
Quasi-particles
The use of term quasiparticle seems to be ambiguous.

Some authors use the term in order to distinguish them from real particles, others to describe
an excitation similar to a single particle excitation as opposed to a collective excitation.
Both definitions mutually exclude each other as with the former definition collective
excitations which are no "real" particles are considered to be quasiparticles. The problems
arising from the collective nature of quasiparticles have also been discussed within the
philosophy of science, notably in relation to the identity conditions of quasiparticles and
whether or not they should be considered "real" by the standards of, for example, entity
realism.

Phonons are the quanta of classical sound waves and sound waves do not need the
notion of atoms.
Magnons are the quanta of classical spinwaves, which also do not need elementary
spins.
Photons inside an isolator are the quanta of classical dressed electromagnetic waves
and do not need the notion of electrons for the definition of the refractive index.
Plasmons are the quanta of the plasma oscillations and they only need charge
density and mass density and no electrons or ions.
Polarons are the quanta of the oscillating polarization in a lightly doped
semiconductor and also do not need elementary charge or mass.

eParticles in physics
Elementary particles
Fermions: Quarks: u d c s t b Leptons: e
-
e
+

-

+

-

+

e

Bosons: Gauge bosons: g W

Z
0


Other: Ghosts


Composite particles
Hadrons: Baryons(list)/Hyperons/Nucleons: p n
b
Mesons(list)/Quarkonia: K
J/
Other: Atomic nuclei Atoms Exotic atoms: Positronium Molecules
Hypothetical
elementary particles
Superpartners: Axino Dilatino Chargino Gluino Gravitino Higgsino Neutralino Sfermion Slepton
Squark
Other: Axion Dilaton Goldstone boson Graviton Higgs boson Tachyon X Y W' Z'
Hypothetical
composite particles
Exotic hadrons: Exotic baryons: Pentaquark Exotic mesons: Glueball Tetraquark
Other: Mesonic molecule
Quasiparticles Davydov soliton Exciton Magnon Phonon Plasmon Polariton Polaron
How good is the conductivity of
polymers, compared to metals

Electrolytes short description
Ionic conducting electrolytes with low
electronic conductivity

Solids, liquids or elastomers

Liquid electrolytes are preferred
liquids with high viscosity due to the
convenience or security
Liquid Electrolytes
Electric currents in electrolytes are flows of electrically charged
atoms (ions).

Classical example of NaCl
if an electric field is placed across a solution of Na
+
and Cl

, the sodium ions

will move constantly towards the negative electrode (anode), while the
chloride ions will move towards the positive electrode (cathode).

If the conditions are right, redox reactions will take place at the
electrode surfaces, releasing electrons from the chloride, and allow
electrons to be absorbed into the sodium.
Liquid electrolytes
Ionic charged species should be near the electrodes

Desirable non reactive salts, which
- easily form ions in the adequate solvents
- does not precipitate over the electrodes
- stable during the photolise process

For polymeric electrolytes are generally used PC
with LiClO
4
(explosive during drying) which can be
substituted by LiBF
4

Choose of the electrolyte depend on the
electrochemical system
Classification of Solid Electrolytes
Solid Electrolytes
organic inorganic
Polymeric
electrolytes
Polyelectrolytes
Macromolecules
(PEO or PPO)
with Li
+
salts
Molecular mass
low - liquids
intermediary -
viscous liquids
high solids
almost rigid
Polymers with ionic
groups which
can give cations
or receive cations
(PolyAMPS)
have a groups
regular distributed
along the chain
that give the protons
Different oxides
(Cr
2
O
3
, Ta
2
O
5
);
Protonic and
Anionic conduction
(high for H
+

good for Li
+
)
Better than organic
due to the stability
for fotolitic degradation
Inorganic Solid Electrolytes
P.M.S. Monk, R.J. Mortimer, D.R. Rosseinsky, Electrochromism:
Fundamentals and Applications, VCH, Weinheim, 1995.
Inorganic electrolytes
Significant resistance to the interphase
contact problems with contacts
Solution:
prototype of ECD with WO
3
Subsequent evaporation (sputtering) of the thin
films one on the other

