Electrolyte and Ion Conduction

Introduction
▪ An electrolyte is a substance that conducts electricity through the movement of

free ions. The electrolyte is usually made by dissolving a salt in solvent such as

water (as in aqueous electrolyte) and acetonitrile (as in organic electrolyte).

▪ Such an electrolyte solution contains free cations and anions. If an electrical

potential is applied to such a solution, the cations in solution migrate to the

negative electrode, while the anions move to the positive electrode.

▪ All the electrochemical reactions occur at the interface between electrode and

electrolyte containing electrochemically active ions, which are mobile and able

to support current flow.

▪ In the electrochemical cells, the electrolyte containing mobile active ions must

exist between two electrodes to complete the electrochemical reactions.

▪ The properties and characteristics of the electrolyte are thus critically important

to the performance of the electrochemical systems.

▪ In the electrolyte, a solvent with good solvating power is necessary to generate

free ions (called as charge carriers), and one with low viscosity is needed to

allow for rapid transport of ions to and from electrodes, resulting in high ionic

mobility.

▪ This chapter will focus on the properties of electrolytes that are commonly used

in the electrochemical systems. It can provide you some intuition regarding the

factors that are important in selecting a suitable electrolyte system for a

practical application or experiments.

 Electrolyte
▪ Substances which ionize when salts dissolve in solvent such as water and

propylene carbonate are called electrolytes. An electric current will flow through

such an electrolyte solution, although solvent itself is a poor conductor of

electricity.

▪ When the current passes along the external circuit, there is a movement of

electrons through the circuit. The current is also able to pass in the electrolyte,

because the electrically charged ions (cations & anions) migrate between two

electrodes in the electrochemical system.

▪ Substances that can’t yield free ions or don’t have free ions are called non-

electrolytes. Note that non-electrolyte is not able to conduct current in a solution,

because there are no charge carriers.

Fig. Solutions of non-electrolytes such as ethanol do not contain free ions and cannot
conduct electricity. Solutions of electrolytes contain ions that permit the passage of
electricity. The ionic conductivity of an electrolyte solution is related to the number of
free ions in the electrolyte.
 Ionic Conductivity
▪ Electrochemical reactions in the electrochemical cells produce or consume ions

at electrodes, and the electrolyte provides the pathway for ions to flow between

electrodes in the cell.

▪ Accordingly, one of the most important quantities that an electrolyte must

possess to be useful in the electrochemical system is an ability to transport free

ions.

▪ The ability of electrolyte to conduct the charged particles (free ions) is called

ionic conductivity (σ).

▪ Ionic conductivity has unit of Ω-1 cm-1, or S/cm. The resistivity, usually denoted

by ρ, is the inverse of ionic conductivity. The unit of resistivity is Ω cm.

 Charge carriers in electrochemical system

Electrochemical Cells Charge Carrier

Lithium-ion Batteries Li+

Electric Double Layer Capacitors Et4N+, BF4-

Proton Exchange Membrane Fuel Cells H+

Dye-sensitized Solar Cells I-, I3-

→ I3-

I- ←

Lithium-ion battery EDLC Fuel cell DSSC

 Electrolytes in Fuel Cells
Phosphoric Acid Molten Carbonate Solid Oxide Proton Exchange
Fuel Cell Fuel Cell Fuel Cell Membrane Fuel Cell
(PAFC) (MCFC) (SOFC) (PEMFC)

Phosphoric Acid Molten Carbonate Solid Oxide Proton Exchange

Electrolyte
(H3PO4) (Li2CO3, K2CO3) (ZrO2 + Y2O3) Membrane (Nafion)

Charge carrier
H+ CO32- O2- H+
(electroactive)

