Lithium-ion battery cathode chemistry

By : Arumugam Manthiram https://doi.org/10.1038/s41467-020-15355-0

• Presented by: Sankalp Sharma

• Roll number : 180671
• CHE635 course project presentation – Summer 2021
Contents
• Free Electron Model (FEM)
• Fermi Dirac Distribution function
• Density of States(DOS) for FEM
• LCAO & MO approach
• Band theory
• Bloch function and Density of states
• Brillouin Zone
• Birth of rechargeable batteries
• Discovery of oxide cathodes
• Layered Oxides
• Spinal Oxides
• Polyanion oxides
• Pros and Cons
• Conclusion
FREE ELECTRON MODEL
In free electron model the
metal is seen as a box in which
electrons are free to move, not
affected by the atomic nuclei or
by each other, just like gas
molecules in a box.
FREE ELECTRON MODEL:

For particle in box we know

E = h2 { (na)2 + (nb)2 + (nc)2} Note Degeneracy

8me a2 b2 c2

• If we substitute kx , ky and kz for naπ/a, nbπ/b and ncπ/c,

E = {(kx)2+(ky)2+(kz)2} x (ℏ)2
2me
• Now kx , ky and kz can be considered as the components of a vector, k, called the wave vector.
FREE ELECTRON MODEL:

E = k2 x (ħ)2
2me
• The highest occupied level is called the
Fermi level and its energy is Fermi
Energy, EF
KF

• So the value of k for EF is KF

• KF is radius of Fermi Sphere

• The electrons will occupy all the levels up

till Fermi Surface

From Introduction to SOLID STATE PHYSICS Charles Kittel

Fermi Dirac Distribution Function:
• The maximum energy that a free electron can have in a material at absolute temperature .i.e.
at 0K is known as Fermi energy level.
• The value of Fermi energy varies for different materials.
• Fermi-Dirac function
f(E) = 1_____
1 + e(E-Ef)/kBT

Fermi Dirac Distribution and

Energy Band Diagram

f(E) Vs (E-EF) plot

From Introduction to SOLID STATE PHYSICS Charles Kittel
DOS for FEM:
• Total number of electronic states, N = (Volume of fermi sphere)/(Volume element in K-space)

• The number with values between k and k+dk is 4/3π2V ((k+dk)3−k3) = 4/π2Vk2dk
• This is Density of states
• In terms of energy N(E)dE : √(2me)3E x (V/2π2h3)dE

A density of states curve based on

the free electron model. The
levels occupied at 0 K are shaded

From Introduction to SOLID STATE PHYSICS Charles Kittel

 LCAO & MO approach
• Free electron model can’t explain
insulators

• Materials have huge number of atoms

Orbital
energies for a
chain of N
hydrogen
atoms as N
increases.

From Introduction to SOLID

STATE PHYSICS Charles Kittel
Band Theory
Band Theory

CONDUCTION BAND

VALENCE BAND

Metals Semiconductors Insulators

 BLOCH FUNCTION:
• The eigen functions of the wave equation for a periodic potential are the product of a plane wave
exp(ik.r) times a function uk(r) with the periodicity of the crystal lattice.

Ψk(r) = uk(r).eikr
Applying Bloch function in 1D:
-----------H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H---------------

Notice Bloch
function is
repeating at an
interval of 2pi/a

From Introduction to SOLID STATE PHYSICS Charles Kittel

Density of States

From Introduction to SOLID STATE PHYSICS Charles Kittel

Brillouin zone
• A Brillouin zone is defined as a Wigner-Seitz
primitive cell in the reciprocal lattice. First Brillouin
zone is the smallest volume entirely enclosed by
planes that are the perpendicular bisectors of the
reciprocal lattice vectors drawn from the origin.
The birth of rechargeable lithium batteries
• Intercalation chemistry

• <2.5V

Li+

TiS2
The discovery of oxide cathodes
Increase the cell voltage
Lithium already in cathodes

Vbattery = Vanode - Vcathode

E of top of S2–:3p > E of top of the O2–:2p band

LAYERED OXIDE CATHODES

SPINEL OXIDE CATHODES

POLYANION CATHODES

From : Arumugam Manthiram’s paper in Nature

Layered Oxides
GOOD CONDUCTIVITY

GOOD REVERSIBILITY

~ 4V OPERATING VOLTAGE

NO NEED OF ELEMENTAL Li

~ 140 mA h/g CAPACITY

From : Arumugam Manthiram’s paper in Nature
LiCoO2
Layered Oxides
• LiCoO2 -> High cost and limited capacity

• NMC -> Nickel Manganese Cobalt Cathode

1 : 1 : 1

• Lesser cost
• Higher capacity
Spinel Oxides
FASTER CHARGE DISCHARGE

3-D STRUCTURAL STABILITY

Li
BETTER REVERSIBILITY

~4V AND <130 mA h/g

Mn is 100x CHEAPER THAN Co

POISONING OF GRAPHITE ANODES LiMn2O4

ELECTROLYTE INSTABILITY
From : Arumugam Manthiram’s paper in Nature
Polyanion Oxides
Operating Voltage :
3.0 V in Fe2(MoO4)3 and Fe2(WO4)3
3.6 V in Fe2(SO4)3

LiTi2(PO4)3, LiZrTi(PO4)3, 2-3 V

NbTi(PO4)3, SbTi(PO4)3

Olivine LiFePO4

THERMAL STABILITY
INDUCTIVE EFFECT
RICH COMPOSITIONAL SPACE
S-O bond is MORE COVALENT than Mo-O bond
LOW COST METAL
ENVIRONMENT FRIENDLY
From : Arumugam Manthiram’s paper in Nature
Conclusion
LAYERED OXIDE CATHODES

SPINEL OXIDE CATHODES

POLYANION CATHODES

• SAFER
• CLEANER
• HIGHER OUTPUT VOLTAGE
and above all
BASE FOR FUTURE
THANK YOu