ITO/counter electrode film/solid electrolyte/electrochromic film/ITO

- inconvenience high price of the production
Other deficiencies
Relative fragility easy to broken

Disintegration of the coatings due to the expansion
and contraction of the electrode films during the
insertion and desinsertion of the ions
Classification of Solid Electrolytes
Solid Electrolytes
organic inorganic
Polymeric
electrolytes
Polyelectrolytes
Macromolecules
(PEO or PPO)
with Li
+
salts
Molecular mass
low - liquids
intermediary -
viscous liquids
high solids
almost rigid
Polymers with ionic
groups which
can give cations
or receive cations
(PolyAMPS)
have a groups
regular distributed
along the chain
that give the protons
Different oxides
(Cr
2
O
3
, Ta
2
O
5
);
Protonic and
Anionic conduction
(high for H
+

good for Li
+
)
Better than organic
due to the stability
for fotolitic degradation
Polyelectrolytes
Chitosan is obtained from chitin (structural
element in the exoskeleton of crustaceans
(shrimps, crabs, etc.)
At least 50% of amino groups.

Chitosan is positively charged and soluble in
Low acidic solution.

Biodegradable and biocompatible.
Classification of Solid Electrolytes
Solid Electrolytes
organic inorganic
Polymeric
electrolytes
Polyelectrolytes
Macromolecules
(PEO or PPO)
with Li
+
salts
Molecular mass
low - liquids
intermediary -
viscous liquids
high solids
almost rigid
Polymers with ionic
groups which
can give cations
or receive cations
(PolyAMPS)
have a groups
regular distributed
along the chain
that give the protons
Different oxides
(Cr
2
O
3
, Ta
2
O
5
);
Protonic and
Anionic conduction
(high for H
+

good for Li
+
)
Better than organic
due to the stability
for fotolitic degradation
Advantages
Polymeric electrolytes can be formed in the form of
very thin films of large surface area giving high
power levels (>100 Wdm
-3
)
Fiona M. Gray Solid Polymer Electrolytes, Fundamentals and technological applications
VCH Publishers, 1991.
Solid Organic Electrolytes
P.M.S. Monk, R.J. Mortimer, D.R. Rosseinsky, Electrochromism:
Fundamentals and Applications, VCH, Weinheim, 1995.
Nafion
Nafion is a sulfonated tetrafluorethylene copolymer discovered in the late 1960s by
Walther Grot of DuPont de Nemours. It is the first of a class of synthetic polymers
with ionic properties which are called ionomers. Nafion's unique ionic properties are a
result of incorporating perfluorovinyl ether groups terminated with sulfonate groups
onto a tetrafluoroethylene (Teflon) backbone. Nafion has received a considerable
amount of attention as a proton conductor for proton exchange membrane (PEM) fuel
cells because of its excellent thermal and mechanical stability.


The chemical basis of Nafion's superior conductive properties
remain a focus of research. Protons on the SO
3
H (sulfonic acid)
groups "hop" from one acid site to another. Pores allow movement
of cations but the membranes do not conduct anions or electrons.
Nafion can be manufactured with various cationic conductivities.
History of PE research
It was already established that
polyethers can interract with
various salts and this properties
was largely used in organometallic
chemistry

