L2: Solid Electrolytes

Professor S.R. Elliott and

Dr S.N. Taraskin
Lecture 1: Structure of Disordered Materials

Lecture Synopsis

Lecture 1:

Structure of Disordered Materials (SRE)

Lecture 2:

Defects (SRE)

Lecture 3:

Examples of Solid Electrolytes (SRE)

Lecture 4:

Mechanisms of Diffusion (SNT)

Lecture 5:

Fundamentals of Diffusion (SNT)

Lecture 6,7:

Random Walk and Approximations (SNT)

Lecture 8:

Conductivity and Disorder (SNT)

Lecture 9:

Depolarization Current (SNT)

Lecture 10:

Impedance Spectroscopy and Radiotracers (SRE)

Lecture 11:

NMR and QENS (SRE)

Lecture 12:

Applications (SRE)

 Solid electrolytes - or superionic conductors or fast-ion conductors - are materials in which

the ionic (cationic/anionic) conductivity is
comparable to that of liquid electrolytes, and
the electronic conductivity is negligible
In solids, atomic diffusion can only occur via
structural defects
- so need to understand disorder
Disorder is defined with respect to a reference
structure
- eg the ideal crystal

Salvador
Dali (1952)

SRE

Galatea
of the
Spheres

The Physics &

Chemistry of
Solids

Crystals
An ideal crystal is generated by the translationally periodic repeat of a unit cell.
A lattice is an infinite array of mathematical points having the translational periodicity of
the crystal
The unit cell is defined by the vectors a, b, c (in 3D)
Any 2 lattice points are connected by the vector

R ua vb wc

Unit cells can be: primitive (P), body-centred (I), side-centred (C), face-centred (F)

Disordered Materials

Two classes of materials have topologically disordered structures:

liquids & glasses

Liquids

Topological disorder plus dynamical disorder (orientational and

translational)

Types of disorder
Topological

Substitutional

Spin

Positional/vibrational

Slow cooling of a melt -> crystallization

- crystal nuclei grow into stable crystallites in liquid, before the
viscosity (exponentially) increases with decreasing temperature

Crystallization of melt is a first-order thermodynamic phase transition

(density discontinuity)

Crystallization

Glasses/Amorphous Solids
Topological (quenched) disorder
Rapid cooling of a melt supercooled liquid
- rapid increase with viscosity with decreasing temperature
precludes crystal nucleation and growth
transforms to a glass at Tg (glass-transition temperature)
glass = a solid liquid on the experimental timescale
amorphous = non-crystalline
Vitrification

Structure of Liquids and Glasses

Structure has no long-range order (LRO): no lattice, no unit cell.

But structure is (generally) orientationally isotropic
Statistical description in terms of spatial correlation functions
e.g. pair distribution functions, i.e. the atomic density function, (r)
Radial distribution function (RDF) is defined as:

J r 4 r 2 r
-it is the average probability of finding an atom in the distance interval
r r + dr from a given atom at r = 0

Area under an RDF peak gives the average atomic coordination number
Positions of RDF peaks give radii of neighbour shells

Short-range Order (SRO)

Absence of LRO in glasses and liquids does not mean that there is
no structural order whatsoever
Glasses and liquids can have (varying degrees of) SRO
- e.g. corner (O)-shared SiO4 tetrahedra in g-SiO2
- well-defined coordination numbers, bond lengths, bond angles

Bond-length and bond-angle disorder (c.f. widths of

first 2 RDF peaks) are not generally sufficient alone to destroy
LRO
Instead, fluctuations in the dihedral angle, , destroy correlations
between nearest-neighbour structural units for covalent systems.
P( )
ideal amorphous

Dihedral angle
ideal crystal

Structure Determination of Glasses and Liquids

X-ray, neutron or electron diffraction (scattering plus interference)
is commonly used to study the atomic structure of materials
For the case of crystals, with well-defined lattice planes (hkl),
Bragg diffraction occurs:

n 2dhkl sinhkl

A crystal acts like a 3D diffraction grating for X-rays etc, and

diffracted beams only lie in particular directions, at angles hkl
For amorphous materials, diffraction occurs over a range of angles
- Bragg spots (for crystals) become diffuse haloes (for glasses)

 Complex amplitude of a wave, scattered by atom i, is:

Fi = fi exp [i(k k0). ri] ,
where

4 sin
K k k0

wavevector transfer

Nb k0 is incident wavevector
k is scattered wavevector

The atomic scattering factor, fi, is constant for neutrons

- strongly decreasing function of K or for X-rays & e-

Total scattering intensity from a collection of (pairs of)

atoms (i,j) is generally:

where

f f expik k .r
i j

ij

rij ri rj

Amorphous materials are spatially isotropic overall.

The orientational average of the phase factor is:

expik k .r
0

ij

4 rij2

expiKrij cos 2r sind

2
ij

giving the Debye scattering equation:

I
i

sin Krij
fi fj Kr
j
ij

sin Krij
Krij

For a monatomic solid (fi = fj = f):

I f
2

sin Krij
f Kr
j
ij
2

Introducing the atomic-density distribution function i(rij)

(for origin atom i) gives:
I f f
2

sin Krij
i rij
dVi
Krij

where j.
Writing i(r) = <i(rij)>, and adding and subtracting a term
in the macroscopic average atomic density, o, gives:
I f 2 f 2 4 r 2 r o
i

where iN.

sin Kr
sin Kr
dr f 2 4 r 2 o
dr
Kr
Kr
i

 The last term in o represents scattering due to the finite

sample size (coinciding with the = 0o transmitted beam)
Hence
I Nf 2 Nf 2 4 r 2 r o

sin Kr
dr
Kr

Defining the structure factor, S(K) as:

SK I K / Nf 2

and the reduced scattering function, F(K), as:

F(K ) K[S(K ) 1]

then
Nb Fourier transform
F(K )

G(r )sin Kr dr

where the reduced RDF, G(r), is given by:

G(r ) 4 r r o J(r )/ r 4 r o

 F(K) and G(r) are therefore related via

a Fourier transform
Can obtain the RDF from measured scattering data
I(K) S(K) F(K)
by an inverse Fourier transform:
2
Nb limits: 0 < K <
G (r ) F ( K ) sin Kr dK