Diffusion Induced Delamination of a

Wrinkled Solid Electrolyte Interphase and

Silicon Thin Film on a Deformable Substrate
in Lithium-ion Batteries

Dual Degree Project - PART II (ME57004) report submitted to

Indian Institute of Technology Kharagpur
in partial fulfilment for the award of the degree of
Dual Degree (B.Tech + M.Tech)
in
Mechanical Engineering - Mechanical Systems Design
by
Deepro Ghosh
(18ME33004)
Under the guidance of
Dr. Jeevanjyoti Chakraborty

Department of Mechanical Engineering

Indian Institute of Technology Kharagpur
Spring Semester, 2022-23
 CERTIFICATE
This is to certify that the project report entitled “Diffusion Induced Delamination
of a Wrinkled Solid Electrolyte Interphase and Silicon Thin Film on a De-
formable Substrate in Lithium-ion Batteries” submitted by Deepro Ghosh (Roll
No. 18ME33004) to Indian Institute of Technology Kharagpur towards partial fulfilment of
requirements for the award of Dual Degree (B.Tech + M.Tech 5Y) in Mechanical Engineering
is a record of bonafide work carried out by her under my supervision and guidance during
Spring Semester, 2022-23.

Dr. Jeevanjyoti Chakraborty

Department of Mechanical Engineering
Indian Institute of Technology Kharagpur
Kharagpur - 721302
West Bengal, India

1
Abstract

In lithium-ion batteries, the active material of the anode is prone to degradation and loss
of capacity when exposed to the electrolytic solution. However, once the surface of the
active material reacts with the electrolyte, a Solid Electrolyte Interphase (SEI) layer is
formed as a result. This thin layer prevents the bulk active material from further chemical
degradation. Hence maintaining the electrochemical and mechanical stability of the SEI
layer is of fundamental importance to the performance of high-capacity anode materials
such as silicon. During cyclical charging and discharging of the battery, the active material
undergoes massive volumetric expansion and compression. This may lead to the mechanical
failure of the SEI layer through fracture or delamination from the active thin film material.
Surface instabilities like wrinkling of SEI layer has also been observed. In this study, we
have investigated the delamination of the SEI layer from the thin film post the wrinkling of
the SEI using finite element modelling. The SEI-electrode system is modelled as a trilayer
system. The interfaces are modelled using the Cohesive Zone Modelling approach. The
results from the present work can be used as guidelines for designing artificial SEI jackets to
prevent the degradation of the active material.

2
Contents

1 Introduction 1

2 Problem Description 5

3 Mathematical Model 7
3.1 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2 Stress Formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3 Cohesive Zone Modelling of the interfaces . . . . . . . . . . . . . . . . . . . . 9
3.4 Non-dimensionalisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.4.1 Diffusion and Stress Equilibrium Equation . . . . . . . . . . . . . . . 12
3.4.2 Cohesive Interface Properties . . . . . . . . . . . . . . . . . . . . . . 13
3.5 Boundary Conditions and Initial Conditions . . . . . . . . . . . . . . . . . . 13
3.6 Software Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

4 Results and Discussion 17

4.1 Elastic SEI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.1.1 Effect of Interfacial Strength and Bonding Energy . . . . . . . . . . . 23
4.1.2 Effect of SEI Stiffness and Bonding Energy . . . . . . . . . . . . . . . 32
4.2 Elastic Perfectly Plastic SEI . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.2.1 Effect of Interfacial Strength and Bonding Energy . . . . . . . . . . . 37

5 Conclusion and Future Work 38

3
Chapter 1

Introduction

The paramount amount of research and development related to batteries is being driven by
an ever-increasing demand for portable electronic devices. Rechargeable lithium-ion batter-
ies have been accepted as one of the most suitable choices to power these devices. Lithium
is the lightest metal making it possible to manufacture high-energy-density storage devices.
The four primary functional components of a lithium-ion battery are the cathode, the anode,
the electrolyte and the separator. A lot of research is being driven towards the development
of high-capacity anode materials as they store the bulk of the lithium when the battery is be-
ing charged. Commercially, positive electrodes generally used are metal oxides or phosphates
(like LiCoO2 , LiF eP O4 ), and negative electrode materials are graphite, tin and some alu-
minium alloys. Recent research has identified silicon as a promising replacement for graphite
as the anode material (Ellis et al. (2010)). Silicon nanospheres and nanowires have exhibited
high energy storage capacity of around 4200 mAhg −1 for Li15 Si4 . However, the high energy
density brings its own challenges. Silicon in its fully lithiated state experiences a volumetric
expansion of 300% (Beaulieu et al. (2001)).
The active material, when exposed to the electrolytic solution, undergoes a degradation
reaction. Once the surface reacts, a thin Solid Electrolyte Interface (SEI) is formed. Accord-
ing to studies such as Lu et al. (2014), Tokranov et al. (2014) and Tokranov et al. (2016), the
SEI that forms in the carbonate electrolytes has bilayer structure. The outer layer consists
of organic decomposition products whereas the inner layer contains more inorganic products
(e.g. Li2 CO3 , LiF , etc).

1
 Chapter 1. Introduction

Figure 1.1: Formation of SEI on silicon anode, credits: Xu (2011)

The SEI layer acts like a protective covering preventing the bulk from further reaction.
Thus the mechanical and electrochemical stability of the SEI layer plays an essential role
in the performance of Li-ion batteries. However, the colossal volumetric change of silicon
during cyclic lithiation and delithiation causes large deformation and mechanical degradation
fracture and delamination of the SEI, and thus the SEI stability is widely recognized as a
major roadblock for developing Si anodes.
A lot of theoretical research has been dedicated to modelling the evolution of stresses in
electrodes during charging or discharging. The modelling of diffusion-induced stress can be
traced back to work by Prussin (1961), where the analogy between diffusion-induced stress
and thermal stress was used. Cheng & Verbrugge (2009) developed analytic solutions for
the evolution of stresses and elastic strain energy within a spherical electrode particle un-
der either galvanostatic (constant current) or potentiostatic (constant potential) mode of
operation. Their work was under the purview of small deformation to model the coupled
chemo-mechanical behaviour of the electrode nanoparticle. However, experimental work,
such as that conducted by Sethuraman et al. (2010), revealed that silicon undergoes plastic
 Chapter 1. Introduction

