Polymer Ionics Introduction

7/31/2019 Polymer Ionics Introduction

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Introduction to the field ofpolymer ionics:

Definitions and historical development

Prof. Dr. Agnieszka Pawlicka


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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 polymerelectrolytes

Poly(ethylene oxide) systems, grafted, crosslinked,plasticized and composite systems;

1.5. Advantages and disadvantages of differentsystems


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What are polymers ?

Polymers are composts formed by an almost regular repetition of units (atomicgroups) connected by chemical bonds which to form linear long chains orbranched, or three-dimensional net (polymerization) .

Monomer

What is a polymer?


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What is a conduction?

Conduction is the movement of electrically charged particles through atransmission medium (electrical conductor).

The movement of charge constitutes an electric current.

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

The physical parameters governing this transport depend upon the

material.

Electrical conduction

Heat conduction or thermal conduction is the spontaneous transfer ofthermal energy through matter, from a region of higher temperature to a regionof lower temperature, and hence acts to even out temperature differences.
http://en.wikipedia.org/wiki/Electric_chargehttp://en.wikipedia.org/wiki/Transmission_mediumhttp://en.wikipedia.org/wiki/Electrical_conductorhttp://en.wikipedia.org/wiki/Current_%28electricity%29http://en.wikipedia.org/wiki/Electric_fieldhttp://en.wikipedia.org/wiki/Fick%27s_lawhttp://en.wikipedia.org/wiki/Heat_transferhttp://en.wikipedia.org/wiki/Heat_transferhttp://en.wikipedia.org/wiki/Temperaturehttp://en.wikipedia.org/wiki/Temperaturehttp://en.wikipedia.org/wiki/Heat_transferhttp://en.wikipedia.org/wiki/Heat_transferhttp://en.wikipedia.org/wiki/Fick%27s_lawhttp://en.wikipedia.org/wiki/Electric_fieldhttp://en.wikipedia.org/wiki/Current_%28electricity%29http://en.wikipedia.org/wiki/Electrical_conductorhttp://en.wikipedia.org/wiki/Transmission_mediumhttp://en.wikipedia.org/wiki/Electric_charge


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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


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Metals: good conductors with electrical conductivity on the order of 107

-1m-1 (105 S/cm) Metallic bonding leads to a sea of electrons that are free to move around.

Insulators: electricalconductivity ~ 10-10 to 10-20-1m-1. Ionic or strong covalent bonds where valence electrons are tightly bound

(localized).

Semiconductors: electricalconductivity ~ 10-6 to 104-1m-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


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Electrical Conduction

Free electronsneeded forelectricalconduction(applied electricfield is sufficient togenerate large

number of freeelectrons).

METALS

SEMICONDUCTORS OR INSULATORS

Due to the bandgap, much more

energy input isnecessary to createcharge carriers(electrons inconduction band orholes in valenceband).


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Fermi level

Fermi level" is the term used to describe the top ofthe collection of electron energy levels at absolutezero temperature.

This concept comes from Fermi-Dirac statistics.Electrons are fermions and by the Pauli exclusionprinciple cannot exist in identical energy states. Soat absolute zero they pack into the lowest availableenergy states and build up a "Fermi sea" of electronenergy states.

The Fermi level is the surface of that sea at absolutezero where no electrons will have enough energy torise above the surface. The concept of the Fermienergy is a crucially important concept for theunderstanding of the electrical and thermalproperties of solids.

Both ordinary electrical and thermal processesinvolve energies of a small fraction of an electronvolt. But the Fermi energies of metals are on theorder of electron volts.

