FULLTEXT01

DEGREE PROJECT IN CHEMICAL SCIENCE AND ENGINEERING,
SECOND CYCLE, 30 CREDITS

STOCKHOLM, SWEDEN 2021
Investigation of Battery
Parameters for Li-ion Battery
State of Health Estimation
CAMILLA SÖDERHIELM
KTH ROYAL INSTITUTE OF TECHNOLOGY

SCHOOL OF ENGINEERING SCIENCES IN CHEMISTRY,
BIOTECHNOLOGY AND HEALTH
Investigation of Battery
Parameters for Li-ion Battery
State of Health Estimation
CAMILLA SÖDERHIELM
Master in Molecular Science and Engineering

Date: June 18, 2021
Supervisor: Markus Pastuhoff, Swedish Defence Research Agency (FOI)
Examiner: Rakel Wreland Lindström, KTH Royal Institute of Technology
Department of Chemical Engineering
Host organisation: Swedish Defence Research Agency (FOI)
Swedish title: Undersökning av batteriparametrar för uppskattning av
litiumjonbatteriers hälsotillstånd
iii
Abstract
Environmental concerns associated with greenhouse gas emissions from conventional combustion
engines have contributed to a transition towards electric mobility. In this transition, lithium-ion (Li-
ion) batteries play an important part as an energy storage system. However, Li-ion batteries can
pose a safety risk due to their reactive chemistry. The Swedish Armed Forces are approaching a
transition towards electric mobility, therefore, understanding Li-ion battery behavior with regard to
non-normal use and ageing is critical for safe military applications. This project aimed to identify
and evaluate battery parameters (impedance, resistance, capacity and surface temperature) suitable
for State of Health (SOH) estimation of Li-ion batteries in military applications. Furthermore, this
project aimed to investigate the ambient temperature’s effect on battery parameters, and identify
the battery’s end of life (EOL) based on battery parameter tracking.
Commercial NMC/graphite Li-ion batteries were exposed to ageing through repeated charge and
discharge cycles. A critical application was mimicked, where the batteries operated at 1C charge
rate (4 A) and 2.5C discharge rate (10 A) between 100 % and 0 % state of charge, for up to
250 charge/discharge cycles. The ageing process was tracked through regular measurements of
impedance, resistance, capacity and surface temperature. In order to investigate the ambient tem-
perature’s effect on the investigated battery parameters, the batteries were aged at either 52 ± 3 ◦ C,
21 ± 3 ◦ C or −15 ± 3 ◦ C.
Impedance measured at 980 Hz was the most stable battery parameter with respect to variations in
state of charge and temperature, and was therefore regarded as the most suitable parameter for SOH
estimation with respect to flexibility. Measurements of resistance and capacity at given temper-
atures were likely reflecting electrochemical ageing phenomena more accurately, hence the most
suitable battery parameters for SOH estimation with respect to accuracy. Tracking of surface tem-
perature provided insufficient information for accurate estimation of the batteries SOH.
Decreasing the ambient temperature from 21 ◦ C to −15 ◦ C had a major effect on capacity and
resistance; the resistance increased and the capacity decreased, corresponding to a decrease in
battery performance.
With respect to capacity fade, neither of the batteries aged at 21 ◦ C reached their EOL within
250 cycles, while batteries aged at 52 ◦ C or −15 ◦ C reached their EOL after 150–200 cycles. With
respect to resistance, one battery kept at 21 ◦ C reached their EOL after 200 cycles, all batteries
kept at 52 ◦ C reached their EOL after 150–200 cycles, and batteries kept at −15 ◦ C reached their
EOL between 200–250 cycles. Finally, with respect to impedance measured at 980 Hz, one battery
kept at 21 ◦ C reached their EOL after 200 cycles, one battery kept at 52 ◦ C reached their EOL after
150 cycles, and batteries kept at −15 ◦ C reached their EOL between 200–250 cycles.
Keywords: Lithium-ion battery, State of Health, low-temperature ageing, high-temperature ageing,
ageing mechanisms
iv
Sammanfattning
Miljöpåverkan från konventionella förbränningsmotorer har bidragit till en övergång till elmotorer.
I denna övergång spelar litiumjonbatterier en viktig roll som energilagringssystem, men på grund
av sin reaktiva kemi kan de utgöra en säkerhetsrisk. I likhet med civilsamhället står Försvarsmakten
inför ett skifte där förbränningsmotorer ska bytas ut mot el- och hybridmotorer. För en säker militär
tillämpning är det därför viktigt att förstå hur litiumjonbatterier beter sig vid åldrande och bortom
ramen för normal användning. Detta projekt syftar till att identifiera batteriparametrar (impedans,
resistans, kapacitet och yttemperatur) att använda för bedömning av batteriets hälsotillstånd. Vi-
dare syftar projektet till att värdera de identifierade batteriparametrarnas lämplighet för militära
applikationer. Som en del av syftet undersöker detta projekt omgivningstemperaturens effekt på
batteriparametrarna, samt använder batteriparametrarna för att uppskatta när ett batteri kan klassas
som förbrukat.
Kommersiella NMC/grafit-litiumjonbatterier åldrades genom full upp- och urladdning. Varje bat-
teri utsattes för maximalt 250 upp- och urladdningscykler vid laddningsströmmar om 4 A och
urladdningsströmmar om 10 A. Åldrandet övervakades genom regelbunden mätning av impedans,
resistans, kapacitet och yttemperatur. Batterierna cyklades vid antingen 52 ± 3 ◦ C, 21 ± 3 ◦ C eller
−15 ± 3 ◦ C för att studera omgivningstemperaturens effekt på de undersökta batteriparametrarna.
Impedansmätningar vid 980 Hz var stabilast med avseende på variationer i omgivningstemperatur
samt batteriets laddningsnivå, och ansågs därför vara den lämpligaste batteriparametern att använda
för uppskattning av batteriets hälsotillstånd när tillämpningen kräver stor flexibilitet. Förändringar
i resistans och kapacitet vid givna omgivningstemperaturer ansågs å andra sidan bättre återspegla
batteriets åldringsgrad. Därför ansågs resistans och kapacitet vara de lämpligaste batteriparametrar-
na för uppskattning av batteriets hälsotillstånd med avseende på precision. Mätning av yttemperatur
gav otillräcklig information för att uppskatta batteriernas hälsotillstånd med precision.
En sänkning av omgivningstemperaturen från 21 ◦ C till −15 ◦ C hade en stor påverkan på resi-
stans och kapacitet; resistansen ökade medan kapaciteten minskade, vilket motsvarar en reducerad
batteriprestanda.
Med avseende på kapacitetsförlust så förbrukades inget av batterierna som förvarades i 21 ◦ C under
cyklingen. Batterier som förvarades i 52 ◦ C och −15 ◦ C var förbrukade efter 150–200 cyklingar.
Med avseende på resistansökning var ett av batterierna som förvarades vid 21 ◦ C förbrukat ef-
ter 200 cyklingar. Samtliga batterier förvarade vid 52 ◦ C var förbrukade efter 150–200 cyklingar,
medan batterier förvarade vid −15 ◦ C var förbrukade efter 200–250 cyklingar. Slutligen, med av-
seende på impedansmätning vid 980 Hz så tog det 200 cyklingar tills dess att ett av batterierna
som förvarades i 21 ◦ C var förbrukat. Ett av batterierna som förvarades i 52 ◦ C var förbrukat efter
150 cyklingar. Batterier förvarade vid −15 ◦ C var förbrukade efter 200–250 cyklingar.
Nyckelord: Litiumjonbatteri, hälsotillstånd, lågtemperaturåldring, högtemperaturåldring,
åldringsmekanismer
v
Acknowledgement
I would like to extend my gratitude to the whole battery team at FOI for being ever so friendly and
helpful. A special thanks to my supervisor Markus for your valuable guidance and trust throughout
the whole process.
I would also like to take the opportunity to thank those of you who have helped and inspired me
during the course of my education, and my dear family and friends who have been the best encour-
agement and support. Finally, thank you Martin for always lifting me up.
Contents
List of Abbreviations viii
1 Introduction 1
1.1 Purpose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Background 4
2.1 Principle of the Li-ion battery . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.1 Cathode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.2 Anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1.3 Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Ageing of Li-ion batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.1 SEI-layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.2 Capacity and temperature . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2.3 Resistance increase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2.4 Internal heat generation and gas evolution . . . . . . . . . . . . . . . . . 9
2.2.5 Lithium plating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2.6 Summary of ageing mechanisms in Li-ion batteries . . . . . . . . . . . . 10
2.3 SOH estimation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.1 Capacity fade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.2 Incremental capacity analysis . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.3 Impedance increase through EIS measurements . . . . . . . . . . . . . . 12
2.3.4 Resistance increase through HPPC-test . . . . . . . . . . . . . . . . . . 14
2.3.5 Summary of SOH estimation methods . . . . . . . . . . . . . . . . . . . 16
3 Methods 17
3.1 Investigated Li-ion battery and battery specifications . . . . . . . . . . . . . . . 17
3.2 Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.2.1 Room-temperature (RT) cycling . . . . . . . . . . . . . . . . . . . . . . 20
3.2.2 High-temperature (HT) cycling . . . . . . . . . . . . . . . . . . . . . . 20
vi
CONTENTS vii
3.2.3 Low-temperature (LT) cycling . . . . . . . . . . . . . . . . . . . . . . . 20