deformation during cyclical charging. Based on these experimental results, researchers have
tried to incorporate finite deformation and plasticity in their modelling of silicon electrodes.
Zhao et al. (2011) considered the coupled plastic deformation and lithiation in a spherical sil-
icon anode. Bower et al. (2011) developed a systematic theory to include finite deformation,
diffusion, plastic flow and electrochemical reaction in the Si anode of Li-ion batteries.
Only recently, studies have been conducted towards the examination of stresses induced
in the SEI due to its growing importance. He et al. (2017) investigated the evolution of
stresses in a heterogeneous elastic SEI to capture the bilayer structure. Tanaka et al. (2018)
used the material point method to study the effect of plasticity on the mechanical failure
of a homogeneous SEI layer. Guo et al. (2020) investigated the mechanical failure of a
bilayer SEI with integrated in-situ AFM, ex-situ FIB measurements and finite element mod-
elling. They discovered the inner inorganic layer is devoid of any cracking, implying higher
fracture toughness. The cracks started at the outer organic layer and got arrested at the
inorganic/organic boundary. Interfacial delamination was only observed between the outer
and inner SEI layers, while the inner layer was well bonded to the underlying Si. Thus the
mechanical well-being of the inner inorganic layer is sufficient for the passivation of the un-
derlying active thin film. Liu et al. (2019) analysed the wrinkling and ratcheting behaviour
of the SEI layer during cyclic lithiation and delithiation.
A lot of research has been geared towards studying the interfacial debonding of the
electrode from the current collector, which may lead to loss of electrical contact. The work
by Lu et al. (2013) assumes the active layer as a thin film and the current collector to a semi-
infinite deformable substrate. Liu et al. (2017) studied interfacial debonding by considering
a finite deformation model. Lu et al. (2019) investigated the delamination of the thin film
and substrate by assuming the substrate to be rigid. Guo et al. (2020) employed cohesive
zone modelling (CZM) to model the interfaces of the outer and inner SEI layer, the inner
SEI layer and silicon thin film layer, and the Si thin film and the Cu substrate layer.
 Chapter 1. Introduction

Figure 1.2: Progressive failure of SEI layer

For our work, we are considering a homogeneous SEI layer. We assume that the SEI
layer is already wrinkled. According to figure 1.2, we investigate the delamination of the SEI
layer in the post-wrinkled regime.
Chapter 2

Problem Description

Figure 2.1: Schematic of the layered structure of SEI, active thin film layer and substrate
during galvanostatic discharging.

Consider a wrinkled Solid Electrolyte Interphase (SEI) layer adhesively bonded to the active
thin film (silicon electrode) as shown in Figure 2.1. The thin film is also adhesively attached
to a substrate (current collector). The thin film is subjected to volumetric contraction by
lithium delithiation through galvanostatic discharging. The lithiated Si, Cu, and SEI are
assumed to be isotropic, elastic-perfectly plastic, and initially stress-free. The interfaces are
modelled using Cohesive Zone Modelling (CZM). The geometry is axisymmetric about r = 0,
and the origin of the cylindrical coordinate system (r, θ, z) is the centre of the interface of the
SEI and the thin film. The substrate is constrained at the bottom and the lateral surface.
When the delithiation starts, diffusion-induced stresses will generate within the thin film,
leading to delamination of the SEI-thin film and thin film-substrate interface. In this study,

5
 Chapter 2. Problem Description

one-way coupling is considered where diffusion drives the stress generation and hence the
ensuing delamination. The coupled diffusion and mechanical problem is solved using the
commercial FEM software ABAQUS/Standard. The influence of the wrinkled morphology
on the subsequent delamination and fracture of the SEI is investigated and compared with
that of a flat SEI layer.
Chapter 3

Mathematical Model

3.1 Diffusion
A cylindrical polar coordinate system of (r, θ, z) is used, and the origin of the coordinate
system is the centre of the interface between the SEI layer and the thin film.
Let c(r, z, t) denote the concentration field of the lithium in a discharging electrode.
The electrode is being discharged with a constant current density of in . The beginning of
our study is set to time t = 0 when the thin film is fully charged. Here we consider an
amorphous silicon disk-like thin film of radius R and thickness H. The radius and thickness
of the substrate are Rs and Hs , respectively. The SEI layer is considered to be of thickness
and amplitude HSEI . Diffusion is only considered to be occurring inside the active layer. The
SEI layer sits like a fully permeable material that does not store any charge. The diffusion
equation in cylindrical coordinates is given as follows:
 
∂c 1 ∂ ∂Jz
= (rJr ) + , (3.1)
∂t r ∂r ∂z

where Jr and Jz denote the flux of the lithium ions in radial and longitudinal directions,
respectively. The flux J can be thermodynamically related to the chemical potential µ as
expressed by Li et al. (2019):

Dc
J=− ∇µ, (3.2)
Rg T

7
 Chapter 3. Mathematical Model

where D is diffusivity, T is absolute temperature and Rg is the gas constant. For a dilute
solution the chemical potential can be written as (Li et al. (2019)):

µ = µ0 + Rg T ln c, (3.3)

The expressions for Jr and Jz are given as:

∂c
Jr = −D , (3.4a)
∂r
∂c
Jz = −D , (3.4b)
∂z

where D is the diffusivity of the active material. Putting Equations (3.4) back in Equation
(3.1), we get:

∂ 2 c 1 ∂c ∂ 2 c
 
∂c
=D + + (3.5)
∂t ∂r2 r ∂r ∂z 2

3.2 Stress Formulation

Using the analogy between thermally induced stress and diffusion-induced stress (DIS)
(Prussin (1961), Cheng & Verbrugge (2009)), the total strain increment can be decomposed
as

Ω
dεij = dεij el + dεij pl + dcδij , (3.6)
3

Ω
where dεij el is the elastic part, dεij pl is the plastic part and
dcδij is the strain increment
3
due to diffusion where Ω is the diffusion partial molar volume of lithium.
The strain tensor εij is given as

1
εij = (ui,j + uj,i ), (3.7)
2

where ui is a component of the displacement vector.