This implies that the vast majority of the electronscannot receive energy from those processesbecause there are no available energy states forthem to go to within a fraction of an electron volt of

their present energy. Limited to a tiny depth ofenergy, these interactions are limited to "ripples onthe Fermi sea".
http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/particles/spinc.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/pauli.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/pauli.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/solids/fermi2.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/solids/fermi2.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/solids/fermi2.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/solids/fermi2.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/pauli.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/pauli.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/particles/spinc.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.html


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Although the Fermi function has a finite value in the gap, there is noelectron population at those energies (that's what you mean by agap). The population depends upon the product of the Fermi function

and the electron density of states. So in the gap there are noelectrons because the density of states is zero. In the conductionband at 0K, there are no electrons even though there are plenty ofavailable states, but the Fermi function is zero. At high temperatures,both the density of states and the Fermi function have finite values inthe conduction band, so there is a finite conducting population.

The Fermi function f(E) gives theprobability that a given availableelectron energy state will beoccupied at a given temperature.The Fermi function comes fromFermi-Dirac statistics and has theform
http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disene.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disfd.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/quantum/disene.html


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Electrical conduction inSemiconductors

Bonding and band gap

Structure m.p. (K) Eg (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 electricalconduction. The smaller the band gap, the less energy isrequired to create charge carriers.

Conductivity of intrinsic (undoped) semiconductors:

kT

Egexp Conductivity increases with T.


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What is a conducting polymer?

Conjugated polymers: long conjugated systems;Energy states related with structural defectsDefects 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 holeslocalized in the interior of bands but are chargeddefects, localized long the polymeric chain.

Conjugated Polymers: Organic semiconductors with -bonds delocalizing along the polymer chain

Conjugated PolymersSynthetic Metals

go


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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 describean excitation similar to a single particle excitation as opposed to a collective excitation.

Both definitions mutually exclude each other as with the former definition collectiveexcitations which are no "real" particles are considered to be quasiparticles. The problemsarising from the collective nature of quasiparticles have also been discussed within thephilosophy of science, notably in relation to the identity conditions of quasiparticles andwhether or not they should be considered "real" by the standards of, for example, entityrealism.

Phonons are the quanta of classical sound waves and sound waves do not need thenotion of atoms.

Magnons are the quanta of classical spinwaves, which also do not need elementaryspins.

Photons inside an isolator are the quanta of classical dressed electromagnetic wavesand 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 chargedensity and mass density and no electrons or ions.

Polarons are the quanta of the oscillating polarization in a lightly dopedsemiconductor and also do not need elementary charge or mass.
http://en.wikipedia.org/wiki/Entity_realismhttp://en.wikipedia.org/wiki/Entity_realismhttp://en.wikipedia.org/wiki/Phononhttp://en.wikipedia.org/wiki/Magnonhttp://en.wikipedia.org/wiki/Photonhttp://en.wikipedia.org/wiki/Plasmonhttp://en.wikipedia.org/wiki/Plasma_oscillationhttp://en.wikipedia.org/wiki/Polaronhttp://en.wikipedia.org/wiki/Polaronhttp://en.wikipedia.org/wiki/Plasma_oscillationhttp://en.wikipedia.org/wiki/Plasmonhttp://en.wikipedia.org/wiki/Photonhttp://en.wikipedia.org/wiki/Magnonhttp://en.wikipedia.org/wiki/Phononhttp://en.wikipedia.org/wiki/Phononhttp://en.wikipedia.org/wiki/Entity_realismhttp://en.wikipedia.org/wiki/Entity_realism


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eParticles in physics

Elementary particlesFermions: Quarks: u d c s t b Leptons: e- e+ - + - + e

Bosons: Gauge bosons: g W Z0Other: Ghosts

Composite particlesHadrons: 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 particlesExotic hadrons: Exotic baryons: Pentaquark Exotic mesons: Glueball Tetraquark