H2+CO32-→
Anode reaction H2 → 2H++2e- H2+O2- → H2O+2e- H2 → 2H++2e-
H2O+CO2+2e-

1/2O2+2H++ 2e-→ 1/2O2+2H++ 2e- →

Cathode reaction 1/2O2+CO2+2e- → CO32- 1/2O2+2e -→ O2-
H2O H2 O

Operating 170 ~ 250 650 ~ 700 900 ~ 1000 70 ~ 90

Temperature (oC) (Low T) (Mid T) (High T) (Low T)

Power (kW) 50 ~ 200 10 ~ 300 10 ~ 220 1 ~ 50

Efficiency (%) 35 ~ 40 40 ~ 60 45 ~ 65 30 ~ 35
▪ Ionic conductivity is an intrinsic physical property of the electrolyte and given by

where l is the distance between electrodes (cm),

R is the resistance of the electrolyte (Ω),

A is the cross-sectional area of the electrode (cm2).

▪ The ionic conductivity characterizes the ability of an electrolyte to conduct ions

and for any material it depends on the temperature but not on the size and

geometry of the electrolyte.

▪ Representative values of ionic conductivity for some commonly used electrolytes

in the electrochemical systems are presented in Table 3.1.

Electrical Conductivity

e- + -

aqueous electrolyte > organic electrolyte

Table. Ionic conductivity of different electrolytes in the electrochemical applications

Electrolyte Solvent σ [10-3 S/cm] Application

H2SO4 (30 wt.%) H2O 730 Lead-acid battery

KOH (29.4 wt.%) H2O 540 Alkaline battery

NH4Cl (25 wt.%) H2O 400 Leclanche battery

LiPF6 (1 M) EC+DME (1:1) 16.6 Lithium-ion battery

LiCF3SO3 (1 M) EC+DME (1:1) 8.3 Lithium-ion battery

LiN(CF3SO2)2 (1 M) EC+DME (1:1) 13.3 Lithium-ion battery

[Et4N]+[BF4]- (1 M) AN 60 Electric double-layer capacitor

[Et4N]+[BF4]- (0.65 M) PC 10.6 Electric double-layer capacitor

LiI, I2 AN 25 Dye-sensitized solar cell

▪ Ionic conductivity in the electrolytes depends on two main factors.

(ⅰ) the number of free ions : ni

(ⅱ) the ability of the free ions to move in an electric field (ionic mobility) : i

▪ It should be noted that both cations and anions in the electrolyte contribute

to the ionic conductivity. Accordingly, the ionic conductivity is expressed by

 =  ni |zi| e i

where ni is the number of carrier ions,

zi is the valency of the carrier ions,

e is the elementary electric charge (1.6  10-19 C),

i is the ionic mobility.

▪ The ionic mobility is related to the diffusion coefficient by the Nernst-Einstein

equation

▪ Since Di is given by kT/6ri (Stoke’s law), the ionic mobility can be expressed

by

where ri is the radius of solvated ion,

 is the viscosity of electrolyte solution.

 ▪ In general, ionic conductivity increases with salt concentration to reach a

maximum value, and then decreases with further increasing salt concentration.

Decrease of ionic
Increase in number of mobility (μi)
charge carrier ions (ni)
▪ A method for the measurement of the ionic conductivity (liquid electrolyte) is

shown below.

▪ The electrode is usually made of platinum. It has a cell constant (K), which is

determined by the distance between the electrodes and their surface area. The

unit of cell constant is cm-1 .

filling level

Fig. Electrode for conductivity measurement of

liquid electrolyte

▪ The ionic conductivity of the liquid electrolyte can be calculated with the

measured solution resistance (R) and known cell constant (K). (σ = K/R)
▪ For solid electrolyte such as polymer electrolyte and inorganic electrolyte,

ac impedance method is usually used to measure the ionic conductivity.

전해질 저항 (R) 측정

𝒕
𝝈=
𝑹𝑨
▪ The dissolution of a salt in solvent can be described as a dissociation of the salt

in positive and negative ions. Solvents with unsymmetrical charge distribution

(polar solvents) possess a high permanent dipole moment.