 Chapter 3. Mathematical Model

For an isotropic, elastic material, the elastic strain is defined as

1
εij el = [(1 + ν)σij − νσkk δij ], (3.8)
E

where σij is a component of the stress tensor, E is the Youngs modulus and ν is the Poisson’s
ratio.
The strain due to diffusion is given by

Ω
εch
ij = cδij (3.9)
3

The plastic strain evolves according to J2 flow theory and the material yields according
to the Von-Mises yield condition with Y as the yield stress of the electrode in the uniaxial
tensile test.
It should be noted that since the SEI layer sits like a permeable jacket and the substrate
is impervious to lithium, diffusion-induced stresses are absent in these domains. Hence, the
total strain εij in these domains consists only of the elastic and plastic components.
In the absence of any body-force the mechanical equilibrium equation is given by:

∇·σ =0 (3.10)

As the geometry is axisymmetric, Equation 3.8 results as,

∂σrr ∂σrz σrr − σθθ

+ + = 0, (3.11a)
dr dz r
∂σrz ∂σz σrz
+ + =0 (3.11b)
dr ∂z r

3.3 Cohesive Zone Modelling of the interfaces

The cohesive behaviour of both interfaces is described by the bilinear traction-separation
(σ − δ) model. The interface cohesive bonding is considered isotropic and linear elastic, and
the normal and shear direction behaviour are uncoupled.
An interface damage parameter M is defined to characterise the extent of interfacial
 Chapter 3. Mathematical Model

decohesion. M varies from 0 to 1, where 0 represents no damage, and 1 corresponds to

complete delamination. The interfacial stresses increase linearly with the separation between
the two interfaces, until damage initiates, that is M is just greater than 0.
The relation between the traction components of the interface and the separation between
the two surfaces of the thin film and substrate or the thin film and the SEI, is given by (Liu
& Yang (2014))

⟨σn ⟩ = (1 − M )K⟨δn ⟩, (3.12a)

σt = (1 − M )Kδt , (3.12b)

where σn and σt are the traction in normal and shear direction, respectively. ⟨δn ⟩ and δt
represent the separation in the normal and shear direction, respectively. K is the interface
stiffness. Here, ⟨·⟩ is known as the Macauley bracket, which is

x, for x ≥ 0

⟨x⟩ = (3.13)
0 for x < 0


A quadratic stress criterion gives the interface damage initiation, as described by Liu &
Yang (2012),

⟨σn ⟩2 + σt2 = σ02 . (3.14)

Here σ0 is the interface strength, which is the peak stress when the interface fails purely in
the normal or shear direction.
The interfacial bonding energy (G0 ) determines the eventual failure of the interface. G0
is the work of adhesion and is equal to the area under the traction-separation curve. A linear
mixed mode fracture energy (Liu & Yang (2014)) is used to characterise the propagation of
interfacial failure as

Gn + Gt = G0 . (3.15)
 Chapter 3. Mathematical Model

Here Gn and Gt are the work done by tractions and their conjugate separations in the normal
or the shear direction, respectively. G0 is the work of adhesion required to initiate complete
failure in either the normal or tangential direction.
The damage parameter M can be defined in terms of the maximum effective separation
δemax , as 
0, for δemax ≤ δe0 = σK0






f max
M = δemax(δe −δe0 ) (3.16)
δ (δ f
−δ 0)
, for δe0 < δemax < δef

 e e e

1, for δemax ≥ δef = 2G0


σ0

The effective separation is defined as,

q
δe = ⟨δn ⟩2 + δt2 (3.17)

Here, δe0 is the effective separation at damage initiation and δef is the effective separation
at complete delamination.
The properties of the cohesive layer at the interface of the SEI and the Si thin film are not
available in the literature due to the difficulties in measuring SEI toughness. Since the SEI
layer grows naturally on the thin film, we have assumed it is bonded more strongly to the
thin film than the cohesive bonding of the thin film and substrate. For numerical purposes,
the interfacial properties of the SEI thin film interface (K, σ0 and G0 ) are considered to be
double or more than that of the thin film-substrate interface. While assuming the interfacial
properties of the SEI thin film interface, the constraint G0 ≥ σ0 2 /2K, from an energy
viewpoint, has been imposed.
 Chapter 3. Mathematical Model

3.4 Non-dimensionalisation

3.4.1 Diffusion and Stress Equilibrium Equation

We use the following non-dimensionalizing scheme for ease in numerical simulations:

r z u
r̃ = ; z̃ = ; ũ = ;
H H H
w cF D tD
w̃ = ; c̃ = ; t̃ = 2 ;
H |in |H H
F F σ
J˜r = Jr ; J˜z = Jz ; σ̃ = ;
|in | |in | σtf
E σY
Ẽ = ; σ˜Y =
σtf σtf

where F is Faraday’s constant and σtf is the yield stress of the active thin film. After the
aforementioned non-dimensionalization is carried out, the non-dimensional fluxes are given
as:

∂c̃
J˜r = − , (3.18a)
∂r̃
∂c̃
J˜z = − . (3.18b)
∂ z̃

The non-dimensional diffusion equation is:

∂ 2 c̃ 1 ∂c̃ ∂ 2 c̃
 
∂c̃
= + + (3.19)
∂ t̃ ∂r̃2 r̃ ∂r̃ ∂ z̃ 2

The stress equilibrium equations will be:

∂ σ̃rr ∂ σ̃rz σ̃rr − σ̃θθ

+ + = 0, (3.20a)
∂r̃ ∂ z̃ r̃
∂ σ̃rz ∂ σ̃zz σ̃rz
+ + = 0, (3.20b)
∂r̃ ∂ z̃ r̃
 Chapter 3. Mathematical Model

3.4.2 Cohesive Interface Properties

We use the following non-dimensionalizing scheme for the cohesive interface properties:

σr,z δr,z Gr,z

σ̃r,z = ; δ̃r,z = ; G̃r,z =
σtf δef G0

3.5 Boundary Conditions and Initial Conditions

The electrode particle is assumed to be charged at t̃ = 0. The relevant initial condition will
be:

c̃ = 1, at t = 0 (3.21)

As de-lithiation is assumed to be galvanostatic, the lithium flux on the surface of the electrode
is constant. The flux boundary conditions for diffusion in the thin film for the case described
in Figure 2.1 will be:

∂c̃
= −1, at z = 0, for 0 ≤ r ≤ R (3.22)
∂ z̃

The flux across the thin film and substrate interface is zero for an electrochemically
inactive current collector. Also, the radial flux is also zero due to the axisymmetry of our
geometry. Hence the relevant boundary conditions are:

J˜z = 0, at z = −H, for 0 ≤ r ≤ R, (3.23a)

J˜r = 0, at r = 0, for − H ≤ z ≤ 0. (3.23b)

Due to the axisymmetric nature of our geometry, the radial displacement at the centreline
of our geometry is zero:

ũ = 0, at r = 0, for − (Hs + H) ≤ z ≤ HSEI . (3.24)

 Chapter 3. Mathematical Model

The substrate is constrained at the bottom and the lateral surfaces. Hence:

ũ = w̃ = 0, at z = −(Hs + H), for 0 ≤ r ≤ Rs , (3.25a)

ũ = w̃ = 0, at r = Rs , for − (Hs + H) ≤ z ≤ −H. (3.25b)

The rest of the surfaces are considered to be traction free. Hence the boundary conditions
for the geometry in Figure 2.1 is:

σ̃zz = σ̃rz = 0, at z = HSEI , for 0 ≤ r ≤ R, (3.26a)