Other: Mesonic molecule

Quasiparticles Davydov soliton Exciton Magnon Phonon Plasmon Polariton Polaron
http://en.wikipedia.org/wiki/List_of_particleshttp://en.wikipedia.org/wiki/Physicshttp://en.wikipedia.org/wiki/Elementary_particlehttp://en.wikipedia.org/wiki/Fermionhttp://en.wikipedia.org/wiki/Quarkhttp://en.wikipedia.org/wiki/Up_quarkhttp://en.wikipedia.org/wiki/Down_quarkhttp://en.wikipedia.org/wiki/Charm_quarkhttp://en.wikipedia.org/wiki/Strange_quarkhttp://en.wikipedia.org/wiki/Top_quarkhttp://en.wikipedia.org/wiki/Bottom_quarkhttp://en.wikipedia.org/wiki/Leptonhttp://en.wikipedia.org/wiki/Electronhttp://en.wikipedia.org/wiki/Electronhttp://en.wikipedia.org/wiki/Positronhttp://en.wikipedia.org/wiki/Positronhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Bosonhttp://en.wikipedia.org/wiki/Gauge_bosonhttp://en.wikipedia.org/wiki/Photonhttp://en.wikipedia.org/wiki/Gluonhttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/Faddeev-Popov_ghosthttp://en.wikipedia.org/wiki/Bound_statehttp://en.wikipedia.org/wiki/Hadronhttp://en.wikipedia.org/wiki/Baryonhttp://en.wikipedia.org/wiki/List_of_baryonshttp://en.wikipedia.org/wiki/Hyperonhttp://en.wikipedia.org/wiki/Nucleonhttp://en.wikipedia.org/wiki/Protonhttp://en.wikipedia.org/wiki/Neutronhttp://en.wikipedia.org/wiki/Delta_baryonhttp://en.wikipedia.org/wiki/Lambda_particlehttp://en.wikipedia.org/wiki/Sigma_%28particle%29http://en.wikipedia.org/wiki/Xi_particlehttp://en.wikipedia.org/wiki/Omega_particlehttp://en.wikipedia.org/wiki/Cascade_Bhttp://en.wikipedia.org/wiki/Cascade_Bhttp://en.wikipedia.org/wiki/Mesonhttp://en.wikipedia.org/wiki/List_of_mesonshttp://en.wikipedia.org/wiki/Quarkoniumhttp://en.wikipedia.org/wiki/Pionhttp://en.wikipedia.org/wiki/Kaonhttp://en.wikipedia.org/wiki/Rho_mesonhttp://en.wikipedia.org/wiki/J/%CF%88_particlehttp://en.wikipedia.org/wiki/Upsilon_particlehttp://en.wikipedia.org/wiki/Atomic_nucleushttp://en.wikipedia.org/wiki/Atomhttp://en.wikipedia.org/wiki/Exotic_atomhttp://en.wikipedia.org/wiki/Positroniumhttp://en.wikipedia.org/wiki/Moleculehttp://en.wikipedia.org/wiki/Hypothetical_particleshttp://en.wikipedia.org/wiki/Hypothetical_particleshttp://en.wikipedia.org/wiki/Superpartnerhttp://en.wikipedia.org/wiki/Axinohttp://en.wikipedia.org/wiki/Dilatinohttp://en.wikipedia.org/wiki/Charginohttp://en.wikipedia.org/wiki/Gluinohttp://en.wikipedia.org/wiki/Gravitinohttp://en.wikipedia.org/wiki/Higgsinohttp://en.wikipedia.org/wiki/Neutralinohttp://en.wikipedia.org/wiki/Sfermionhttp://en.wikipedia.org/wiki/Sleptonhttp://en.wikipedia.org/wiki/Squarkhttp://en.wikipedia.org/wiki/Axionhttp://en.wikipedia.org/wiki/Dilatonhttp://en.wikipedia.org/wiki/Goldstone_bosonhttp://en.wikipedia.org/wiki/Gravitonhttp://en.wikipedia.org/wiki/Higgs_bosonhttp://en.wikipedia.org/wiki/Tachyonhttp://en.wikipedia.org/wiki/X_and_Y_bosonshttp://en.wikipedia.org/wiki/W%27_bosonhttp://en.wikipedia.org/wiki/Z%27_bosonhttp://en.wikipedia.org/wiki/Category:Hypothetical_composite_particleshttp://en.wikipedia.org/wiki/Category:Hypothetical_composite_particleshttp://en.wikipedia.org/wiki/Exotic_hadronhttp://en.wikipedia.org/wiki/Exotic_baryonhttp://en.wikipedia.org/wiki/Pentaquarkhttp://en.wikipedia.org/wiki/Exotic_mesonhttp://en.wikipedia.org/wiki/Glueballhttp://en.wikipedia.org/wiki/Tetraquarkhttp://en.wikipedia.org/wiki/Mesonic_moleculehttp://en.wikipedia.org/wiki/Quasiparticlehttp://en.wikipedia.org/wiki/Davydov_solitonhttp://en.wikipedia.org/wiki/Excitonhttp://en.wikipedia.org/wiki/Magnonhttp://en.wikipedia.org/wiki/Phononhttp://en.wikipedia.org/wiki/Plasmonhttp://en.wikipedia.org/wiki/Polaritonhttp://en.wikipedia.org/wiki/Polaronhttp://en.wikipedia.org/wiki/Polaronhttp://en.wikipedia.org/wiki/Polaritonhttp://en.wikipedia.org/wiki/Plasmonhttp://en.wikipedia.org/wiki/Phononhttp://en.wikipedia.org/wiki/Magnonhttp://en.wikipedia.org/wiki/Excitonhttp://en.wikipedia.org/wiki/Davydov_solitonhttp://en.wikipedia.org/wiki/Quasiparticlehttp://en.wikipedia.org/wiki/Mesonic_moleculehttp://en.wikipedia.org/wiki/Tetraquarkhttp://en.wikipedia.org/wiki/Glueballhttp://en.wikipedia.org/wiki/Exotic_mesonhttp://en.wikipedia.org/wiki/Pentaquarkhttp://en.wikipedia.org/wiki/Exotic_baryonhttp://en.wikipedia.org/wiki/Exotic_hadronhttp://en.wikipedia.org/wiki/Category:Hypothetical_composite_particleshttp://en.wikipedia.org/wiki/Category:Hypothetical_composite_particleshttp://en.wikipedia.org/wiki/Z%27_bosonhttp://en.wikipedia.org/wiki/W%27_bosonhttp://en.wikipedia.org/wiki/X_and_Y_bosonshttp://en.wikipedia.org/wiki/Tachyonhttp://en.wikipedia.org/wiki/Higgs_bosonhttp://en.wikipedia.org/wiki/Gravitonhttp://en.wikipedia.org/wiki/Goldstone_bosonhttp://en.wikipedia.org/wiki/Dilatonhttp://en.wikipedia.org/wiki/Axionhttp://en.wikipedia.org/wiki/Squarkhttp://en.wikipedia.org/wiki/Sleptonhttp://en.wikipedia.org/wiki/Sfermionhttp://en.wikipedia.org/wiki/Neutralinohttp://en.wikipedia.org/wiki/Higgsinohttp://en.wikipedia.org/wiki/Gravitinohttp://en.wikipedia.org/wiki/Gluinohttp://en.wikipedia.org/wiki/Charginohttp://en.wikipedia.org/wiki/Dilatinohttp://en.wikipedia.org/wiki/Axinohttp://en.wikipedia.org/wiki/Superpartnerhttp://en.wikipedia.org/wiki/Hypothetical_particleshttp://en.wikipedia.org/wiki/Hypothetical_particleshttp://en.wikipedia.org/wiki/Moleculehttp://en.wikipedia.org/wiki/Positroniumhttp://en.wikipedia.org/wiki/Exotic_atomhttp://en.wikipedia.org/wiki/Atomhttp://en.wikipedia.org/wiki/Atomic_nucleushttp://en.wikipedia.org/wiki/Upsilon_particlehttp://en.wikipedia.org/wiki/J/%CF%88_particlehttp://en.wikipedia.org/wiki/Rho_mesonhttp://en.wikipedia.org/wiki/Kaonhttp://en.wikipedia.org/wiki/Pionhttp://en.wikipedia.org/wiki/Quarkoniumhttp://en.wikipedia.org/wiki/List_of_mesonshttp://en.wikipedia.org/wiki/Mesonhttp://en.wikipedia.org/wiki/Cascade_Bhttp://en.wikipedia.org/wiki/Cascade_Bhttp://en.wikipedia.org/wiki/Omega_particlehttp://en.wikipedia.org/wiki/Xi_particlehttp://en.wikipedia.org/wiki/Sigma_%28particle%29http://en.wikipedia.org/wiki/Lambda_particlehttp://en.wikipedia.org/wiki/Delta_baryonhttp://en.wikipedia.org/wiki/Neutronhttp://en.wikipedia.org/wiki/Protonhttp://en.wikipedia.org/wiki/Nucleonhttp://en.wikipedia.org/wiki/Hyperonhttp://en.wikipedia.org/wiki/List_of_baryonshttp://en.wikipedia.org/wiki/Baryonhttp://en.wikipedia.org/wiki/Hadronhttp://en.wikipedia.org/wiki/Bound_statehttp://en.wikipedia.org/wiki/Faddeev-Popov_ghosthttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/W_and_Z_bosonshttp://en.wikipedia.org/wiki/Gluonhttp://en.wikipedia.org/wiki/Photonhttp://en.wikipedia.org/wiki/Gauge_bosonhttp://en.wikipedia.org/wiki/Bosonhttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Neutrinohttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Tau_leptonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Muonhttp://en.wikipedia.org/wiki/Positronhttp://en.wikipedia.org/wiki/Positronhttp://en.wikipedia.org/wiki/Electronhttp://en.wikipedia.org/wiki/Electronhttp://en.wikipedia.org/wiki/Leptonhttp://en.wikipedia.org/wiki/Bottom_quarkhttp://en.wikipedia.org/wiki/Top_quarkhttp://en.wikipedia.org/wiki/Strange_quarkhttp://en.wikipedia.org/wiki/Charm_quarkhttp://en.wikipedia.org/wiki/Down_quarkhttp://en.wikipedia.org/wiki/Up_quarkhttp://en.wikipedia.org/wiki/Quarkhttp://en.wikipedia.org/wiki/Fermionhttp://en.wikipedia.org/wiki/Elementary_particlehttp://en.wikipedia.org/wiki/Physicshttp://en.wikipedia.org/wiki/List_of_particles