3.3 Experimental procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3.1 Cycling ageing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3.2 Characterisation test . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.3.2.1 Capacity measurements . . . . . . . . . . . . . . . . . . . . . 21
3.3.2.2 Impedance measurements through GEIS . . . . . . . . . . . . 22
3.3.2.3 Resistance measurements through HPPC-test . . . . . . . . . . 22
3.3.2.4 State of charge estimation . . . . . . . . . . . . . . . . . . . . 22
3.3.3 Characterisation at beginning of cycling and end of cycling . . . . . . . . 24
3.3.4 X-ray diffraction analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.3.5 Cell disassembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4 Results 26
4.1 Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.1.1 Charge and discharge capacity . . . . . . . . . . . . . . . . . . . . . . . 26
4.1.2 Incremental capacity analysis . . . . . . . . . . . . . . . . . . . . . . . 28
4.2 Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.3 Impedance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.3.1 Impedance spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.4 Surface temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.5 Temperature’s effect on battery parameters
before and after ageing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.6 Battery disassembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.7 X-ray diffraction analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5 Discussion 45
5.1 Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.2 Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5.3 Impedance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5.4 Surface temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.5 Deviating batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.6 Limitations and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6 Conclusions 50
Bibliography 52
A Contact Loss Due to CID Activation 58
B Magnitude of Impedance at 980 Hz 59
C X-ray Diffraction Spectra Fitting 60

viii CONTENTS
List of Abbreviations
Abbreviation Definition
AC Alternating current
BMS Battery management system
BOL Beginning of life
CEI Cathode-electrolyte interface
CC Constant current
CID Current interrupt device
CL Conductivity loss
CV Constant voltage
DC Direct current
DOD Depth of discharge
ECM Equivalent circuit model
EIS Electrochemical impedance spectroscopy
EOL End of life
FOI Swedish Defence Research Agency
GEIS Galvanostatic electrochemical impedance spectroscopy
HPPC Hybrid Pulse Power Characterisation
HT High-temperature (52 ± 3 ◦ C)
ICA Incremental capacity analysis
LAM Loss of active material
LCO LiCoO2
LFP LiFePO4
Li-ion Lithium-ion
LLI Loss of lithium inventory
LT Low-temperature (−15 ± 3 ◦ C)
NMC Li[Nix Mny Co1−x−y ]O2
OCV Open circuit voltage
RT Room-temperature (21 ± 3 ◦ C)
SEI Solid-electrolyte interface
SOC State of charge
SOH State of health
USABC U.S. Advanced Battery Consortium
XRD X-ray diffraction
Chapter 1
Introduction
Lithium-ion (Li-ion) batteries have become increasingly important for the transition towards elec-
tric mobility and are used for power storage in various applications, ranging from portable devices
and electric scooters to electric vehicles, hybrid electric vehicles, trucks and buses [1][2]. Replac-
ing the conventional combustion engine with an electric powertrain can be an important contri-
bution to a more sustainable transport sector through a reduction of greenhouse gas emissions, as
well as a reduction of air pollution [3].
The Li-ion battery is the most applicable energy storage system to power electric vehicles, and it
is estimated that the number of electric vehicles on the roads worldwide will exceed 125 millions
by year 2030 [2][3]. Replacing combustion engines with electrical power systems is however not
only of commercial interest. Li-ion batteries are being tested in more demanding conditions such as
mining, space, and military applications [4]. The Swedish Armed Forces are currently approaching
a transition towards electrical and hybrid engines; a transition in which Li-ion batteries will play
an important part.
Behind the increasing popularity of using Li-ion batteries as a power source lies its high power
capability, high energy density, long cycling life and wide temperature range; properties which
make them suitable for various mobile applications. These properties are linked to the chemistry
of the battery cell. Its electrodes are able to store and reversibly release large amounts of Li-ions,
and its organic electrolyte enables a wider potential and temperature window compared to that of
aqueous battery chemistries, such as the lead acid battery [4][5].
On the other hand, the Li-ion battery is associated with safety risks considering its complex and
highly reactive battery chemistry. The behavior of the Li-ion battery is nonlinear since its perfor-
mance depends on external factors such as temperature, as well as internal factors such as degree
of ageing. A figure of merit critical for battery reliability and safety is the battery’s State of Health
(SOH). The SOH represents the battery’s degree of ageing as compared to its initial state. In order
to evaluate the SOH, one must find indicators to the extent in which the battery deviates from its
1
2 CHAPTER 1. INTRODUCTION
fresh state, for instance in terms of capacity decrease or resistance increase [4][6].
Furthermore, the Li-ion battery’s reactive chemistry makes it susceptible to abuse. Thermal or
electrical abuse such as elevated or lowered temperatures, overcharge or overdischarge may trigger
unwanted side reactions inside the cell. These side reactions can irreversibly damage the electrolyte
and electrode material, leading to performance degradation, accelerated ageing and imbalanced
cells. If the thermal or electrical abuse cannot be hindered, the side reactions may accelerate and
ultimately cause internal short circuit of the cell. Internal short circuit is closely associated with
a series of self-sustained exothermic side reactions and rapid temperature increase; a phenomenon
called thermal runaway. The onset of thermal runaway can have catastrophic consequences, such
as gas evolution, ignition and explosion [7].
The gases released upon thermal runaway of Li-ion batteries have previously been investigated by
The Swedish Defence Research Agency (FOI), and various substances causing respiratory irritation
were identified [8]. This raises safety concerns regarding the use of Li-ion batteries in military
applications with enclosed spaces that cannot be quickly evacuated, such as submarines. In order
to prevent battery failure and the risk of thermal runaway, the battery’s parameters must be closely
monitored during operation. For this purpose, a monitoring system called battery management
system (BMS) is incorporated into the battery pack. The BMS serves to ensure that the batteries
operate in a safe state by monitoring battery parameters in real time. Hence, the BMS should detect
critical values and act on them, for example by disconnecting a failing battery in a battery module
[4][6].
For optimal performance and safety, all battery cells must be evenly matched with respect to their
ageing condition before being installed into a battery pack and connected to other cells. However,
once the batteries are installed they can still be driven away from the matched state, even under
normal operating conditions or under storage [9]. In addition, real life operating conditions vary
substantially and can be very complex, hence a risk of unforeseeable battery abuse. This has been
the case in previous accidents involving Li-ion batteries. Electric vehicles have caught fire due
to charging failures and there have been accidents involving Boeing 787 aircrafts, where Li-ion
battery packs caught fire due to spontaneous internal short circuit [10].
Akin accidents raise concerns if Li-ion batteries are to be used in military applications. While oc-
casional battery failures in portable devices or electric vehicles may not involve major economical
or physical damage to humans, the damage could be immense if battery failures would occur in
aircrafts or submarines. Hence, there is a need to better understand the Li-ion battery behavior
with regard to ageing and non-normal operating conditions. In light of this, the Swedish Defence
Research Agency is investigating Li-ion battery safety parameters for military applications. As a
part of their work, this project investigates the ageing behavior of Li-ion batteries under varying
loads and temperatures.
CHAPTER 1. INTRODUCTION 3
1.1 Purpose
This project aims to investigate the ageing behavior of Li-ion batteries at various temperatures,
evaluate methods for SOH estimation and identify SOH parameters. The purpose is to identify
and characterise battery parameters on ageing Li-ion battery cells and evaluate their applicability
as SOH parameters for military applications. The long-term aim is to improve the safety of using
Li-ion batteries in military applications by implementing SOH parameters into a BMS.
1.2 Objectives
This project seeks to answer the following questions based on military applications:
• Which battery parameters are suitable for SOH estimation?
• At which point does a battery reach their end of life based on battery parameters?
• What effect does ambient temperature have on the investigated battery parameters?
1.3 Limitations
This project is limited to the investigation of battery parameters for SOH estimation on commer-
cially available cylindrical Samsung SDI INR21700-40T batteries with NMC cathodes and graphite
anodes. Furthermore, this project is limited to experimental methods for SOH estimation.
Chapter 2
Background
In this chapter, the principles of the Li-ion battery will be accounted for, and problems related to
the ageing of the battery will be discussed. Firstly, the general principle of a Li-ion battery cell will
be described together with an account of the most important battery parameters related to ageing.
Following that, an evaluation of the battery parameters and their relevance for the battery’s SOH
will be discussed, and previous research on the area will be reviewed continuously.
2.1 Principle of the Li-ion battery

A Li-ion battery is an electrochemical cell that transforms chemical energy into electric energy
through redox reactions between its electrode materials. The electrodes, one positive (cathode)
and one negative (anode), constitutes high energy active materials, binders and current collectors.
When the electrodes are further connected by an external circuit, electrons flow between the elec-
trodes through the external circuit allowing the redox reactions to occur without direct contact
between the electrodes [5].
The active material on the anode is typically made of graphite, while the active material on the
cathode is commonly a lithium metal phosphate or a lithium metal oxide. Using a binder, the
active electrode material is adhered to a current collector, typically aluminum foil on the cathode
and copper foil on the anode [5]. The electrodes are immersed in an electrolyte containing solved
lithium salt, and a separator is situated in the electrolyte between the electrodes. The function of
the separator is to provide electric insulation between the electrodes, only allowing Li-ions to pass
through [1][5].
Both electrode materials have a layered crystalline structure with a small space between the layers
into which the Li-ions can enter. The principle of charge and discharge relies on intercalation of
Li-ion between these layers. Intercalation is the reversible incorporation of a material into a crystal
lattice. During charging of the battery, the Li-ions intercalate, or insert, into the space between the
4
CHAPTER 2. BACKGROUND 5
layers of the graphite anode. When the battery discharges, the Li-ions migrate back towards the
cathode where they intercalate between the metal-oxide layers, as depicted in Figure 2.1 [5] [11].
charge discharge
e- e-
V
+ -
+ charge
Li
Negative current collector

Positive current collector
intercalation
e- Li+ Li+ e-
discharge +
Li
intercalation
Cathode active material Anode active material