σ̃rr = σ̃rz = 0, at r = R, for − H ≤ z ≤ HSEI , (3.26b)

σ̃zz = σ̃rz = 0, at z = −H, for R ≤ r ≤ Rs , (3.26c)

 Chapter 3. Mathematical Model

3.6 Software Description

(a)

(b)

Figure 3.1: Position of cut lines for (a) wrinkled SEI, (b) planar SEI

The coupled thermal-displacement module of ABAQUS/Standard (Smith (2009)) was used

to analyse the deformation in the wrinkled and the planar SEI. The thermal analysis lever-
aged the analogy between thermal and diffusion-induced stresses. Quadrilateral elements
of element size one-tenth of the SEI layer thickness were used in the SEI domain. Finite
sliding was used to describe the interfacial interactions with the SEI interface and substrate
interface, serving as the master surfaces. The diffusion-induced delamination process was
simulated for multiple interfacial strengths and bonding energies of the SEI-thin film interface
and for different Young’s modulus of the SEI layer.
 Chapter 3. Mathematical Model

Table 3.1: Values of material properties and operating parameters

Material property or parameter Value

D, diffusivity of Si 10−16 m2 s−1 a
Etf , Young’s modulus of active thin film (Si) 90 GPa b
Esb , Young’s modulus of substrate 122 GPa c
ESEI , Young’s modulus of SEI layer 3-10 GPa f
σtf , Yield stress of active thin film (Si) 1.5 GPa c
σsb , Yield stress of substrate 0.1 GPa c
σSEI , Yield stress of SEI layer 1% of ESEI f
νtf , Poisson’s ratio of active thin film (Si) 0.22 c
νsb , Poisson’s ratio of substrate 0.35 c
νSEI , Poisson’s ratio of SEI layer 0.30
cs , Maximum surface concentration 0.36 × 106 mol m−3 d
Rg , universal gas constant 8.314 JK−1 mol−1
T , temperature 298.15 K
F , Faraday’s constant 96500 C/mol
Ω, diffusion partial molar volume 1.20 × 10−5 m3 mol−1 c
K, Interface stiffness (thin film-substrate) 1500 GPa/µm c
σ0 , Interface strength (thin film-substrate) 0.15 GPa c
G0 , Interfacial Bonding Energy (thin film-substrate) 1 J/m2 e
R, Radius of film 10 µm
H, Height of film 1 µm
HSEI , Thickness of SEI layer 0.1H
a
Ma et al. (2015)
b
Yeerella et al. (2020)
c
Liu et al. (2017)
d
Sarkar et al. (2017)
e
Haftbaradaran et al. (2012)
f
Guo et al. (2020)
Chapter 4

Results and Discussion

4.1 Elastic SEI

Figure 4.1, 4.2, 4.3 and 4.4 shows the temporal evolution of the stress components of σ̃rr and
σ̃zz respectively in the battery anode structure where the SEI-thin film interface properties
are K = 3000 GP a/µm, σ0 = 0.30 GP a, G0 = 2 J/m2 , and ESEI = 10 GP a. Due to the
outflux of lithium, the thin film shrinks in size. As expected, according to Pal et al. (2014),
He et al. (2012), Lu et al. (2013) and Lu et al. (2019), the galvanostatic discharging process
leads to a concave and radially contracting deformation. It can be observed that the thin
film separates from the substrate through mode I failure. For the planar SEI, the failure
mechanism at the SEI-thin film interface is mode II, whereas, in the case of the wrinkled
SEI, the failure mode is complicated. At the outer edge, delamination initiates through the
slipping of the SEI on the thin film; however, at a later time, the crests of the SEI start
separating from the thin film in the normal direction, indicating mode I failure.
In Figure 4.1a, in the wrinkled SEI, there is highly compressive radial stress in the
crests near the interface with the thin film. However, extremely high tensile stresses are
concentrated in the thin film near the troughs. The magnitude of the compressive stress
zones in the SEI keeps on decreasing with time. After the crests of the SEI are completely
delaminated from the thin film as seen in 4.2c, the radial stress in the peaks is highly tensile.
In Figure 4.1b, in the planar SEI, there exists a zone of highly compressive stress near
the outer edge. It is observed that the upper section of the thin film is in tensile stress.

17
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.1: Temporal evolution of σ̃rr at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.1; (c), (d) t̃ = 0.2.
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.2: Temporal evolution of σ̃rr at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.3; (c), (d) t̃ = 0.4
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.3: Temporal evolution of σ̃zz at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.1; (c), (d) t̃ = 0.2
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.4: Temporal evolution of σ̃zz at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.3; (c), (d) t̃ = 0.4
 Chapter 4. Results and Discussion

In Figure 4.1b and 4.1d, and 4.2b and 4.2d due to continued delithiation, the thin film
separates from the substrate and keeps on pushing on the SEI layer, which leads to an
increase in the span of the zone of high compressive stress in the SEI which shifts towards
the centre of the structure. Another interesting observation is that initial zones of tensile
stress decrease, and as the discharging continues, compressive stress zones increases. If we
compare the evolution of σ̃rr in Figure 4.1 and 4.2 and σ̃zz in Figure 4.3 and 4.4, due to a
bending type of contraction of the thin film the axial stress σ̃rr generated is much greater
than the longitudinal stress σ̃zz . The longitudinal stress, σ̃zz generated in the SEI, is almost
compressive throughout, with the exception of being tensile near the interface with thin film
in the crest region.
 Chapter 4. Results and Discussion