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How good is the conductivity ofpolymers, compared to metals


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Electrolytes short description

Ionic conducting electrolytes with lowelectronic conductivity

Solids, liquids or elastomers

Liquid electrolytes are preferred

liquids with high viscosity due to theconvenience or security


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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 theelectrode surfaces, releasing electrons from the chloride, and allow

electrons to be absorbed into the sodium.
http://en.wikipedia.org/wiki/Electrolytehttp://en.wikipedia.org/wiki/Atomhttp://en.wikipedia.org/wiki/Ionhttp://en.wikipedia.org/wiki/Sodiumhttp://en.wikipedia.org/wiki/Chlorinehttp://en.wikipedia.org/wiki/Redoxhttp://en.wikipedia.org/wiki/Redoxhttp://en.wikipedia.org/wiki/Chlorinehttp://en.wikipedia.org/wiki/Sodiumhttp://en.wikipedia.org/wiki/Ionhttp://en.wikipedia.org/wiki/Atomhttp://en.wikipedia.org/wiki/Electrolyte


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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 PCwith LiClO4 (explosive during drying) which can be

substituted by LiBF4

Choose of the electrolyte depend on theelectrochemical system


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Classification of Solid Electrolytes

Solid Electrolytes

organic inorganic

Polymeric

electrolytes Polyelectrolytes

Macromolecules

(PEO or PPO)

with Li+

saltsMolecular mass

low - liquids

intermediary -

viscous liquids

highsolids

almost rigid

Polymers with ionic

groups which

can give cationsor receive cations

(PolyAMPS)

have a groups

regular distributed

along the chain

that give the protons

Different oxides

(Cr2O3, Ta2O5);

Protonic and

Anionic conduction

(high for H+

good for Li+)Better than organic

due to the stability

for fotolitic degradation


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Inorganic Solid Electrolytes

P.M.S. Monk, R.J. Mortimer, D.R. Rosseinsky, Electrochromism:Fundamentals and Applications, VCH, Weinheim, 1995.


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Inorganic electrolytes

Significant resistance to the interphasecontact problems with contacts

Solution:

prototype of ECD with WO3Subsequent 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


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Other deficiencies

Relative fragility easy to broken

Disintegration of the coatings due to the expansionand contraction of the electrode films during the

insertion and desinsertion of the ions


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Solid Electrolytes

organic inorganic

Polymeric


Macromolecules

(PEO or PPO)

with Li+

saltsMolecular mass

low - liquids

intermediary -

viscous liquids

highsolids

almost rigid

Polymers with ionic

groups which


(PolyAMPS)

have a groups

regular distributed

along the chain


Different oxides

(Cr2O3, Ta2O5);

Protonic and

Anionic conduction

(high for H+





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Polyelectrolytes

Chitosan is obtained from chitin (structuralelement in the exoskeleton of crustaceans(shrimps, crabs, etc.)

At least 50% of amino groups.

Chitosan is positively charged and soluble inLow acidic solution.

Biodegradable and biocompatible.
http://upload.wikimedia.org/wikipedia/commons/9/90/Pandborealispile.jpghttp://upload.wikimedia.org/wikipedia/commons/f/fb/Chitosan_Haworth.gif


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Solid Electrolytes

organic inorganic

Polymeric


Macromolecules

(PEO or PPO)

with Li

+

saltsMolecular mass

low - liquids

intermediary -

viscous liquids

highsolids

almost rigid

Polymers with ionic

groups which


(PolyAMPS)

have a groups

regular distributed

along the chain


Different oxides

(Cr2O3, Ta2O5);

Protonic and

Anionic conduction

(high for H+





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AdvantagesPolymeric electrolytes can be formed in the form of

very thin films of large surface area giving highpower levels (>100 Wdm-3)

Fiona M. Gray Solid Polymer Electrolytes, Fundamentals and technological applicationsVCH Publishers, 1991.


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Solid Organic Electrolytes

P.M.S. Monk, R.J. Mortimer, D.R. Rosseinsky, Electrochromism:Fundamentals and Applications, VCH, Weinheim, 1995.


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Nafion

Nafion is a sulfonated tetrafluorethylene copolymer discovered in the late 1960s byWalther Grot of DuPont de Nemours. It is the first of a class of synthetic polymerswith ionic properties which are called ionomers. Nafion's unique ionic properties are aresult of incorporating perfluorovinyl ether groups terminated with sulfonate groupsonto a tetrafluoroethylene (Teflon) backbone. Nafion has received a considerableamount of attention as a proton conductor for proton exchange membrane (PEM) fuelcells because of its excellent thermal and mechanical stability.