(LiMO2 or LiFePO4) (Graphite)
Figure 2.1. An illustration of Li-ion intercalation be-

tween the sheets of the cathode and anode active ma-
terial. Adapted from [5].
2.1.1 Cathode
LiCoO2 (LCO) was the first commercially used cathode material, with a specific capacity of ap-
proximately 155 Ah/kg and a nominal voltage of 3.9 V vs. Li/Li+ . While having good electric
properties, the LCO material is also associated with high toxicity and high costs due to the use of
cobalt. In addition, its layered structure is associated with thermal instability at elevated tempera-
tures which raises safety concerns [2][5].
Another common cathode active material is the Li[Nix Mny Co1−x−y ]O2 (NMC) which shows sim-
ilar properties to LCO but with a better thermal stability and lower material cost [5]. It can be de-
signed for either high energy or high power applications depending on the relative content (denoted
x and y) of nickel, manganese and cobalt. Nickel increases the energy density while manganese
reduces the resistance, and keeping the cobalt content relatively low reduces the costs and toxicity.
An NMC111 battery contains equal amounts of nickel, manganese and cobalt, and provides a spe-
cific capacity of approximately 150 Ah/kg and a nominal voltage of 3.8 V vs. Li/Li+ [2][5]. With
high nickel content the specific capacity increases and with high manganese and cobalt content, the
structural stability increases. For instance, the NMC811 battery has an 80 % nickel-content and
provides a discharge capacity exceeding 185 Ah/kg. Seeing that the NMC material can be tailored
to meet specific requirements it has become a popular electrode material in Li-ion battery power-
trains for electric vehicles [2]. However, a high relative nickel content is associated with a severe
capacity fade upon ageing, while a high manganese content generally provide cycling stability [12].
6 CHAPTER 2. BACKGROUND
LiFePO4 (LFP) is another popular cathode material for electric vehicle batteries. It is a relatively
cheap electrode material with high thermal stability since the phosphate protects the material from
deteriorating at overcharge and at elevated temperatures. Thus, the LFP material remains stable at
temperatures up to 350 ◦ C in both charged and discharged state, and it can tolerate high current
rates [5]. A major drawback however, is the relatively low capacity and energy density (specific
capacity of 160 Ah/kg and nominal voltage of 3.45 V vs. Li/Li+ ). Yet another drawback is a high
self-discharge rate, which can pose a problem as a battery module may become imbalanced with
age [2].
2.1.2 Anode
Graphite is the most commonly used electrode material for the anode in commercial Li-ion bat-
tery cells. It is abundant, safe, and have a high specific capacity (370 Ah/kg) [2]. As previously
mentioned, the Li-ion battery charging process is based on Li-ion intercalation into the electrode
material. As the battery charges and the Li-ions intercalate into the graphite particles, the graphitic
sheets undergo structural changes in several stages, from stage IV to stage I as depicted in Fig-
ure 2.2. Each stage denotes the number of graphite layers being fully intercalated with Li-ions; for
instance, in stage II every second layer is fully intercalated. With each stage, both during charge
and discharge, the graphite particles are subjected to volume changes and mechanical strain [13].
This makes graphite susceptible to elevated C-rates1 since the mechanical stress increases on the
graphite lattice during the intercalation process. The volume change and mechanical strain is par-
ticularly pronounced in the transition between stage II and stage I at high SOC [13][14].
= Li+
Stage I
Stage II
Stage III
Stage IV
0 10 20 30 40 50 60 70 80 90 100
SOC [%]
Figure 2.2. A sketch of the step-wise structural changes of graphite as

Li-ions intercalate. With each stage, graphite layers are opened and inter-
calated with Li-ions. The greatest volume change occurs in the transition
between stage I and II at high state of charge (SOC). Adapted from [13].
1
C-rate indicates the current required for a full charge or discharge, based on the battery capacity. For
instance, charging a 5 Ah battery at C/10-rate corresponds to 0.5 A charge current during 10 hours [5].
2.1.3 Electrolyte
Li-ion batteries commonly contain an organic electrolyte with solved lithium salt. The electrolyte
conducts Li-ions between the electrodes. Organic electrolytes remain stable between a wider
electrochemical window than aqueous electrolytes and therefore enable Li-ion batteries to oper-
ate within a wider potential range than batteries containing an aqueous electrolyte [2]. Organic
carbonates are commonly used as electrolyte, including ethyl carbonate, dimethyl carbonate and
propylene carbonate. The lithium salt is usually LiPF6 , LiBF4 or LiClO4 [2].
The benefit of using an organic electrolyte comes at the expense of thermal stability, since organic
electrolytes are flammable. For that reason, additives are commonly used to improve the thermal
stability. Moreover, additives can be used to improve the conductivity and protect the electrode ma-
terial from overcharge. Additives can also facilitate the formation of the solid electrolyte interface
layer (SEI-layer) [15]. The SEI-layer forms as the electrolyte degrades in contact with the anode.
Once it is formed, the SEI-layer protects the electrolyte from decomposing further, while it allows
Li-ions to pass through [2]. It is an essential part of the battery performance and its relevance for
battery ageing will be further discussed in the section below.
2.2 Ageing of Li-ion batteries

Ageing of a Li-ion battery is the degradation of performance with time. The degradation can occur
both during operation (cycling ageing) or under rest (calendar ageing) [16]. There are several
factors causing battery ageing, which can be categorized into either internal or external factors.
The external factors are due to the physical conditions of the battery, such as operating temperature,
C-rate, depth of discharge (DOD), and the set cut-off voltage. In contrast, the internal factors refer
to phenomena occurring inside the battery. The internal ageing factors are commonly called loss
of active material (LAM), loss of lithium inventory (LLI) and conductivity loss (CL) [17].
LAM involves loss of electrode material and electrolyte due to irreversible degradation through side
reactions inside the cell. LLI occurs through Li-ion consuming side reactions, such as the formation
of SEI-layer. A common side reaction, causing both LAM and LLI, is gas evolution. Lastly, CL
occurs due to degradation of current collectors and/or binders in the electrodes [17][18].
2.2.1 SEI-layer
SEI-layer formation and degradation are among the most important ageing mechanisms in Li-ion
batteries [19]. Since the interface between the anode and the electrolyte is not thermodynamically
stable, part of the Li-ions will react with the electrolyte upon the first cycles and form the SEI-
layer on the surface of the anode. The formed SEI-layer is passivating and protects the anode
from exposure to the organic electrolyte, but it also leads to capacity fade as the lithium ions are
irreversibly consumed. In addition, the intercalation and de-intercalation process in the anode slows
down, hence, capacity fade and increased resistance are linked to SEI-layer growth [5][11][19].
Ruptured or non-uniform SEI-layer will lead to further electrolyte decomposition and growth of
the SEI-layer. SEI-layer rupture occurs continuously during operation as the intercalation/ de-
intercalation process causes volume changes to the graphitic lattice, as described under section
2.1.2 Anode. As a result, the graphite surface is repeatedly exposed to the electrolyte, more SEI-
layer is built and more Li-ions are consumed, hence LLI [13].
SEI-layer build up also occurs on the cathode, also called cathode-electrolyte interface layer (CEI-
layer). NMC electrodes suffer from a degradation phenomena called transition metal dissolution,
where the nickel and manganese content in the electrode decreases due to side reactions. For
instance, at high SOC, nickel is dissolved into the electrolyte and consumed through side reac-
tions, leading to LAM and CEI-layer build up. Another phenomenon at high SOC is migration
of dissolved transition metal to vacant Li-ion intercalation sites. Repeated charge to high SOC is
therefore associated with capacity loss due to LAM and decreased amounts of Li-ion intercalation
sites [12]. Furthermore, the dissolved transition metals can migrate to the anode and integrate with
the SEI-layer, leading to SEI-layer growth [20]. Increasing thickness of the SEI-layer is closely
related to mass transport and charge transfer limitations, which further increase the cell resistance.
Apart from performance losses, it can in a worst case scenario lead to thermal runaway [21].
2.2.2 Capacity and temperature

The term capacity refers to the amount of electrical charge Q [Ah] the battery can deliver until a
voltage limit is reached, called cutoff voltage [22]. In an electric vehicle application, capacity is an
important indicator of the available range of the vehicle [23]. A battery’s capacity depends heavily
on temperature and load, since the capacity is linked to reaction rates in the battery, mass transport
and diffusion phenomena [22]. Limitations in these phenomena are mainly seen at temperatures
below 0 ◦ C. For instance, the SOC in a Li-ion battery has previously been shown to decrease with
23 % when the temperature decreased from 25 ◦ C to −15 ◦ C during operation [16]. The SOC is
defined as the ratio of the battery’s current capacity Q(t) to the nominal capacity Qn according
to Equation 2.1. The nominal capacity is the quantity of charge a fully charged battery delivers,
depending on battery application such as temperature or load [22][24].
Q(t)
SOC(t) = (2.1)
Qn
An increase in temperature on the other hand favours reaction rates at the electrode surfaces. In
addition, the ionic conductivity in the electrodes and electrolyte increases. For a Li-ion battery, the
optimal temperature of operation usually ranges between 15 ◦ C to 35 ◦ C [16].
2.2.3 Resistance increase

Resistance is another important battery parameter for both performance and SOH indication since it
is related to the available power. The resistance increases due to several processes occurring inside
the battery, both during operation and storage. Among the causes to an increasing resistance due
to ageing are SEI-layer build up, diminished contact in the electrodes and gas evolution [18][23].
However, another factor affecting the resistance is the temperature. As the temperature decreases,
the viscosity of the organic electrolyte increases, leading to a lower ionic conductivity. The lithium
ions travel more slowly through the electrolyte and in the electrode material. As a result, the charge
transfer resistance of the Li-ion battery increases and the performance decreases [16].
2.2.4 Internal heat generation and gas evolution