In 1973 - dr. P.V.Wright described
conducting properties of
poly(ethylene oxide)-salt systems
without solvent.
Photos during - ISPE-2006, Foz do Igua, Brazil
Photos during - ISPE-2006
Foz do Igua
Brazil
The latter workers also observed that the
dissolution of potassium iodide in
poly(ethylene oxide) disrupts the
crystallinity of the polymer producing an
elastomeric material at room temperature.
We wish to report the preparation of
crystalline complexes of sodium and
potassium salts with poly(ethylene
oxide).
Important observation
The work of Iwamoto et al. and the extensive studies
of alkali metal ion-cyclic ether complexes, indicate that
the ether oxygen atoms interact directly with the
cations and not with the anions as suggested by
Lundberg et al. in their solution study. Similarities in
the infra-red spectra of the poly(ethylene oxide)
complexes and the cyclic ether complexes suggest
that the cations may be similarly disposed towards the
oxygen atoms.
P.V. Wright et al. POLYMER, 1973, Vol 14, November 589
Photos during
ISPE-2004
Mragowo
Poland
a.c. and d.c.
conductivity results
1 cal = 4.186 J
ISPE-2004
Mragowo-
Poland
M.B. Armand, in: Fast Ion transport in Solids, ed. W. Van Gool
(North-Holland, Amsterdam, 1973)p. 665.
" ...but it is realistic to expect that in a
near future a whole set of electrolytes
will be available for either Li, Na or K.
Especially thin film polymers will be
suitable for an all solid state system, as
a good contact is easily achieved with
soft materials..."
In 1978 Prof. M. Armand showed the technological importance
of these new materials for storage energy devices.

Interesting due to the reserach on lithium rechargeables
bateries, which can contain different films, also polymeric.
Others applications also can be possible.

Use of the alternative sources of energy as solar energy and
wind, which generate the electricity. These need the low price
and high eficiency energy storage systems.
Photos during
ISPE-2004
Mragowo
Poland
Polymeric electrolytes history
D.Fauteux et al. Electrochim Acta, 40 (1995) 2185
New class of materials
Polymeric electrolytes (solid polymeric electrolytes;
SPEs) are new class of solid state ionics

Differences between polymeric electrolytes and ionic
conducting materials as ceramics, glass, inorganic
crystals:

a) Charge transport - below
Tg
b) Conductivity values 100-1000 times lower than
other materials
Flexibility of SPEs
Important due to the volume change
during the electrochemical cycling,

Accommodation without physical
degradation of the interfacial contacts
frequently observed in crystalline or
vitreous solid electrolytes
Polymeric gels
Polymeric gels may exist in two distinct phases,
swollen and
collapsed states - the volume of gels can decrease as much as 1000 times.

Volume transition of gels occurs when the gels are stimulated by change of
chemical or physical factors such as
temperature,
solvent
composition,
pH, and
electric field .

The ability of gels to undergo such significant but reversible changes in volume in
response to a precisely programmed stimulus allows unique new systems to be
made.

The number of applications based on volume phase transitions of polymeric gel
increases continuously.

Applications include
temperature-sensitive gels and glucosesensitive gels for controlled delivery insulin
systems [6],
light triggered optical shutter [7],
chemical sensors [8], and
even an artificial pancreas [9].

In such application, the knowledge of the diffusion coefficient of ions and
molecules as a fundamental measure of molecular mobility and electrostatic
interactions is of great importance.
Physical Properties of
Polymeric Gels
J. P. Cohen Addad (Editor)
ISBN: 978-0-471-93971-9
Hardcover
324 pages
December 1995
Gel electrolytes
Polymers containing a low-molecular-
weight fraction that assist ionic transport.

Current state of art in the field of
polymer electrolytes
PEO-based polymeric electrolytes
Modification of PEO
Other polymers with PEO
Conductivity of 10
-2
S/cm
Transparency
Good adhesion to glass properties
New salts

Chemical and Physical
modifications
Grafted systems
PEO with other polymers
PEO on other polymers

Plasticized systems
Addition of plasticizers
PVA, Glycerol, Ethylene glycol, etc.

Composites-based system
Addition of nanoparticles of Al
2
O
3
, TiO
2
, SiO
2
etc.
Addition of carbon nanotubes
Advantages and Disadvantages
Low crystallinity
High conductivity
Good stability
Low glass transition temperature
Transparency