4.1.1 Effect of Interfacial Strength and Bonding Energy

Figures 4.5, 4.6, 4.7 and 4.8 show the spatial variation evolution of the radial stress σ̃rr across
the cutlines as depicted in 3.1a, for different bonding energies. The stiffness of the SEI-thin
film interface is constant (K = 3000 GP a/µm) across all cases, and the Youngs modulus of
the SEI is taken as ESEI = 10 GP a. The interfacial strength considered is σ0 = 0.30 GP a.
The radial stresses generated in the SEI are highly compressive in nature, as evident from
Figure 4.5 to 4.8. The peak compressive stress is achieved at the top surface of the SEI layer.
Hence this will ensure that if any crack is present at the top surface of the SEI layer, it will
not propagate. The effect of the variation of the interfacial bonding energy is not felt in the
initial stages of the simulation (from Figure 4.5 to 4.6). However, at a later stage in Figure
4.8, we can see that there is a stark difference in the radial stress in the SEI corresponding
to G̃ = 0.02, as compared to the higher bonding energies. The magnitude of the compressive
stress is less compared to the stresses generated for the higher bonding energies.
The stress within the thin film evolves from compressive to tensile as we move from the
thin-film substrate interface to the thin film-SEI interface. The stress within the thin film is
mostly unaffected by the bonding energy at the thin film-SEI interface.
From Figures 4.9 to 4.12, we plot the variation of the Damage Parameter M (equation
3.16), evaluated at the thin film-SEI interface across various timestamps. In Figures 4.9,4.10
and 4.11, the process of delamination in a wrinkled SEI and a planar SEI have been compared.
It can be observed that in the wrinkled SEI delamination initiates at one of the peaks (4.9a)
near the outer edge, unlike the planar SEI (figure 4.9b) where the separation from the thin-
film initiates at the outer edge of the SEI. In the case of the planar SEI, the debonding
process progresses towards the centre from the outer edge. However, in the wrinkled SEI,
delamination initiates at every peak and spreads from there, as can be seen in Figures 4.9c,
4.9e and 4.9g. The progression of delamination is extremely aggressive in the wrinkled SEI
as compared to the planar one. As can be seen from the figures 4.10 to 4.12, delamination is
suppressed with the increase of interfacial strength. No initiation of delamination is observed
for the planar SEI system with interfacial strength σ0 = 1.20GP a. Hence it can be argued
that a planar SEI is more resistant to delamination compared to a wrinkled SEI.
 Chapter 4. Results and Discussion

1.0 G̃ =0.02
G̃ =0.02
G̃ =0.04 0.025
0.8 G̃ =0.04
G̃ =0.06
G̃ =0.06
0.6 G̃ =0.08 0.000
G̃ =0.08
G̃ =0.1
−0.025 G̃ =0.1
0.4
−0.050
σ̃rr

0.2

σ̃rr
0.0 −0.075

−0.2 −0.100

−0.4 −0.125

−0.6 −0.150
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.02 0.04 0.06 0.08
z̃ z̃

(a) (b)
1.00 G̃ =0.02 0.050
G̃ =0.02
G̃ =0.04
0.75 G̃ =0.04
G̃ =0.06 0.025
G̃ =0.06
G̃ =0.08
0.50 0.000 G̃ =0.08
G̃ =0.1
G̃ =0.1
0.25 −0.025
σ̃rr

σ̃rr
0.00 −0.050
−0.25 −0.075
−0.50 −0.100
−0.75 −0.125

−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
z̃ z̃

(c) (d)
0.8 −0.10
G̃ =0.02 G̃ =0.02
G̃ =0.04 G̃ =0.04
0.6 G̃ =0.06
−0.12
G̃ =0.06
G̃ =0.08 G̃ =0.08
−0.14
0.4 G̃ =0.1 G̃ =0.1
−0.16
σ̃rr

0.2
σ̃rr

−0.18
0.0 −0.20

−0.2 −0.22

−0.24
−0.4
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
z̃ z̃

(e) (f)
0.05 G̃ =0.02
G̃ =0.04 0.00011 G̃ =0.02
G̃ =0.06 G̃ =0.04
0.04 G̃ =0.08 G̃ =0.06
0.00010 G̃ =0.08
G̃ =0.1
G̃ =0.1
0.03
0.00009
σ̃rr

σ̃rr

0.02
0.00008

0.01
0.00007

0.00
0.00006

−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
z̃ z̃

(g) (h)

Figure 4.5: Variation of σ̃rr along the thickness direction in the thin film and SEI respectively
at t̃ = 0.1 at (a), (b) r̃ = 0.25, (c), (d) r̃ = 0.50, (e), (f) r̃ = 0.75
, and (g), (h) r̃ = 1.00
 Chapter 4. Results and Discussion

1.0 G̃ =0.02 −0.05 G̃ =0.02

G̃ =0.04 G̃ =0.04
G̃ =0.06 G̃ =0.06
0.5 G̃ =0.08 −0.10 G̃ =0.08
G̃ =0.1 G̃ =0.1
−0.15
σ̃rr

0.0

σ̃rr
−0.20
−0.5
−0.25

−1.0
−0.30
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.02 0.04 0.06 0.08
z̃ z̃

(a) (b)
0.8
G̃ =0.02
G̃ =0.02
G̃ =0.04 −0.15
0.6 G̃ =0.04
G̃ =0.06
G̃ =0.06
G̃ =0.08
0.4 −0.20 G̃ =0.08
G̃ =0.1
G̃ =0.1
0.2
σ̃rr

−0.25

σ̃rr
0.0
−0.30
−0.2

−0.4 −0.35

−0.6
−0.40
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
z̃ z̃

(c) (d)
G̃ =0.02 G̃ =0.02
0.6 G̃ =0.04 −0.40 G̃ =0.04
G̃ =0.06 G̃ =0.06
0.4 G̃ =0.08
−0.42 G̃ =0.08
G̃ =0.1 G̃ =0.1
0.2 −0.44
σ̃rr

σ̃rr

0.0 −0.46

−0.2 −0.48

−0.4 −0.50

−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
z̃ z̃

(e) (f)
G̃ =0.02
0.000150
0.10 G̃ =0.04 G̃ =0.02
G̃ =0.06 0.000125 G̃ =0.04
0.08 G̃ =0.08 G̃ =0.06
G̃ =0.1 0.000100 G̃ =0.08
G̃ =0.1
0.06 0.000075
σ̃rr

σ̃rr

0.04 0.000050

0.000025
0.02
0.000000
0.00
−0.000025
−0.02 −0.000050
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
z̃ z̃

(g) (h)

Figure 4.6: Variation of σ̃rr along the thickness direction in the thin film and SEI respectively
at t̃ = 0.2 at (a), (b) r̃ = 0.25, (c), (d) r̃ = 0.50, (e), (f) r̃ = 0.75
, and (g), (h) r̃ = 1.00
 Chapter 4. Results and Discussion

1.00 −0.15
G̃ =0.02 G̃ =0.02
0.75 G̃ =0.04 G̃ =0.04
−0.20
G̃ =0.06 G̃ =0.06
0.50 G̃ =0.08 G̃ =0.08
G̃ =0.1 −0.25 G̃ =0.1
0.25
−0.30
0.00
σ̃rr

σ̃rr
−0.25 −0.35

−0.50 −0.40
−0.75
−0.45
−1.00
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.02 0.04 0.06 0.08
z̃ z̃

(a) (b)
0.6 G̃ =0.02
G̃ =0.02
G̃ =0.04
−0.40 G̃ =0.04
G̃ =0.06
0.4 G̃ =0.06
G̃ =0.08
G̃ =0.08
G̃ =0.1 −0.45
0.2 G̃ =0.1
σ̃rr