A Li-ion battery generates heat upon charge/discharge which increases the internal temperature.
The heat generation is mainly due to exothermic chemical reactions, charge transfer resistance in
the SEI layer and ohmic resistance of the electrolyte. The effect of internal heat generation is more
prominent at high C-rates. In the worst case scenario, overheating a Li-ion battery may lead to
thermal runaway [16]. In a previous project on battery safety parameters performed at FOI, the
onset of thermal runaway for NMC batteries was detected at ∼ 120 ◦ C [25]. From a safety aspect,
it is therefore crucial to accurately control the operation temperature of a Li-ion battery.
High internal temperatures as well as overcharge can lead to gas evolution inside the battery, with
risk of cell rupture and ignition on flammable gases. In order to avoid excessive internal pressure
build up and risk of thermal runaway, the batteries may be equipped with a safety device called
current interrupt device (CID). The purpose of the CID is to prevent initiation of thermal runaway
by electrically isolating the positive terminal, hence interrupting the flow of current. The CID is
activated by an increase in internal pressure and gases formed inside the cell are released through
a vent, thus, the internal pressure is relieved and cell rupture due to internal build up of gases is
avoided [26].
2.2.5 Lithium plating

One of the reasons for the Li-ion battery’s susceptibility to electrical abuse is the risk of internal
short circuit. The internal short circuit can be a result of growth of metallic lithium on the anode
surface. If the anode potential decreases below 0 V vs. Li/Li+ , the Li-ions reduce to metallic
lithium. The formed metallic lithium may then deposit on the anode surface. This phenomenon
is known as lithium plating. Lithium plating not only leads to severe capacity reduction due to
the consumption of Li-ions, but it also poses safety risks as the plate formation may grow into
dendrites eventually short circuiting the cell. Lithium plating can also occur due to mass transport
limitations. Under harsh conditions such as low temperatures combined with high C-rates, the
kinetics of the lithium intercalation process slows down and the diffusion rate of Li-ions becomes
limited. Instead of intercalating into the electrode material, the Li-ions will plate on the anode
surface [14][27].
2.2.6 Summary of ageing mechanisms in Li-ion batteries

A summary of possible ageing mechanisms occurring in Li-ion batteries, and the correlating ex-
ternal and internal factors are presented in Table 2.1.
Table 2.1. Ageing mechanisms and the correlating external and internal causes, summarised from [19].
External cause Ageing mechanism Ageing effect Internal cause

High temperature > 35 ◦ C Electrolyte decomposition SEI growth LLI
Micropore clogging LAM
SEI dissolution LAM
Gas evolution LLI
Electrode decomposition Precipitation of new phases LAM

Transition metal dissolution SEI growth LAM
Low temperatures < 5 ◦ C Lithium plating Dendrite growth LLI
SEI growth LLI
High C-rates > 2C Lithium plating Dendrite growth LLI
SEI growth LLI
Overdischarge Current collector corrosion Conductivity loss CL
Binder decomposition Conductivity loss CL
Overcharge Binder decomposition Conductivity loss CL
Electrode decomposition Gas evolution LAM
2.3 SOH estimation methods

As discussed, there are several phenomena contributing to the ageing of a battery and the associ-
ated degradation in performance. Among the indicators of a battery’s degree of deterioration is
the SOH. SOH is however not a directly measurable parameter like voltage or current. Instead,
SOH is a figure of merit depicting the battery’s degree of degradation as compared to its unused
state, or beginning of life (BOL). There are several methods and research trends for evaluating a
battery’s SOH, ranging from evaluating experimental data, modelling of battery components to
machine learning [28]. Regardless of method; capacity, resistance and temperature are three im-
portant battery parameters that strongly correlate to battery performance, and tracking their changes
upon battery ageing can be necessary to accurately evaluate the SOH. Furthermore, impedance is a
battery parameter which can provide information about electrochemical ageing phenomena. Their
implementation in SOH estimations will be further discussed in this section together with descrip-
tions of different methods used to evaluate SOH. Due to the scope of this project, focus will remain
on experimental methods for the evaluation of SOH.
2.3.1 Capacity fade

A method for SOH estimation commonly adopted in literature is tracking of the battery’s capacity
fade with respect to its initial capacity [6][29]. Batteries in electric vehicles and hybrid electric
vehicles are commonly considered fully exhausted once the capacity decreases below 80 % of its
initial state. At that point, also called end of life (EOL), the battery should be replaced but the exact
point of EOL depends on the application [6][30]. Evaluating the SOH accurately based on capacity
fade is time consuming as it often requires a full charge/discharge cycle. In addition, this method
requires relatively low C-rates since elevated C-rates are associated with voltage losses, which can
result in misleading capacity readings [13].
2.3.2 Incremental capacity analysis

Incremental capacity analysis (ICA) is a method for studying the intercalation steps in the electrodes
as the battery charges or discharges. The obtained information can be used for investigation of
ageing phenomena. Voltage plateau regions can be observed along the charge or discharge phase of
a Li-ion battery. The plateaus are linked to the step-wise intercalation/de-intercalation processes in
the graphitic anode, described under 2.1.2 Anode. By differentiating the capacity with respect to the
voltage (Equation 2.2 [30]), and plotting the differentiated capacity against the voltage, the plateaus
are transformed into peaks. Each peak corresponds to a phase equilibrium during the charge or
discharge process, while the valleys correspond to a transition between the phases [30][31]. See
an example of a dQ/dV vs. V plot at the left of Figure 2.3
dQ Qt − Qt−1
= (2.2)
dV Vt − Vt−1
Each peak has unique characteristics in terms of intensity and position, and the shape of the peaks
depend on the type of electrode material [31][32]. Starting from low voltages, the first peak at 3.4
– 3.5 V stems from the intercalation of Li-ions into the graphite anode. For batteries containing an
NMC cathode, the second peak starting at ∼3.6 V arises as the crystal lattice of the NMC undergoes
a phase transition from hexagonal to monoclinic (H1 −→ M). In the case of a nickel-rich NMC
cathode with NMC811 composition, the third peak starting at 3.8 V stems from M −→ H2 crystal
phase transition, while the fourth peak at ∼4.1 V originates from H2 −→ H3 transition [33]. As a
battery ages, changes in peak features can be observed. Variations in peak height or peak area are
indications on capacity fade, while a shift in position indicates resistance increase [34]. Changes
in peak features have been used as a SOH-indicator in several previous studies on battery ageing
[19] [28] [30] [35].
Figure 2.3. A charge curve (left) and a dQ/dV vs. V plot (right) for an NMC/graphite cell, with peaks
corresponding to anodic intercalation stages, with crystal phase transitions marked. Adapted from [33][34].
ICA only requires monitoring of current, voltage and time during a full charge or discharge cycle.
However, a major drawback with ICA is the requirement of a constant charge/discharge current.
This is not always applicable, particularly in cases where the current varies substantially, e.g. during
discharge in electric vehicles. Another drawback is artifacts due to kinetic phenomena associated
with higher C-rates, and information related to degradation phenomena may be mistakenly omitted.
In order to avoid misinterpretations of the dQ/dV curve, the capacity must be measured under
quasi-equilibrium, hence, at low C-rates, e.g. C/25 [30] [36]. However, charging a battery at
C/25 rate requires at least 25 hours of charging. This may not be a practical solution in military
applications if the situation requires faster charging. Yet, Li et al. [30] conducted ICA on NMC
batteries charged at C/2 rate and were able to perform a SOH estimation based on changes in peak
characteristics.
2.3.3 Impedance increase through EIS measurements

Impedance is the total contribution of capacitive, inductive and resistive phenomena in the cell,
which all oppose the flow of current through the cell. The battery’s impedance increases as the
battery ages and can therefore serve as a battery parameter for SOH estimation. Electrochemical
impedance spectroscopy (EIS) is a non-invasive method that is used to measure the impedance of
an electrochemical cell. EIS can be performed either galvanostatically or potentiostatically. In a
galvanostatic EIS, a small sinusoidal current is applied to the cell and the voltage response through
the cell is measured. In potentiostatic EIS, a sinusoidal voltage is applied, and the subsequent cur-
rent response is measured. In both methods, the sinusoidal signal is applied over a wide frequency
range, commonly ranging from 100 kHz to 100 mHz [37][38]. Using complex notation and in-
√
troducing the imaginary unit j (j = −1), the impedance Z(ω) [Ω] can be written according to
Ohm’s law using the sinusoidal current I(ω) [A] and sinusoidal voltage V (ω) [V]:
V (ω) V0 ejϕ2
Z(ω) = = = Z0 ej(ϕ2 −ϕ1 ) (2.3)
I(ω) I0 ejϕ1
where ϕ1 and ϕ2 is the phase shift in the sinusoidal current and voltage, respectively. The impedance
in Equation 2.3 can be expressed as a complex number through Euler’s formula, with an imaginary
part Zim and a real part Zre , and ϕ = ϕ2 − ϕ1 :
Z(ω) = Z0 (cos(ϕ) + jsin(ϕ)) = Zre + Zim (2.4)
The imaginary part of the impedance, Zim describes the impeding phenomena of an inductor and
a capacitor, and the real part Zre describes the impeding phenomena of a resistor. The main in-
formation of the electrochemical phenomena can be obtained from a Nyquist plot. In a Nyquist
plot, the negative imaginary part of the impedance, −Zim , is plotted against the real part Zre , of-
ten resulting in one or more semi-circles along the real axis. Inductive phenomena dominate at
negative −Zim values, at higher frequencies. Instead, capacitive phenomena dominate at positive
−Zim values, at mid to low frequencies. Information about frequency dependence can be obtained
from a Bode plot, where the magnitude of the impedance, |Z|, and the phase angle, ϕ, are plotted
against the frequency in logarithmic scale. In order to interpret the meaning of the Nyquist plot,
the equivalent circuit model (ECM) is commonly applied. The ECM consists of the elements in
an ideal circuit, namely resistor, inductor, and capacitor. Thus, it represents the total system of an
electrochemical cell. By applying the ECM to the Nyquist plot, the purely resistive elements in
an electrochemical cell can be roughly approximated by the position and shape of the semi-circles
along the real axis [37][39]. See an example of a Nyquist plot and its resistive elements, and a
Bode plot in Figure 2.4 (a) and (b), respectively.
The intercept of the real axis (Zim = 0) has been attributed to the ohmic resistance, R0 , being a
sum of the resistance of the electrolyte, current collectors and electrodes. The diameter of a single
semi-circle has been attributed to the kinetically controlled charge transfer resistance RCT . The
protruding 45◦ straight line has been correlated to diffusionally controlled phenomena, denoted
RD [40][41].
According to [27], the measured impedance depends heavily on age, temperature and SOC. Fur-
thermore, it should be stressed that interpretation of Nyquist plots is non-trivial. According to Mei
et al. [40], previous literature have suggested several contradicting physical interpretations of the
resistive elements.
Kinetic control Diffusional control
Low frequency
R0 RCT RD
High frequency
(a) (b)
Figure 2.4. (a) Nyquist plot (blue) with R0 , RCT and RD marked in red along the real impedance axis
ZRe . Adapted from [41]. (b) Bode plot showing the log of the impedance |Z|, and phase angle, as a
function of log frequency.
Despite the complexity of EIS measurements and Nyquist plot interpretations, a similar and simpli-
fied AC-based technique is often applied in industry to measure the internal impedance of batteries.
Instead of measuring the impedance of a wide frequency range, a single frequency is applied. A
frequency of 1000 Hz is commonly used to measure the internal impedance of smaller size Li-ion
batteries (e.g. 3 Ah) [41]. Furthermore, single-frequency EIS measurements can be incorporated
into a BMS [9].
2.3.4 Resistance increase through HPPC-test

