Muhammad Hilmy Alfaruqi

Email: hilmy@uts.ac.id / hilmy.alfaruq@gmail.com

WA: +82-10-4985-6302
Quiz Charge:

(C) LiFePO4 → Li1-xFePO4 + xLi+ + xe-

(A) xLi+ + xe- + C → LixC
1) LiFePO4  ~170 mAh/g
Discharge:

(C) Li1-xFePO4 + xLi+ + xe- → LiFePO4

2) LiV3O8  ~93 mAh/g (A) LixC → xLi+ + xe- + C

3) Li2Mn2O4  ~285 mAh/g

Adv. Mater., 19 (2007) 657

Quiz

∆G0 = ∆G0 product – ∆G0 reactant

∆G0 = nFE0

1) LiFePO4  ~3.2 V
2) LiMn2O4  ~3.4 V

Adv. Mater., 19 (2007) 657

LIB – Cathode Materials
Demand characteristics of cathode materials:

• Cathode materials should display reversible behavior and a flat potential so as to enhance energy efficient during
charge and discharge.
• Cathode materials should have high energy density and high power density.
• High cycle efficiency must be maintained.
• Structural stability is necessary to prevent the volume changes when lithium ions intercalate and deintercalate
during charge and discharge.
• Cathode materials should have electrochemical and thermal stability to prevent reactions with electrolyte.
• The particles of cathode materials must be globular with narrow grain size distribution to protect aluminum film
when making electrodes and to improve both particle-to-particle contact and electrical conductivity.
LIB – Layered Structure Cathode Materials

Structure and electrochemical properties:

• LiMO2 has the strong ionic character and the most densely
packed crystal structure.
• The spaces between oxygen ions are filled with transition
metal ions and lithium ions, so as to increase bulk density.
• The most densely packed layer of oxygen ions can be
achieved through Hexagonal Close Packed (HCP) and
Cubic Close Packed (CCP) arrangement.
• Ex: LiCoO2, LiMnO2, LiNiO2
LIB – Layered Structure Cathode Materials
 LIB – Layered Structure Cathode Materials
 Tetrahedral sites are occupied by ions
with an ionic radius ratio:
0.225 < r/R < 0.414
 Octahedral sites are filled with:
0.414 < r/R < 0.732
 Ionic radius ratio of 3d transition metals
ions: 0.5397 ≤ r(M3+)/R(O2-) ≤ 0.7024.
 And that of lithium ions: r(Li+)/R(O2-) =
0.7143.
 Because of those reasons, these ions
reside in the octahedral sites of LiMO2.
LIB – Cathode Materials Olivine
3Å
020 020

LiFePO4 structure

J. Alloys Compd., 509 (2011) 8130-8135

LIB – Cathode Materials
Pourbaix Diagram
Invented in 1930’s by Marcel Pourbaix (Belgian)
ENVIRONMENT

MATERIALS

ENVIRONMENT
Definition of Corrosion

 The destructive attack of a metal by chemical or electrochemical reaction with

its environment.
 Corrosion returns the metal to its oxidized state in chemical compounds that are
similar or even identical to the minerals from which the metal are extracted.
Definition of Corrosion

Aqueous corrosion:
Zn + 2HCl  ZnCl2 + H2
2Al + 3H2O  Al2O3 + 6H+

Rusting (karat):
2Fe + 2H2O + O2  2Fe(OH)2
2Fe(OH)2 + H2O + O2  2Fe(OH)3
Definition of Corrosion

Anodic reaction in corrosion:

1) Metal corrosion: M  M+n + ne-
2) Ferrous ion oxidation: Fe2+  Fe3+ + e-
3) Oxygen evolution: 2H2O  O2 + 4H+ + 4e-

Cathodic reaction in corrosion:

1) Hydrogen evolution in acid solution: 2H+ + 2e-  H2
2) Oxygen reduction in acid solution: O2 + 4H+ + 4e-  2H2O
3) Oxygen reduction in neutral or basic solution: O2 + 2H2O + 4e-  4OH-
4) Metal ion reduction: M3+ + e-  M2+
5) Metal deposition: M+ + e-  M
Thermodynamics of Corrosion

The tendency for any chemical reaction, including corrosion, is measured by the ∆G.
1) Mg + H2O + ½ O2  Mg(OH)2 ∆G˚ = -142.6 cal/mol; 1 cal = 4.1868 J
2) Cu + H2O + ½ O2  Cu(OH)2 ∆G˚ = -28.6 cal/mol
3) Au + 3/2H2O + ¾ O2  Au(OH)3 ∆G˚ = +15.7 cal/mol

Tendency to corrosion: Mg > Cu >> Au

G = G + RT ln Q
aA + bB ↔ cC + dD
Q = [C]c [D]d / [A]a [B]b
Thermodynamics of Corrosion

G = G + RT ln Q
nFE = nFE + RT ln Q
Pourbaix Diagram / E-pH Diagram

Graphical representations of thermodynamic and

electrochemical equilibria between metal and water,
indicating thermodynamically stable phases as a
function of electrode potential and pH.
E
 Predicts the spontaneous direction of reactions.
 Estimates the composition of corrosion products.
 Predicts environmental changes that will prevent or
reduce corrosion attack.
pH
Water Stability Diagram

In pure water there are two possible cathodic

reactions:
1) O2 + 4H+ + 4e- ↔ 2H2O
Oxygen dissolved in water is in equilibrium with water.
E = 1.23 – 0.0592pH

2) 2H+ + 2e- ↔ H2
Water is in equilibrium with gaseous hydrogen.
E = -0.0592pH
Standard Reduction Potential at 25o C
E = 1.23 – 0.0592pH  From where?
O2 + 4H+ + 4e- ↔ 2H2O
Pourbaix Diagram / E-pH Diagram

 A map of the most stable species in a solution,

as a function of the pH vs. electrochemical
potential E.
 Depend on temperature, pressure and most
E
important, the concentration of the reagent
present.
 Used for discussing the corrosion behavior of
different metals.

pH
Only the region between the blue line, representing
the stability region of pure water, are places where
stable Cu species can exist.
Pourbaix Diagram / E-pH Diagram

Lines represent equilibria between pairs of species.

There are three types:

Vertical lines involve non-redox equilibria which

E
only depend on pH i.e. there is a H+ in the reaction.
Cu2+ + H2O ↔ Cu(OH)2(s) + 2H+
Horizontal lines involve only electrons (redox) not
H+ e.g.
Cu2+ + 2e- ↔ Cu(s)
Sloped lines: involve both e- and H+ pH

2Cu2+ + 2H2O + 2e- ↔ Cu2O(s) + 2H+ Only the region between the blue line, representing
the stability region of pure water, are places where
stable Cu species can exist.