▪ The interaction between ions and dipoles on solvent molecules (ion-dipole

interaction) is important for dissolving a salt in the electrolytes. The shell

formed around the ions by solvent molecules is termed solvation (hydration in

aqueous electrolytes).

▪ In order to dissolve salt in a solvent, the interaction energies between solvent

molecules as well as the lattice energy of the salt must be overcome. The ion-

dipole interactions provide the necessary energy for the compensation of the

strong lattice energy.

http://www.youtube.com/watch?v=CLHP4r0E7hg
Structure of Water

Intermolecular force between water molecules

▪ Lattice energy is defined as the energy required to separate a mole of an ionic
solid into free ions.
▪ It is a measure of the cohesive forces that bind ions. Two main factors that
contribute to the magnitude of the lattice energy are the charge and radius of
the bonded ions.
▪ Lattice energy is inversely proportional to solubility. That is, the higher the
lattice energy, the lower the solubility in solvent.
▪ The ionic conductivity of electrolyte depends on the number of ions present,

and it is normal to introduce the molar conductivity m, which is defined as

m =  / c

where c is the concentration of the electrolyte.

▪ If c is measured in the unit of mol/cm3, then the unit of Λm is S cm2/mol.

▪ The molar conductivity is found to change with the concentration.

① The number of free ions in the solution is not exactly proportional to the

concentration of the electrolyte.

② Ions interact strongly with one another, thus the ionic mobility is decreased

with increasing salt concentration.

The concentration dependence of molar conductivity indicates that there are two

classes of electrolyte. (strong electrolyte and week electrolyte).

1) Strong Electrolyte

▪ Strong electrolyte is a solution that is fully dissociated into free ions when salt

is dissolved in solvent.

▪ Molar conductivity depends slightly on the concentration of the salt (in general

decreases slightly with salt concentration).

▪ A good example is potassium chloride in water.

Strong electrolyte

Week electrolyte
▪ For strong electrolytes, Kohlrausch's law describes the observed concentration

dependence of the molar conductivity

m = mo - K c1/2

where mo is the limiting molar conductivity (the molar conductivity in the limit

of zero concentration when the ions are effectively far apart and do not interact

with one another)

K is the constant which depends on the stoichiometry of the electrolyte

c is the concentration of electrolyte solution

▪ By plotting Λm vs c1/2, the value of mo can be determined.

2) Week Electrolyte

▪ Weak electrolyte is solution that normally exist in a partially dissociated state

such that a large portion of the salt exists in an uncharged form, usually a

neutral molecule.

▪ A good example of a weak electrolyte is acetic acid in water. 0.1 M solution of

acetic acid in water is only about 1 % dissociated into protons and acetate ions.

▪ This fact makes the ionic conductivity of an acetic acid solution much less than

would be expected if one assumed full dissociation of the acid into free protons

and acetate ions. In this case, molar conductivity sharply falls to low values as

the concentration increases.

▪ Normally, the electrolytes chosen for making solvent-salt combinations for use

in electrochemical experiments are strong electrolytes. All the electrolytes in

Table 3.1 are strong electrolytes.

Strong electrolyte

Week electrolyte
(1) Strong electrolyte
• complete dissociation, high ionic conductivity
• examples : HCl, NaCl, NaOH, KOH

(2) Weak electrolyte

• partial dissociation, low ionic conductivity
• examples : acetic acid, NH3

(3) Non-electrolyte
• no dissociation, close to zero ionic conductivity
• examples : sugar, Fe2O3, Al2O3
 Transference Number
▪ The transference number (or transport number, t) is defined as the ratio of the

current derived from the specific ions (cation or anion) to the total current.

▪ For a solution containing two kinds of ions, the transference number of the

cation is given by

where i+ is the current carried by the cation,

i is the total current through the electrolyte,

+ is the ionic conductivity contributed by cation,

 is the total ionic conductivity,

▪ Because the total current is the sum of the cation and anion current, the sum of

the transference numbers for all the ions in electrolyte always equals unity.

t+ + t- = 1
▪ Differences in transference number arise from the differences in ionic mobility.