Another battery parameter commonly used as a figure of merit for SOH estimation is the resistance.
According to Noura et al. [28], the battery’s EOL limit for vehicle applications has in previous
studies been set to the point when the resistance reaches 160 % of its initial value. A non-invasive
method to evaluate the resistance is through the Hybrid Pulse Power Characterization test (HPPC-
test). The HPPC-test was proposed by U.S. Advanced Battery Consortium (USABC) and is a well
established and simple method for measuring the resistance in electrochemical systems [28][37].
In the HPPC-test, a constant DC charge or discharge current pulse is applied for a short period
of time, typically ranging between 1–30 seconds, but a common practice is to apply the pulse for
10 seconds. The voltage response from the applied current is then used to calculate the resistance,
using Ohm’s law [37] [42][43]:
∆Vpulse V0s − V10s

Rpulse = = (2.5)
∆Ipulse Imax
Imax [A] is the magnitude of the discharge current pulse, applied for 10 s, and V0s − V10s [V]
corresponds to the voltage drop when the current pulse is applied. The total resistance of the
10 seconds pulse, Rpulse [Ω], comprises several contributions to the resistance. Ohmic resistance
(R0 ) arises due to resistance of electrodes, current collectors and electrolyte. Another contribution
is the charge transfer resistance (RCT ) due to activation of reactions and charge transfer at the
interface between electrolyte and electrode. Finally, another contribution is the polarisation (or
diffusion) resistance (Rp ) due to limitations in mass transport in electrodes and electrolyte [37]
[43]. Figure 2.5 illustrates a typical discharge pulse and the corresponding voltage response in a
HPPC-test. According to [37], the voltage response due to the applied current occurs due to many
complex processes and each of the resistive contributions cannot be separated easily.
Voltage [V] Current [A]
V0 s 0
ΔVpulse ΔIpulse
Imax
V10 s
0 10 Time [s] 0 10
Time [s]
Figure 2.5. Current pulse (red) and voltage response (black) during HPPC, adapted
from [37].
Apart from cycling ageing and calendar ageing, a battery’s SOC and operating temperature can also
have a major effect on the measured resistance [37]. Hence, tracking the resistance at various SOC
and temperatures along battery ageing can be a necessity in order to estimate the SOH accurately
for certain battery chemistries and applications.
2.3.5 Summary of SOH estimation methods

A summary of the described experimental SOH estimation methods and their advantages and lim-
itations are presented in Table 2.2.
Table 2.2. Summary of experimental-based methods for SOH estimation, and respective advan-
tage and limitations. Collected and summarized from [17][27][28]
SOH evaluation method Advantage Limitations

Resistance measurements Direct and simple Less suited for online estimation
(HPPC) Accurate Affected by SOC and temperature
Impedance measurements Provide information about Results depend on battery
(EIS) electrochemical phenomena chemistry, SOC and temperature
Accurate
Capacity fade Direct and simple Requires full cycle charge/discharge
Accurate cycle, hence time consuming
ICA Provide information about Requires low C-rate,
degradation phenomena hence time consuming
Chapter 3
Methods
This chapter presents the chosen methods and methodology for investigating battery parameters
for SOH estimation on Li-ion batteries. The methodology is based on an assumption of a military
application, where the batteries are used under non-standard operating conditions with regard to
temperature and load. Moreover, it is assumed that the application requires full discharge capacity,
and that SOH estimation is performed under severe time constraints. Hence, the experimental setup
was not designed to allow for optimal thermal equilibrium before measuring battery parameters.
Battery parameters for SOH estimation were characterised on commercial batteries aged through
cycling ageing for a maximum of 250 cycles. The batteries were cycled at three operating temper-
atures in order to resemble different battery usage scenarios, and battery parameters were contin-
uously measured upon ageing.
3.1 Investigated Li-ion battery and battery specifications

Ageing behavior and battery parameters were investigated on the commercial power optimised
battery model INR21700–40T, manufactured by Samsung SDI. This battery model has wound
NMC cathodes and graphite anodes, and standardised cylindrical dimensions of 21 mm in diameter
and 70 mm in length. The manufacturer’s nominal battery specifications are presented in Table 3.1.
This battery model is equipped with a CID on the positive terminal.
17
18 CHAPTER 3. METHODS
Table 3.1. Nominal specifications of Samsung INR21700–40T power optimised

lithium ion battery cell [44]. Standard and rated charge/discharge parameters
were obtained at 23 ◦ C.
Battery parameters Specification

Nominal Voltage 3.6 V
Upper cutoff voltage 4.2 V
Lower cutoff voltage 2.5 V
Standard discharge capacity ≥ 4000 mAh

Standard discharge current 0.8 A
Standard charge current 2A
Rated discharge capacity ≥ 3900 mAh

Rated discharge current 10 A
Rated charge current 6A
Initial internal impedance ≤ 12 mΩ (at 1 kHz AC and 100 % SOC)
Recommended operating temperature Charge: 0 – 45 ◦ C

(Ambient) Discharge: −20 – 60 ◦ C
Recommended operating temperature Charge: 0 – 50 ◦ C

(Surface) Discharge: −20 – 80 ◦ C
According to the battery manufacturer, the INR21700–40T should not be charged at temperatures
below 0 ◦ C nor above 45 ◦ C [44]. However, according to the USABC, the recommended ambient
temperature range for batteries in electric vehicle applications ranges from 52 ◦ C down to −30 ◦ C
[45][46]. Therefore, to take into account the event of battery usage outside of the manufacturer
recommended limits, the batteries were cycled at three approximate temperatures (± 3 ◦ C) within
the range recommended by USABC; at 52 ◦ C, at −15 ◦ C and at room temperature, at 21 ◦ C. The
latter temperature is the only one within the manufacturer’s recommended range, and therefore
serves as a reference for normal battery usage.
The following battery parameters were investigated upon battery ageing:
• Impedance through GEIS
• Resistance through HPPC
• Charge and discharge capacity
• Surface temperature
In order to gain further information about degradation phenomena, the incremental capacity was
investigated at room temperature at 21 ◦ C prior to ageing and after ageing. In a post-mortem
study, the NMC and graphite electrode surfaces were investigated visually, and the NMC electrode
was investigated through X-ray diffraction analysis (XRD) to further investigate ageing induced
changes.
CHAPTER 3. METHODS 19
3.2 Experimental setup

A total of 9 batteries were aged; three at either room temperature (RT) at 21 ± 3 ◦ C, high temper-
ature (HT) at 52 ± 3 ◦ C or low temperature (LT) at −15 ± 3 ◦ C. For battery cycling and battery
parameter measurements, the EIS capable battery cycling system BioLogic BCS-815 was used.
The battery cycling system logged voltage, surface temperature and capacity continuously dur-
ing battery cycling, with measurement points every other second. The impedance was measured
through galvanostatic EIS (GEIS).
The battery terminals were connected to the battery cycling system through cables with 4 mm
banana plugs. Banana sockets were spot welded to the battery terminals using a nickel strip as
an extension. The negative and positive terminal of each battery, as well as the nickel strip, were
electrically isolated using Kapton tape. The connection is illustrated in Figure 3.1
The surface temperature was measured directly on the metallic surface at the center of each battery
using K-type thermocouples, as shown in Figure 3.1. A small piece of the outer polymer wrapping
(approximately 1 cm2 ) was cut off from each of the batteries and the K-type thermocouple was
attached to the metal surface using aluminum tape. The surface temperature was logged by the
BioLogic BCS-815 battery cycling system. For safety purposes, the batteries were placed on a
fireproof electrical insulation material.
Figure 3.1. A battery connected to the cycling

system through banana connectors at each ter-
minal. A thermocouple is connected to the mid-
dle part of the cylindrical surface of the battery.
3.2.1 Room-temperature (RT) cycling