0.0 −0.50

σ̃rr
−0.2
−0.55
−0.4
−0.60
−0.6
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
z̃ z̃

(c) (d)
0.6 −0.46
G̃ =0.02
G̃ =0.04
0.4 −0.48 G̃ =0.06
G̃ =0.08
0.2 −0.50 G̃ =0.1

−0.52
σ̃rr

0.0
σ̃rr

−0.54
−0.2 G̃ =0.02
G̃ =0.04
−0.56
−0.4 G̃ =0.06
G̃ =0.08
G̃ =0.1
−0.58
−0.6
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
z̃ z̃

(e) (f)
G̃ =0.02 0.00005
0.125 G̃ =0.04
0.00000
G̃ =0.06
0.100 G̃ =0.08 −0.00005
G̃ =0.1
0.075
−0.00010
0.050
σ̃rr

σ̃rr

−0.00015
0.025 −0.00020
G̃ =0.02
0.000 −0.00025 G̃ =0.04
G̃ =0.06
−0.025 −0.00030 G̃ =0.08
G̃ =0.1
−0.050 −0.00035
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
z̃ z̃

(g) (h)

Figure 4.7: Variation of σ̃rr along the thickness direction in the thin film and SEI respectively
at t̃ = 0.3 at (a), (b) r̃ = 0.25, (c), (d) r̃ = 0.50, (e), (f) r̃ = 0.75
, and (g), (h) r̃ = 1.00
 Chapter 4. Results and Discussion

G̃ =0.02 G̃ =0.02
0.75 G̃ =0.04 −0.35 G̃ =0.04
G̃ =0.06 G̃ =0.06
0.50 G̃ =0.08 −0.40 G̃ =0.08
G̃ =0.1 G̃ =0.1
σ̃rr 0.25 −0.45

σ̃rr
0.00 −0.50

−0.25 −0.55

−0.50 −0.60

−0.75 −0.65

−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.02 0.04 0.06 0.08
z̃ z̃

(a) (b)
G̃ =0.02
G̃ =0.02
0.6 G̃ =0.04
G̃ =0.04
G̃ =0.06
0.4 −0.55 G̃ =0.06
G̃ =0.08
G̃ =0.08
G̃ =0.1
0.2 G̃ =0.1
−0.60
σ̃rr

0.0

σ̃rr
−0.2 −0.65

−0.4
−0.70
−0.6

−0.8
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
z̃ z̃

(c) (d)
0.6 G̃ =0.02
G̃ =0.04
−0.2 G̃ =0.06
0.4
G̃ =0.08
−0.3 G̃ =0.1
0.2
σ̃rr

σ̃rr

0.0 −0.4
−0.2 G̃ =0.02
G̃ =0.04
−0.5
−0.4 G̃ =0.06
G̃ =0.08 −0.6
−0.6 G̃ =0.1

−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
z̃ z̃

(e) (f)
0.125
G̃ =0.02 −0.0001
G̃ =0.04
0.100 G̃ =0.06
G̃ =0.08 −0.0002
0.075 G̃ =0.1

0.050 −0.0003
σ̃rr

σ̃rr

0.025
−0.0004
0.000 G̃ =0.02
G̃ =0.04
−0.025 −0.0005 G̃ =0.06
G̃ =0.08
−0.050
G̃ =0.1
−0.0006
−1.0 −0.8 −0.6 −0.4 −0.2 0.0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
z̃ z̃

(g) (h)

Figure 4.8: Variation of σ̃rr along the thickness direction in the thin film and SEI respectively
at t̃ = 0.4 at (a), (b) r̃ = 0.25, (c), (d) r̃ = 0.50, (e), (f) r̃ = 0.75
, and (g), (h) r̃ = 1.00
 Chapter 4. Results and Discussion

G̃ =0.02 0.40 G̃ =0.02

0.4 G̃ =0.04
0.35 G̃ =0.04
G̃ =0.06 G̃ =0.06
G̃ =0.08 0.30 G̃ =0.08
0.3 G̃ =0.1 G̃ =0.1
0.25
M

0.20

M
0.2
0.15

0.1 0.10
0.05
0.0 0.00
0 2 4 6 8 10 0 2 4 6 8 10
r r

(a) (b)
0.8 G̃ =0.02 G̃ =0.02
0.7
G̃ =0.04 G̃ =0.04
0.7
G̃ =0.06 0.6 G̃ =0.06
0.6 G̃ =0.08 G̃ =0.08
G̃ =0.1 0.5 G̃ =0.1
0.5
0.4
M

M
0.4
0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10
r r

(c) (d)
G̃ =0.02 G̃ =0.02
0.8 G̃ =0.04 0.8 G̃ =0.04
G̃ =0.06 G̃ =0.06
G̃ =0.08 G̃ =0.08
0.6 G̃ =0.1 0.6 G̃ =0.1
M

0.4 0.4

0.2 0.2

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10
r r

(e) (f)
1.0 G̃ =0.02 G̃ =0.02
G̃ =0.04 G̃ =0.04
0.8
G̃ =0.06 G̃ =0.06
0.8
G̃ =0.08 G̃ =0.08
G̃ =0.1 G̃ =0.1
0.6
0.6
M

0.4
0.4

0.2 0.2

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10
r r

(g) (h)

Figure 4.9: Spatial variation of the Damage Parameter M along the interface of the thin film
and SEI for interfacial strength σ0 = 0.30 GPa, for a wrinkled and planar SEI respectively,
at (a), (b)t̃ = 0.1, (c), (d)t̃ = 0.2, (e), (f) t̃ = 0.3, (g), (h) t̃ = 0.4.
 Chapter 4. Results and Discussion

0.30 G̃ =0.02
G̃ =0.02 G̃ =0.02
G̃ =0.04
0.04 G̃ =0.04 0.04 G̃ =0.04
G̃ =0.06
G̃ =0.06 G̃ =0.06 0.25
G̃ =0.08 G̃ =0.08
G̃ =0.08
0.02 G̃ =0.1 0.02 G̃ =0.1 G̃ =0.1
0.20

M
M

M
0.00 0.00 0.15

0.10
−0.02 −0.02
0.05
−0.04 −0.04
0.00
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(a) (b) (c)

0.40
G̃ =0.02 0.6 G̃ =0.02 G̃ =0.02
0.05 G̃ =0.04 G̃ =0.04 0.35 G̃ =0.04
G̃ =0.06 0.5 G̃ =0.06 G̃ =0.06
G̃ =0.08 G̃ =0.08 0.30 G̃ =0.08
0.04 G̃ =0.1
G̃ =0.1 0.4 G̃ =0.1
0.25
0.03
M
0.20
M