Thus, the ionic mobility is used to calculate the transference number, as given in

the following equation,

▪ For example, in an aqueous solution of hydrogen chloride, more than half of the

current is carried by the positively charged hydrogen ions (cations) and less than

half is carried by the negatively charged chloride ions (anions), because the

hydrogen ions are able to move faster, i.e., hydrogen ions have higher mobility

than chloride ions.

Q. Please show that
▪ If the cation transference number (t+) is close to 1, it implies that the ion

conduction in the electrolyte is mainly accomplished by the cation.

▪ A large Li+ transference number can reduce concentration polarization of

electrolytes during charge–discharge cycles in the lithium-ion batteries, and

thus produce higher power density.

▪ Thus, it is highly desirable that the cation transference number of lithium

ions approaches 1 in the electrolyte system.

▪ However, many electrolyte systems, either liquid or polymeric, have cation

transference numbers less than 0.5.

 Rechargeable Lithium-Ion Batteries

Negative Positive
electrode electrode

LiCoO2
C (LiC6)

anode (-) : LixC6 → C6 + x Li+ + x e cathode (+) : Li1-xCoO2 + x Li+ + x e → LiCoO2

Proton Exchange Membrane Fuel Cell (PEMFC)

anode (-) : H2 → 2H+ + 2e- cathode (+) : 1/2O2 + 2H+ + 2e- → H2O
Polymer Electrolyte for PEMFC

Single Ion Conductor (t+=1)

Case I : When the mobility of cation is higher than that of anion,

t+ > 0.5, t- < 0.5 (HCl solution)

Case II : When the mobility of cation is almost the same to that of

anion,

t+ ≈ t- ≈ 0.5 (KCl, NH4NO3 solution)

Case III : When the mobility of cation is lower than that of anion

t+ < 0.5, t- > 0.5 (KOH solution)

 Transference Number Measurements
▪ When an electrolyte has more than one mobile charged species, it is important

to determine not only the total ionic conductivity, but also the portion of the

current which is carried by each species, which is given by the transference

number.

▪ Many different techniques have been applied to transference number

measurements in the electrolyte.

▪ Among them, we will learn about moving boundary method, which depends on

the movement of the boundary between two adjacent electrolytes under the

influence of an electric field.

Moving Boundary Method

▪ One of the most accurate techniques is the moving boundary method, in which

the motion of a boundary between two ionic solutions having a common ion is

observed as a current flows.

▪ Let MX be the salt of interest and NX a salt giving a denser solution. The

solution of NX is called the indicate solution and it occupies the lower part of a

vertical tube.

▪ The MX solution (leading solution) occupies the upper part of the tube. There

is a sharp boundary between the two solutions.

▪ The mobility of the M ions must be greater than that of the N ions.
 -
leading solution
HCl

μM+> μN+

indicate solution
CdCl2
+
▪ When a current i is passed for time t, the boundary moves from AB to CD,

so all the M ions in the volume between AB and CD must have passed

through CD.

▪ That number is clANA, so that charge that the M ions transfer through the

plane is z+clAeNA. (z+clAF)

▪ The total charge transferred when a current i flows for time t is it.

▪ Therefore, the fraction due to the motion of the M ions, which is their

transference number is

▪ Hence, by measuring the distance moved, the transference number can be

determined.
Cells and Electrolytes

▪ Current flow between two electrodes in the electrochemical cells occurs

through the electrolyte and is related with electrolyte resistance.

▪ The magnitude of the resistance depend on the ionic conductivity of the

electrolyte and the geometric arrangement of electrodes in the cell. The

inverse quantity of resistance is conductance, and its unit is S or -1,

𝒅
𝑹=
𝝈𝑨
▪ Ohmic loss is given by iR, where i is the current and R is the solution

resistance. Note that the ohmic loss usually represents a source of error in

attempts to control and measure the potential of a working electrode relative

to a reference electrode while current is flowing.