Batteries cycled at RT were kept in a cylindrical stainless steel container with cable inlets. The
temperature inside the container was logged using Pico TC-08 USB thermocouple data logger.
The ambient temperature measured approximately 21 ± 3 ◦ C during the complete cycling session.
3.2.2 High-temperature (HT) cycling

In order to create an HT environment, an external heating system was mounted on a cylindrical
stainless steel container. The external heating system comprised a copper pipe wound around the
outer surface of the cylindrical stainless steel container and isolated with polyethylene foam. A 1:1
mix of water and glycol was used as a heating medium. The heating medium was continuously
pumped through the external copper pipe using a Lauda RK20–KS circulator. The circulator was
set to maintain the heating medium at a temperature of 90 ◦ C, which resulted in an ambient tem-
perature of approximately 52 ± 3 ◦ C inside the cylinder throughout the complete cycling session.
3.2.3 Low-temperature (LT) cycling

For LT cycling, the batteries were kept in a freezer. For safety purposes in case of thermal runaway,
the batteries were placed in a stainless steel container equipped with a fireproof electrical insula-
tion material on the bottom. The ambient temperature inside the freezer measured approximately
−15 ± 3 ◦ C.
3.3 Experimental procedure

This section describes the experimental procedure for battery cycling, parameter characterisation
and investigation of battery ageing.
3.3.1 Cycling ageing

The batteries were aged through repeated full charge and discharge cycles between 100 % and 0 %
SOC, in order to resemble a critical application that requires full discharge capacity. The discharge
current was set to 2.5C (10 A), the rated discharge current according to the battery specifications
shown in Table 3.1. To avoid battery failure due to excessive stress on the cells at elevated and
lowered temperatures, the charge current was set to 1C (4 A). This is slightly below the rated charge
current of 6 A according to the manufacturer specification. The batteries were cycled according
to a constant-current, constant-voltage regime (CC-CV) with the CV-steps included to ensure full
charge/discharge. Approximately 5 min rest were allowed between each charge and discharge.
After 250 cycles, the ageing cycling was terminated. The cycling ageing sequence is shown in
Figure 3.2.
A characterisation test was performed before initiating the cycling ageing and after every 50 cycles,
with the purpose of tracking changes in battery parameters, see next section, 3.3.2 Characterisation
test. Prior to initiating the characterisation test, a resting period of 20 min after cycling ageing was
allowed for HT and RT cycled batteries. For LT cycled batteries, the resting period was extended to
a minimum of 2 hours to allow them to cool down after cycling ageing, and thus take into account
the effect of low internal temperature during capacity measurements.
Start cycling
ageing
CC Charge
1C (4 A )
4.2 V cutoff
CV
4.2 V
C/20 cutoff
CC Discharge
2.5C (10 A)
2.5 V cutoff
CV
2.5 V
C/20 cutoff
50 cycles
No
finished?
Yes
Go to
characterisation
test
Figure 3.2. Cycling ageing sequence, repeated 50 times and followed by

a characterisation test. The batteries were exposed to a maximum of 250
cycles.
3.3.2 Characterisation test

The characterisation test, visualised in Figure 3.3, was performed on each battery at the beginning
of and after every 50 cycles along the cycling ageing process. The test was divided into four steps.
Since the magnitude of impedance and the resistance are reported to depend on SOC [27] [37],
these two battery parameters were measured at three different SOC; 100 %, 80 % and 50 % SOC,
respectively.
3.3.2.1 Capacity measurements

The first step comprised a full CC-CV charge cycle at C/2 (2 A) with C/20 (0.2 A) cutoff at CV-step,
followed by approximately 10 min rest and a full discharge at C/2. According to a JRC Technical
report of standards for performance assessments of Li-ion batteries for electric vehicles [47], the
average charge and discharge rate of an electric vehicle is commonly set to C/3 rate for battery
testing. In this project however, capacity measurements were based on the standard charge current
in the manufacturer specification.
3.3.2.2 Impedance measurements through GEIS

The impedance was measured after approximately 20 min rest at OCV. For HT and RT cycled
batteries, the impedance was measured through GEIS using a 50 mA AC amplitude. The fre-
quency ranged from 10 kHz to 100 mHz, with 40 measurement points and two average measures
per frequency. Love et al. [48] found that the noise in EIS measurements increased significantly
with lower temperatures, and that increasing the current amplitude reduced the noise. Therefore,
a 100 mA amplitude current was used during EIS measurements at LT (−15◦ C), and the low fre-
quency range was extended to 10 mHz in order to include the diffusionally controlled region, which
was shifted towards lower frequencies at low temperatures.
3.3.2.3 Resistance measurements through HPPC-test

Following the EIS measurements and 10 min rest at OCV, the discharge resistance was measured
through HPPC-test; a single discharge pulse at 1C (4 A) was applied for 10 seconds at 100 % SOC,
80 % SOC and 50 % SOC, and the resistance was calculated through Ohm’s law in Equation 2.5.
3.3.2.4 State of charge estimation

SOC corresponding to 80 % and 50 % was reached through Coulomb counting. Coulomb counting,
also called Ah-counting, is a balancing method used to estimate the SOC by integrating the current
over time as the battery charges or discharges. The SOC was calculated starting from 100 % SOC
according to 3.1 [43],
∫
I dt
SOC(t) = SOCstart − 100 · (3.1)
Qn
where SOCstart equals 100% SOC, and the nominal capacity Qn corresponds to the capacity of a
full discharge cycle at investigated temperatures. It should be noted that this method do not account
for errors resulting from e.g. current sensors reading, and errors may accumulate to the calculated
SOC value [49], hence, the calculated SOC is an approximation. To correct for capacity losses due
to ageing, the Qn value was updated regularly during the ageing process. For batteries cycled at RT,
Qn was updated after 100 cycles of cycling ageing. For batteries cycled at HT and LT, the capacity
fade was expected to occur faster due to temperature’s accelerating effect on battery degradation
and for that reason, the Qn value was updated after every 50 ageing cycles.
Start
characterisation
test
Step 1 CC-CV Charge

to 100 % SOC
Full charge and

discharge cycle
at standard
CC Discharge
charge C-rate
to 0% SOC
CC-CV Charge
100 % SOC
Step 2
Impedance and
internal GEIS
resistance
measurements
at 100 % SOC
HPPC
CC Discharge
to 80 % SOC
Step 3
Impedance and
internal GEIS
resistance
measurements
at ? 80 % SOC
HPPC
CC Discharge
to 50% SOC
Step 4
Impedance and
internal GEIS
resistance
measurements
at ? 50 % SOC
HPPC
CC Discharge
to 0% SOC
Go to cycling
ageing
Figure 3.3. Characterisation test sequence. Step 1 constitutes capacity

measurements, while step 2, 3 and 4 constitutes impedance and resistance
measurements at 100 %, 80 % and 50 % SOC.
3.3.3 Characterisation at beginning of cycling and end of cycling

In order to investigate the temperature’s effect on the investigated battery parameters, the character-
isation test in Figure 3.3 was performed on all batteries at RT (21 ◦ C) prior to initiating the cycling
ageing session at HT (52 ◦ C) or LT (−15 ◦ C). In addition, a charge sequence at C/10 (0.4 A) was
performed in order to qualitatively investigate the electrode characteristics through ICA. The cho-
sen C-rate, which has also been adopted by [19] for ICA, is hence a compromise between accuracy
and time requirement, seeing that C/25 rate is commonly adopted in literature [30].
Once the cycling ageing protocol and intermittent characterisation tests were completed, batteries
tested at HT and LT were placed in RT again. After approximately 8 hours of rest, the characteri-
sation test and C/10 charge sequence were performed one last time.
3.3.4 X-ray diffraction analysis

In order to investigate the structural changes of the electrode material after battery cycling, a post-
mortem X-ray diffraction (XRD) analysis was performed on the NMC cathode material. XRD is a
technique used to characterise the crystal structure of a material by illuminating it with X-rays and
detecting the scattered light. Qualitative and quantitative information about the crystal structure
can be obtained based on the intensity and angle of the scattered X-ray light. [50].
A crystal lattice is constructed by so called unit cells. A unit cell is a group of atoms which are
repeatedly and symmetrically arranged in all dimensions, building up the crystal lattice. The ge-
ometry and size of the unit cell is described by the length of the lattice vectors a, b and c along
a three dimensional axis. When the atoms in a crystal are illuminated by X-ray light, the light is
scattered and due to the ordered arrangements of atoms, the scattered light forms a diffraction pat-
tern. The constructive interference from the diffraction pattern corresponds to diffraction peaks in
a spectrum. Through Bragg’s law (Equation 3.2), the diffraction peaks can be associated with the
angle, 2θ, at which the constructive interference is observed [51]:
λ = 2dhkl sinθ (3.2)
where λ is the wavelength of the X-ray light, 2θ is the angle where constructive interference of
the scattered light is observed, and dhkl is the distance between the parallel planes of atoms in the
crystal lattice. The indices h, k and l denotes the positions where the plane intercepts vector a, b
and c of the unit cell.
The intensity and position of the diffraction peaks depend on the geometry of the unit cell. If the
arrangement of atoms changes so that the geometry of the unit cell changes, the diffraction pattern
and peak position changes as well. Therefore, changes in peak position serves as an indicator on
structural changes in the crystal [51]. According to [52], changes in position of the (1 0 8) and
(1 1 0) peaks are correlated to changed content of lithium in the aged NMC material.
For practical reasons, XRD measurements were carried out at two different occasions using two
different X-ray diffractometers. At the first occasion, XRD was performed on NMC electrodes of
RT-cycled batteries using a Bruker 2D Phaser 2nd Gen X-ray diffractometer with Cu Kα radiation
source (λ = 1.54184 Å). The electrodes were measured over a range of 15◦ − 70◦ (2θ), with an
increment of 0.024◦ and measuring time of 0.7 seconds per step.
At the second occasion of XRD-measurements, the NMC electrode of a HT-cycled battery was
investigated using a Siemens Diffraktometer D5000 with Cu Kα radiation source (λ = 1.54184 Å).
The electrode was measured over a range of 33◦ – 53◦ (2θ) and 63◦ – 67◦ (2θ), with an increment
of 0.015◦ and measuring time of 5 seconds per step.
At each occasion, XRD measurements were also performed on the NMC electrode of an uncycled
battery used as a reference.
3.3.5 Cell disassembly