The chemical basis of Nafion's superior conductive propertiesremain a focus of research. Protons on the SO3H (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.
http://en.wikipedia.org/wiki/Copolymerhttp://en.wikipedia.org/wiki/1960shttp://en.wikipedia.org/wiki/DuPonthttp://en.wikipedia.org/wiki/Ionomerhttp://en.wikipedia.org/wiki/Polytetrafluoroethylenehttp://en.wikipedia.org/wiki/Proton_conductorhttp://en.wikipedia.org/wiki/Proton_exchange_membrane_fuel_cellhttp://en.wikipedia.org/wiki/Proton_exchange_membrane_fuel_cellhttp://en.wikipedia.org/wiki/Sulfonic_acidhttp://en.wikipedia.org/wiki/Cationhttp://en.wikipedia.org/wiki/Artificial_membranehttp://en.wikipedia.org/wiki/Anionhttp://en.wikipedia.org/wiki/Electronhttp://en.wikipedia.org/wiki/Image:Nafion_structure.pnghttp://en.wikipedia.org/wiki/Electronhttp://en.wikipedia.org/wiki/Anionhttp://en.wikipedia.org/wiki/Artificial_membranehttp://en.wikipedia.org/wiki/Cationhttp://en.wikipedia.org/wiki/Sulfonic_acidhttp://en.wikipedia.org/wiki/Proton_exchange_membrane_fuel_cellhttp://en.wikipedia.org/wiki/Proton_exchange_membrane_fuel_cellhttp://en.wikipedia.org/wiki/Proton_conductorhttp://en.wikipedia.org/wiki/Polytetrafluoroethylenehttp://en.wikipedia.org/wiki/Ionomerhttp://en.wikipedia.org/wiki/DuPonthttp://en.wikipedia.org/wiki/1960shttp://en.wikipedia.org/wiki/Copolymer


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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

We wish to report the preparation of


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Photos during - ISPE-2006Foz do Igua

Brazil

The latter workers also observed that the

dissolution of potassium iodide inpoly(ethylene oxide) disrupts thecrystallinity of the polymer producing anelastomeric material at room temperature.

We wish to report the preparation ofcrystalline complexes of sodium andpotassium salts with poly(ethyleneoxide).


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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 byLundberg 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


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Photos duringISPE-2004

MragowoPoland


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a.c. and d.c.conductivity results

1 cal = 4.186 J


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ISPE-2004Mragowo-

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 electrolyteswill be available for either Li, Na or K.Especially thin film polymers will besuitable for an all solid state system, asa good contact is easily achieved withsoft materials..."


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In 1978 Prof. M. Armand showed the technological importanceof these new materials for storage energy devices.

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

Use of the alternative sources of energy as solar energy andwind, which generate the electricity. These need the low priceand high eficiency energy storage systems.


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Photos duringISPE-2004Mragowo

Poland


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Polymeric electrolytes history

D.Fauteux et al.Electrochim Acta, 40 (1995) 2185


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New class of materials

Polymeric electrolytes (solid polymeric electrolytes;SPEs) are new class of solid state ionics

Differences between polymeric electrolytes and ionicconducting materials as ceramics, glass, inorganiccrystals:

a) Charge transport - below Tgb) Conductivity values 100-1000 times lower than

other materials


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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


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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 ofchemical 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 inresponse to a precisely programmed stimulus allows unique new systems to bemade.

The number of applications based on volume phase transitions of polymeric gelincreases 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 andmolecules as a fundamental measure of molecular mobility and electrostaticinteractions is of great importance.

Physical Properties ofPolymeric GelsJ. P. Cohen Addad (Editor)

ISBN: 978-0-471-93971-9Hardcover324 pagesDecember 1995
http://eu.wiley.com/WileyCDA/Section/id-302479.html?query=J.+P.+Cohen+Addadhttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=J.+P.+Cohen+Addadhttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=J.+P.+Cohen+Addadhttp://eu.wiley.com/WileyCDA/Section/id-302479.html?query=J.+P.+Cohen+Addad


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Gel electrolytes

Polymers containing a low-molecular-

weight fraction that assist ionic transport.


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Current state of art in the field ofpolymer 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


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Chemical and Physicalmodifications

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 Al2O3, TiO2, SiO2 etc. Addition of carbon nanotubes


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Advantages and Disadvantages

Low crystallinity

High conductivity

Good stability

Low glass transition temperature

Transparency

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Polymer Ionics Introduction

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