▪ It is thus desirable to keep such a loss as low as possible, and one way to

achieve this is to use electrolytes having ionic conductivity as high as

possible.
Solvents

▪ Many organic solvents in addition to water are used in the electrolyte for

electrochemical experiments.

▪ One important property is the ability of a solvent to dissolve and dissociate

salts to achieve a reasonable high ionic conductivity (i.e., high dielectric

constant, > 20). The second property is that a solvent should have a low

viscosity for efficient ionic migration. ( < 1 cP)

▪ Other factors that should be considered include liquid range, volatility and

electrochemical stability. Table 3.3 presents a summary of selected properties

of commonly used solvents in electrochemistry and Fig 3.3. presents the

chemical structures of some of the solvents.

1.75

2.53
Dimethyl
Carbonate (DMC)

Ethylene
Carbonate (EC)
 Solid Electrolytes

▪ Most electrolytes are liquid solutions, but some electrolytes are solids (polymer

or inorganic) and some of those are crystalline solids.

<Liquid electrolyte> <Solid electrolyte>

Li+
 1) Polymer Electrolyte
A salt is dissolved in a solvating polymer matrix
Conduction Mechanism : Local segmental motion of polymer chain

O O O O O
M+
M+
O O O under electrical fieldO O O O O
X- X-
First suggestion by M. B. Armand

➢ Requirements of polymer for achieving high ionic conductivity

- Excellent Solvating Properties

- High Flexibility (Low Tg)

- Amorphous Structure
▪ Fast ion transport in solid polymer electrolytes is predominantly due to the

existence of amorphous phase in the polymeric host.

→ The larger the degree of amorphosity, the higher would be the ionic

conductivity.
crystalline region
 2) Inorganic Electrolyte
In order for an ion to move through an inorganic electrolyte, 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
 Sodium-sulfur battery
▪ A sodium-sulfur battery is an electrochemical cell composed of sodium anode,
-alumina solid electrolyte and sulfur cathode.

▪ This battery has a high energy density, high efficiency and long cycle life. Its
operating temperatures is about 300 to 350 °C.

▪ During the discharge process, the molten Na at anode

donates electrons to the external circuit. The sodium
ion is transported through the beta-alumina solid
electrolyte to the sulfur cathode. At cathode, the
electron reacts with sulfur to form sodium polysulfide.
The discharge process can be represented as follows:

2 Na + 4 S → Na2S4 (Ecell ~ 2 V)

▪ During the charging process, the reverse reaction takes

place.

Na2S4 → 2 Na + 4 S
 Ionic Liquid Electrolyte
▪ An ionic liquid is a molten salt in which the ions are poorly coordinated,

which results in liquid phase below 100 °C, or even at room temperature

(room temperature ionic liquids, RTIL). The term “ionic liquid” is often

extended to salts having a melting point below 100 oC.

▪ It consists of organic cation and inorganic anion. At least one ion has a

delocalized charge, which prevents the formation of a stable crystal lattice.

▪ It exhibits high ionic conductivity even without any solvent.

It has attractive properties such as non-flammability and

non-volatility.

EMI-BF4
 N+
ㅎ

Piperidinium

ㅐㅐㅐㅐㅐㅐㅐㅐㅐㅐㅐㅐ

Fig. Base structures of some cations and anions for ionic liquids.
Characteristics of ionic liquid

1. Liquid phase in a wide temperature range

Tesla model S catches fire

2. Non-flammable

3. No volatility (Low vapor pressure)

Charged cathode High current

4. Good electrochemical stability Li0.5CoO2 Overcharge
High temperature

5. A lot of combinations of cation and anion

1.2M LiPF6 in EC/DMC