In order to access the electrode material for XRD analysis, six batteries were disassembled; two
uncycled, two cycled at RT, one cycled at HT, and one cycled at LT. The batteries were fully dis-
charged down to 2.5 V prior to cell disassembly, after which the OCV measured approximately 3 V.
For the LT cycled battery, the OCV measured 3.6 V after two discharge attempts. The batteries
were cut open using an angle grinder with a ceramic blade and the electrode material and separator
were extracted. Pieces of the anode and cathode electrodes were cut out and washed with acetone
in order to remove residual electrolyte.
Chapter 4
Results
This chapter introduces the results from the ageing of 9 batteries at either HT (52 ◦ C), LT (−15 ◦ C)
or RT (21 ◦ C). The chapter is divided into sections according to the investigated battery parame-
ters. Under each section, a comparison is made between battery parameters at each investigated
temperature. Lastly, the results from the XRD analysis are presented.
For better readability, individual cells kept at HT, RT or LT during cycling are henceforth denoted
H, R or L, respectively, with numbers 1, 2 and 3 used to indicate individual cells. In the figures,
red coloured graphs represent batteries cycled at HT, green coloured graphs represent RT, and blue
coloured graphs represent LT.
To enable a straight forward comparison between individual cells and cycling temperature, the
following EOL limits were adopted for SOH estimation, seeing that these limits are commonly
adopted in literature [29] [28]: 80 % capacity retention, 160 % of the initial resistance and 160 %
of the initial impedance.
4.1 Capacity
This section presents the capacity measurements at C/2-rate (2 A) from the characterisation tests.
Furthermore, the ICA measured at beginning and end of cycling are presented.
4.1.1 Charge and discharge capacity

Examples of charge and discharge curves at C/2-rate are presented in Figure 4.1. (a) and (b) shows
the HT charge and discharge capacity as a function of cell voltage, respectively. (c) and (d) shows
the charge and discharge curves at RT, respectively. Finally, (e) and (f) shows the charge and
discharge curves at LT, respectively. With increasing cycle number, a capacity fade can be observed
as the charge and discharge curves are shifted towards lower capacities. The capacity fade was most
prominent for batteries kept at LT, followed by batteries kept at HT.
26
CHAPTER 4. RESULTS 27
(a) (b)
(c) (d)
(e) (f)
Figure 4.1. (a) Charge curves and (b) discharge curves at C/2, HT (H1). (c) charge curves and
(d) discharge curves at C/2, RT (R2). (e) charge curve and (f) discharge curve at C/2, LT (L2).
28 CHAPTER 4. RESULTS
The discharge capacity Q measured at each characterisation test was normalised to the initial dis-
charge capacity, Qinit , measured at the first characterisation test. In Figure 4.2, the normalised
discharge capacity, Q/Qinit , is presented as a function of number of ageing cycles. Figure 4.2 (a)
shows the discharge capacity fade for all batteries cycled at RT, HT and LT, while (b) shows the
discharge capacity fade for two batteries showing deviation with respect to ageing behavior (H2
and R1). For better readability, the results from these batteries are henceforth presented separately.
(a) (b)
Figure 4.2. (a) Relative discharge capacity fade at C/2 for HT (red), RT (green) and LT (blue)
cycling. (b) Discharge capacity fade for two deviating batteries (H2 and R1).
As seen in (a) and (b), neither of the batteries kept at RT reached the EOL limit of 80 % remaining
capacity after 250 cycles. For the batteries kept at HT however, H1 and H3 reached their EOL after
200 cycles, while H2 reached their EOL earlier, slightly before 150 cycles. Each of the batteries kept
at LT passed the EOL limit between 150–200 cycles, with a major capacity drop after 200 cycles.
The last data point after 250 cycles is missing for L1 due to time constraints.
Two out of three batteries at HT lost contact with the cycling system before reaching 250 cycles;
H2 lost contact after 220 ageing cycles, while H3 lost contact after 239 ageing cycles. For that
reason, Figure 4.2 lacks measurement points for H2 and H3 after 200 cycles. The contact loss
appeared as a drop in OCV towards 0 V, see Appendix A, Figure A.1. The contact loss is likely
due to the activation of the CID, which activates upon internal pressure build up and for safety
purposes eliminates contact between the terminals, hence the drop in OCV.
4.1.2 Incremental capacity analysis

To gain more information about battery degradation based on capacity, ICA was performed at RT
prior to and after ageing. Figure 4.3 below shows the dQ/dV vs V plot for battery R2 (a), H1 (b)
and L3 (c). As reported by Li et al. [30], noise is a common phenomenon in the derivative of the data
due to high sampling frequency. Therefore, filtering of the experimental data is commonly required
in order to identify the peaks in a dQ/dV vs.V plot. However, care must be taken when filtering
the data since the peaks may be deformed and important characteristics may be omitted if the data
is too smoothed. Li et al. [30] proposes a smoothing algorithm for ICA using moving average
pre-filtering followed by Gaussian filter. Reduced noise without oversmoothing was observed by
Li et al. [30] using moving average smoothing points corresponding to 0.55 % of the total number
of experimental data points, followed by Gaussian filter using smoothing points corresponding to
3 % of the number of data points. The same approach was therefore adopted in this study.
Four peaks can be identified in each spectra. The fourth peak (IV) is a typical feature of NMC811,
and corresponds to the H2 −→ H3 phase transition [33]. In an NMC811 electrode, the relative
nickel-content is at least 80 %.
A decrease in peak height and shift towards higher voltages can be observed for peaks I, II and III in
each graph. According to [19], a simultaneous decrease in peak height and voltage shift indicates
LLI. This phenomenon is most prominent for the LT cycled battery, as neither of peaks I, II and III
can be distinguished with certainty after cycling. Furthermore, [19] report that a decrease in peak
height at a constant voltage indicates LAM. This phenomenon is observed for peak IV of the HT
cycled battery, and could possibly indicate LAM at the NMC electrode.
(a) RT cycled battery.
(b) HT cycled battery.
(c) LT cycled battery.
Figure 4.3. Incremental capacity curves measured at 21 ◦ C, before and

after ageing at various temperatures; (a) at RT, (b) at HT and (c) at LT.
Identified peaks are marked (I-IV).
4.2 Resistance
The resistance R measured through HPPC-test at each characterisation test was normalised to the
initial resistance, Rinit . In Figure 4.4, the normalised resistance, R/Rinit , is presented as a function
of numbers of ageing cycles; (a) shows the normalised resistance at 100 % SOC, (b) at 80 % SOC
and (c) at 50 % SOC. The normalised resistance for deviating batteries (H2 and R1) are presented
separately in (d).
(a) 100 % SOC. (b) 80 % SOC.
(c) 50 % SOC. (d) Deviating batteries.
Figure 4.4. Normalised resistance with number of cycles measured at (a) 100 % SOC (b) 80 % SOC
and (c) 50 % SOC and d) relative change for two deviating batteries.
In (a), (b), and (c), the resistance increase behaved similarly for batteries kept at LT and RT during
the initial 100 cycles, with a slightly higher increase at 100 % SOC. For batteries kept at HT
however, the resistance increased more rapidly with number of cycles, indicating a faster resistance
build-up. Furthermore, the resistance varied more with SOC at HT, as the highest resistance was
measured at 100 % SOC. For instance, according to the resistance increase observed at 100 % SOC
(a), batteries H1 and H3 reached their EOL after approximately 150 and 200 cycles, respectively.
However, at 80 % and 50 % SOC, these batteries never reach their EOL within the cycling frame.
After 100 cycles at LT, the batteries behaved inconsistently. The resistance for L3 increased, while
the resistance of batteries L1 and L2 first decreased, followed by a rapid increase after 150 cycles.
Between 200–250 ageing cycles, batteries L2 and L3 breached the EOL limit at each SOC.
For battery R1 in (d), the resistance increased more rapidly than R2 and R3, ultimately reaching
∼ 300 % of its initial resistance after 250 cycles. A sharp initial decrease in resistance was observed
for battery H2, which reached their EOL after 150 cycles.
4.3 Impedance
Changes in magnitude of impedance |Z| were investigated with number of ageing cycles, and a
single point frequency was investigated for SOH estimation. A frequency of 980 Hz was adopted
as it turned out to be the frequency point closest to 1000 Hz, which is the single point frequency
commonly adopted for battery testing [41]. The magnitude of the impedance was extracted through
the impedance–frequency dependence of Bode-plots, see an example in Appendix B Figure B.1.
Figure 4.5 shows the impedance normalised to the initial impedance, |Z|init , as a function of num-
ber of ageing cycles. Figure 4.5 (a) shows the normalised impedance at 50 % SOC and (b) shows
the normalised impedance at 50 % SOC for the two deviating batteries (H2 and R1). During the
characterisation test of H2 at cycle 150 and 200, the battery cycling system failed to measure the
impedance at 100 % and 80 % SOC, hence, only measurement points at 50 % SOC are presented.
However, the variation in impedance with respect to SOC appeared to be negligible at a frequency
of 980 Hz.
(a) (b)
Figure 4.5. (a) Relative change in impedance at 980 Hz with number of cycles at 50 % SOC
and b) relative change for two deviating batteries.
After 250 cycles, the impedance had increased by approximately 4–5 % at RT, and approximately
10 % at HT. This could indicate slightly accelerated degradation at elevated temperatures. However,
the results in (a) show that neither of the batteries kept at RT nor HT reached their EOL with respect
to single point impedance measurements at 980 Hz. Interestingly, the impedance began to increase
sharply for batteries kept at LT after 150 ageing cycles. Between 200–250 ageing cycles, the EOL
limit had been breached, and battery L2 had reached a relative increase of approximately 260 %,
and battery L3 had reached a relative increase of approximately 170 %. Battery L1 was only cycled
to 200 ageing cycles due to the time constraints of this project, but a sharp increase was nevertheless
observed after 200 ageing cycles.
The impedance increase deviated strongly for two batteries shown in d), as it reached up to a roughly
300 % increase compared to the initial impedance for R1, and almost 800 % for H2. For R1, the
behavior in impedance resembles the behavior with regard to resistance, seen in Figure 4.4 (d). For
H2 however, a resistance increase of ∼800 % is not reflected in the resistance measurements. This
measurement point could be an outlier due to experimental error during the impedance measure-
ment, seeing that the battery cycling system failed to measure the impedance at 100 % and 80 %
at this point.
4.3.1 Impedance spectra