M
0.3

0.02 0.15
0.2
0.10
0.01 0.1
0.05
0.00 0.0 0.00
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(d) (e) (f)

0.8
G̃ =0.02 G̃ =0.02 G̃ =0.02
0.7 G̃ =0.04 0.5 G̃ =0.04 0.8 G̃ =0.04
G̃ =0.06 G̃ =0.06 G̃ =0.06
0.6 G̃ =0.08 G̃ =0.08 G̃ =0.08
G̃ =0.1 0.4 G̃ =0.1 G̃ =0.1
0.5 0.6

0.4 0.3
M

M
0.4
0.3 0.2
0.2 0.2
0.1
0.1
0.0 0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(g) (h) (i)

0.8 1.0
G̃ =0.02 G̃ =0.02 G̃ =0.02
0.7 G̃ =0.04 G̃ =0.04 0.8 G̃ =0.04
G̃ =0.06 G̃ =0.06 G̃ =0.06
0.6 0.8
G̃ =0.08 G̃ =0.08 G̃ =0.08
G̃ =0.1 G̃ =0.1 0.6 G̃ =0.1
0.5
0.6
0.4
M

0.4
0.3 0.4

0.2 0.2
0.2
0.1
0.0 0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(j) (k) (l)

Figure 4.10: Spatial variation of the Damage Parameter M along the interface of the thin film
and SEI for interfacial strength σ0 = 0.60 GPa, for a wrinkled and planar SEI respectively,
at (a), (b) t̃ = 0.1, (c), (d) t̃ = 0.2, (e), (f) t̃ = 0.3, (g), (h) t̃ = 0.4, (i), (j) t̃ = 0.5, (k), (l)
t̃ = 0.6.
 Chapter 4. Results and Discussion

G̃ =0.02 G̃ =0.02 G̃ =0.02

0.04 G̃ =0.04 0.04 G̃ =0.04 0.04 G̃ =0.04
G̃ =0.06 G̃ =0.06 G̃ =0.06
G̃ =0.08 G̃ =0.08 G̃ =0.08
0.02 G̃ =0.1 0.02 G̃ =0.1 0.02 G̃ =0.1
M

M
0.00 0.00 0.00

−0.02 −0.02 −0.02

−0.04 −0.04 −0.04

0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(a) (b) (c)

0.175
G̃ =0.02 G̃ =0.02 G̃ =0.02
0.04 G̃ =0.04 G̃ =0.04 0.04 G̃ =0.04
0.150
G̃ =0.06 G̃ =0.06 G̃ =0.06
G̃ =0.08 G̃ =0.08 G̃ =0.08
0.125
0.02 G̃ =0.1 G̃ =0.1 0.02 G̃ =0.1
0.100
M
M

M
0.00 0.00
0.075

−0.02 0.050 −0.02

0.025
−0.04 −0.04
0.000
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(d) (e) (f)

0.5
G̃ =0.02 G̃ =0.02 G̃ =0.02
G̃ =0.04
0.7 G̃ =0.04
0.04 G̃ =0.04
0.4 G̃ =0.06 G̃ =0.06 G̃ =0.06
0.6
G̃ =0.08 G̃ =0.08 G̃ =0.08
G̃ =0.1 G̃ =0.1 0.5 G̃ =0.1
0.03
0.3
0.4
M

M
M

0.2 0.02
0.3

0.2
0.1 0.01
0.1

0.0 0.00 0.0

0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(g) (h) (i)

0.06 G̃ =0.02
1.0 G̃ =0.02 0.06 G̃ =0.02
G̃ =0.04 G̃ =0.04 G̃ =0.04
0.05 G̃ =0.06 G̃ =0.06 0.05 G̃ =0.06
0.8
G̃ =0.08 G̃ =0.08 G̃ =0.08
G̃ =0.1 G̃ =0.1 G̃ =0.1
0.04 0.04
0.6
M
M

0.03 0.03
0.4
0.02 0.02
0.2
0.01 0.01

0.00 0.0 0.00

0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
r r r

(j) (k) (l)

Figure 4.11: Spatial variation of the Damage Parameter M along the interface of the thin film
and SEI for interfacial strength σ0 = 0.90 GPa, for a wrinkled and planar SEI respectively,
at (a), (b) t̃ = 0.1, (c), (d) t̃ = 0.2, (e), (f) t̃ = 0.3, (g), (h) t̃ = 0.4, (i), (j) t̃ = 0.5, (k), (l)
t̃ = 0.6.
 Chapter 4. Results and Discussion

G̃ =0.02 G̃ =0.02
0.04 G̃ =0.04 0.04 G̃ =0.04
G̃ =0.06 G̃ =0.06
G̃ =0.08 G̃ =0.08
0.02 G̃ =0.1 0.02 G̃ =0.1
M

M
0.00 0.00

−0.02 −0.02

−0.04 −0.04

0 2 4 6 8 10 0 2 4 6 8 10
r r

(a) (b)
G̃ =0.02
0.08 G̃ =0.02
G̃ =0.04
0.04 G̃ =0.04 0.07 G̃ =0.06
G̃ =0.06
G̃ =0.08
G̃ =0.08 0.06
0.02 G̃ =0.1 G̃ =0.1
0.05

M
0.04
M

0.00
0.03
−0.02
0.02

−0.04 0.01
0.00
0 2 4 6 8 10 0 2 4 6 8 10
r r

(c) (d)
G̃ =0.02 1.0 G̃ =0.02
0.4 G̃ =0.04 G̃ =0.04
G̃ =0.06 G̃ =0.06
0.8
G̃ =0.08 G̃ =0.08
0.3 G̃ =0.1 G̃ =0.1
0.6
M

0.2
0.4

0.1 0.2

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10
r r

(e) (f)

Figure 4.12: Spatial variation of the Damage Parameter M along the interface of the thin
film and SEI for interfacial strength σ0 = 1.20 GPa, for a wrinkled SEI at (a) t̃ = 0.1, (b)
t̃ = 0.2, (c) t̃ = 0.3, (d) t̃ = 0.4, (e) t̃ = 0.5, (f) t̃ = 0.6.
 Chapter 4. Results and Discussion

4.1.2 Effect of SEI Stiffness and Bonding Energy

G̃ =0.02 G̃ =0.02
0.8
G̃ =0.04 G̃ =0.04
G̃ =0.06 0.8 G̃ =0.06
G̃ =0.08 G̃ =0.08
0.6 G̃ =0.1 G̃ =0.1
0.6
M

M
0.4
0.4

0.2 0.2

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10
r r

(a) (b)
1.0 G̃ =0.02
G̃ =0.04
G̃ =0.06
0.8
G̃ =0.08
G̃ =0.1
0.6
M

0.4

0.2

0.0
0 2 4 6 8 10
r

(c)

Figure 4.13: Spatial variation of the Damage Parameter M along the interface of the thin
film and SEI for interfacial strength σ0 = 0.30 GPa, for a wrinkled SEI of Youngs Modulus
(a) E = 3 GPa at t̃ = 0.6, (b) E = GPa at t̃ = 0.6, (c) E = 10 GPa at t̃ = 0.4.

In Figure 4.13, we depict the variation of the Damage Parameter M along the thin film-SEI
interface to study the effect of the stiffness of the SEI on the progression of debonding.
From figure 4.13c, it is evident that a higher stiffness of the SEI leads to multiple points of
delamination initiation, which coincides with the peaks of the SEI. It can also be observed
that at the later stages of discharging, the interfacial bonding energy has little effect on the
delamination index (M).
 Chapter 4. Results and Discussion

4.2 Elastic Perfectly Plastic SEI

(a)

(b)

(c)

(d)

Figure 4.14: Temporal evolution of σ̃rr at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.1; (c), (d) t̃ = 0.2.
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.15: Temporal evolution of σ̃rr at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.3; (c), (d) t̃ = 0.4
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.16: Temporal evolution of σ̃zz at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.1; (c), (d) t̃ = 0.2
 Chapter 4. Results and Discussion

(a)

(b)

(c)

(d)

Figure 4.17: Temporal evolution of σ̃zz at different times for wrinkled and planar SEI: (a),
(b) t̃ = 0.3; (c), (d) t̃ = 0.4
 Chapter 4. Results and Discussion

Figure 4.14 and 4.15, and 4.16 and 4.17 shows the temporal evolution of the stress compo-
nents of σ̃rr and σ̃zz respectively where the SEI is considered to be elastic perfectly plastic.
The SEI-thin film interface properties are K = 3000 GP a/µm, σ0 = 0.30 GP a, G0 = 2 J/m2 .
The stiffness of the SEI is ESEI = 10 GP a, and the yield stress is σSEI = 1 GP a. The na-
ture of the variation of stresses in the thin film and the SEI is similar to the elastic SEI
case (Figure 4.1 to 4.4) with regard to the location of compressive and tensile zones. One
significant difference is that there is no noticeable separation of the SEI layer from the thin
film. The yielding of the SEI layer results in a lower magnitude of interfacial stresses, thus
arresting the progression of delamination.

4.2.1 Effect of Interfacial Strength and Bonding Energy

1.0
G̃ =0.02 G̃ =0.02
G̃ =0.06 0.4 G̃ =0.06
0.8 G̃ =0.08 G̃ =0.08
G̃ =0.1 G̃ =0.1
0.3
0.6
M

0.2
0.4

0.2 0.1

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10
r r

(a) (b)

Figure 4.18: Spatial variation of the Damage Parameter M along the interface of the thin
film and SEI at t̃ = 0.6, where the interfacial strength is (a) σ0 = 0.30 GPa, (b) σ0 = 0.90
GPa.

In Figure 4.18, the variation of the Damage Parameter M is plotted along the thin film-SEI
interface to study the effect of the interfacial strength and bonding energy on the progres-
sion of debonding. On comparing Figure 4.18a with 4.9g and Figure 4.18b with 4.11k, we
understand that the presence of yielding of the SEI helps in mitigating the complete delam-
ination of the SEI layer from the thin film. For an interfacial strength of σ0 = 1.20 GPa,
no initiation of delamination is observed. The initiation of delamination in the case of an
elastic, perfectly plastic SEI is through mode II sliding.
Chapter 5

Conclusion and Future Work

The failure of a battery anode structure through the delamination of the SEI layer and
the active thin film under galvanostatic discharging has been investigated with the help of
Finite Element Modelling. The thin film represents the active material which is taken to be
silicon, whereas the substrate models the current collector, which is assumed to be copper.
We have assumed that the SEI layer is in a post-wrinkled stage The thin film, SEI layer,
and substrate have been modelled as homogeneous, linear and isotropic elastic and perfectly
plastic solid. The thin film is assumed to undergo axisymmetric infinitesimal deformations
due to the diffusion of lithium ions. The interfaces have been modelled using the Cohesive
Zone Modelling (CZM) method. The influence of this shape on the evolution of stresses and
the process of delamination has been studied and compared with that of a planar SEI.
A parametric study has been conducted by changing the interfacial properties of the thin
film-SEI interface and the stiffness of the SEI layer to understand the cohesive failure of the
SEI layer and the active thin film. The effect of plasticity has also been studied by considering
a case for an elastic perfectly plastic SEI. In the case of the elastic SEI, it is observed that
the process of delamination initiates at the peaks of the wrinkled SEI, as compared to a
planar SEI, where it beings from the outer edge of the interface. In the wrinkled SEI, it is
predominantly mode I failure as compared to the mode II failure for a planar SEI. It was
found that the stresses evolving in the wrinkled SEI are highly compressive in nature. This
leads to the conclusion that even if a small crack is present at the surface of the SEI, it
is highly unlikely that it will result in crack propagation. The interfacial bonding energy

38
 Chapter 3. Conclusion and Future Work

has some impact on the evolution of stresses in the SEI layer; however, at later stages of
discharging, it affects the delamination process, as indicated by the Damage Parameter M,
slightly. It was also observed that for all combinations of interfacial strength and bonding
energy, delamination in the wrinkled SEI was more pronounced than in a planar SEI. The
curved nature of the SEI results in some stress concentration which is responsible for the
aggravated onset of delamination. It was also observed that a less stiff SEI was crucial in
mitigating the progression of delamination compared to a SEI with a higher Youngs modulus.
While studying the discharging process by considering an elastic, perfectly plastic SEI, it
proved that the role of plasticity is crucial in this process. As the SEI yields, the final stress
levels are not as high as when considering a purely elastic SEI. Hence, the interfacial stresses
generated will be lower in magnitude as well, thus arresting the progressive failure at the
interface. Moreover, it was observed that the initiation of failure in the plastic case was
through mode II criteria, as compared to the mode I failure initiation of an elastic wrinkled
SEI.
The work can be further extended by considering the heterogeneity of the SEI layer to
incorporate the true inorganic and organic layered morphology of the SEI. As silicon under-
goes massive volumetric deformation, finite deformation modelling needs to be incorporated
through the implementation of user subroutines. The two-way coupling between stress and
diffusion should be implemented as well. Competitive analysis between delamination and
fracture of the SEI can be studied. This will further enable us to research building spe-
cially engineered jackets which can help in the passivation of the active material while being
robust.
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