To investigate the type of resistive contribution captured at 980 Hz, impedance spectra of the full
frequency range were analyzed. The impedance spectra are visualised in Figure 4.6 in the form of
Nyquist plots. (a) shows impedance spectra recorded at HT, (b) at RT and (c) at LT after a selection
of ageing cycles, with the measurement point at 980 Hz marked in an expanded view (d). Recall
that a 50 mA current amplitude was used for the HT and RT cycled batteries, which resulted in
noisy readings. For batteries cycled at LT, the current amplitude was increased to 100 mA, hence
the reduced noise.
Figure 4.6 (a) shows the impedance spectra of a battery cycled at HT. The spectra recorded at
beginning of cycling ageing (blue) lacks the semi-circle corresponding to the kinetically controlled
charge transfer resistance, RCT . As the cycling ageing proceeded, a semi-circle appeared and
increased both in diameter and radius with number of cycles. This phenomenon was observed for
all three batteries cycled at HT, at each SOC. After 250 cycles, both the diameter and radius of the
semi-circle had increased drastically.
For a battery cycled at RT (b), the diameter of the semi-circle increased with number of cycles as
well, indicating that the charge transfer resistance increased with ageing. This phenomenon was
observed for all three batteries cycled at RT, at each SOC. For batteries cycled at LT, the radius and
diameter of the semi-circles in (c) either decreased or remained constant between 1–150 ageing
cycles. However, it was observed for all LT cycled batteries and at each SOC, that after 200 cycles,
the diameter of the semi-circle increased. A major increase in charge transfer resistance RCT was
observed after 250 ageing cycles. Note that the scale of the imaginary part of the impedance (y-
axis) in Figure 4.6 (c) is almost 25 times that of the batteries cycled at HT and RT in (a) and (b),
indicating a stronger capacitive contribution to the imaginary part of the impedance at LT. A slight
shift along the real axis (Zim = 0) with number of cycles can be observed in the impedance spectra
for each cycling temperature, corresponding to an increased ohmic resistance R0 with number of
cycles [40].
(a) HT impedance spectra. (b) RT impedance spectra.
(c) LT impedance spectra. (d) Expanded view of LT impedance spectra.
Figure 4.6. Nyquist plots at 80 % SOC at beginning, midst and end of ageing; (a) shows impedance
at HT (H1), (b) at RT (R2) and (c) at LT (L2) (d) expanded view of LT spectra, with readings at
980 Hz marked.
In order to investigate the SOC dependence of the impedance, Figure 4.7 shows impedance spectra
recorded at HT at the first characterisation test, and at the characterisation test after 200 ageing cy-
cles. Impedance spectra at 100 %, 80 % and 50 % SOC are visualised. At the first characterisation
test (cycle 1), there were negligible variations in impedance spectra with SOC. After 200 ageing
cycles, changes in impedance spectra had occurred. At 100 % SOC, the diameter and radius of the
semi-circle had increased drastically, however, they decreased with decreasing SOC. These phe-
nomena were observed for all batteries kept at HT. For RT and LT cycled batteries, these variations
with SOC were observed as well, however to a lower extent.
Figure 4.7. Impedance spectra of a single battery recorded

at 100 %, 80 % and 50 % SOC, at beginning of cycling and
after 200 ageing cycles at HT (52 ◦ C).
4.4 Surface temperature

In order to show how the surface temperature of the batteries changed with ageing, the maximum
surface temperature was collected from the capacity test of each characterisation test along cycling
ageing. The results are shown in Figure 4.8; (a) showing maximum surface temperature at C/2
charge and (b) at C/2 discharge.
For batteries kept at RT and HT, the surface temperature increased by approximately 4 ◦ C and 6 ◦ C,
respectively, at C/2 charge. During discharge, the surface temperature increased by approximately
6 ◦ C and 8 ◦ C at RT and HT, respectively. For the LT cycled batteries, the surface temperature
rose by approximately 10 ◦ C during charge, and by approximately 10–20 ◦ C during discharge. No
trend in temperature change with ageing could be observed for RT and HT cycled batteries. For
LT cycled batteries, the surface temperature appeared to increase slightly at C/2 discharge after
150 cycles.
(a) (b)
Figure 4.8. Temperature variation with number of ageing cycles at (a) charge and (b) discharge
at C/2 (2 A).
Figure 4.9 presents the maximum surface temperature of each tested battery during the cycling
ageing as a function of cycling number. (a) shows the surface temperature at 1C (4 A) charge,
and (b) shows the surface temperature at 2.5C (10 A) discharge. At 1C charge, the maximum
surface temperature rose by approximately 10 ◦ C for batteries cycled at RT and HT, reaching a
temperature of approximately 30–34 ◦ C and 62–68 ◦ C, respectively. For batteries cycled at LT, the
surface temperature rose from −15 ◦ C to a maximum of approximately 10 ◦ C, indicating the effect
of internal heat generation upon battery operation.
(a) (b)
Figure 4.9. Temperature variation with number of ageing cycles at (a) 1C charge and (b) 2.5C
discharge.
As shown in (b), the effect of internal heat generation was even more prominent at 2.5C rate (10 A)
discharge. The surface temperature rose by approximately 30 ◦ C for batteries cycled at RT, however,
no variation with ageing could be observed. Similarly, the surface temperature of batteries H1 and
H3 rose by approximately 30 ◦ C. However, a higher surface temperature increase was observed for
battery H2, which reached a maximum surface temperature of 92 ◦ C (corresponding to a 40 ◦ C
absolute increase). After 220 ageing cycles, the CID on battery H2 was activated, resulting in a
contact loss with the cycling system. Likewise, the CID of battery H3 was activated after 239 ageing
cycles. The maximum surface temperature read 88 ◦ C for H2 and 77 ◦ C for H3 at the discharge
cycle prior to the CID activation.
For LT cycled batteries, the surface temperature began to increase after approximately 150 dis-
charge cycles. Recall that according to the results in section 4.1.1 Charge and discharge capacity,
the batteries kept at LT reached their EOL with respect to capacity fade after 150 cycles. For batter-
ies L2 and L3, which were cycled to 250 cycles, the surface temperature increased to a maximum
of approximately 40 ◦ C and 50 ◦ C, respectively. In Figure 4.10, surface temperature rise of L3
after 150 cycles is clearly visualised, with a sharp increase after 200 cycles. After 236 cycles, the
maximum surface temperature dropped to ∼36 ◦ C. Such a drop in maximum surface temperature
was only observed for L3.
Figure 4.10. Variation in surface temperature of battery L3 during 250

discharge cycles at 10 A and −15 ◦ C. Each 50th increment of ageing cycles
is marked.
4.5 Temperature’s effect on battery parameters

before and after ageing
In order to investigate temperature’s effect on battery parameters, the discharge capacity, resistance
and magnitude of impedance (measured at 980 Hz) for HT and LT cycled batteries are summarised
in Table 4.1. The table includes battery parameters measured during a first characterisation test
prior to initiating the 250 charge/discharge cycles protocol. The battery parameters were measured
both at 21 ◦ C (RT) and approximately 8 hours after changing the temperature to either 52 ◦ C (HT)
or −15 ◦ C (LT). Furthermore, the table includes the normalised change in measurements (%) with
respect to RT.
Increasing the temperature to 52 ◦ C led to a decrease in resistance. For cells H1 and H3, the
resistance decreased to 86 % and 76 % of the initial resistance measured at 21 ◦ C, respectively.
For the deviating battery H2 however, the resistance increased instead by approximately 250 %.
In general, the discharge capacity decreased by up to 10 % by increasing the temperature. An
increased temperature had no effect on the magnitude of impedance at 980 Hz, except for the
deviating battery H2, for which the impedance increase was almost threefold.
Cooling down the batteries to −15 ◦ C increased the resistance by approximately 340 % relative to
the resistance measured at 21 ◦ C. Furthermore, decreasing the temperature to −15 ◦ C led to a 12–
13 % increase in impedance. The discharge capacity retention after cooling the batteries measured
approximately 87 %.
Table 4.1. Battery parameters measured at 21 ◦ C (RT) and after changing temperature to either 52 ◦ C
(HT) or −15 ◦ C (LT). Battery parameters are obtained at 100 % SOC before initiating ageing cycling.
Cell ID QRT QHT QHT /QRT RRT RHT RHT /RRT |Z|RT |Z|HT |Z|HT /|Z|RT
[mAh] [mAh] [%] [mΩ] [mΩ] [%] [mΩ] [mΩ] [%]
H1 4130 3700 90 22 19 86 12 12 100
H2 3780 3600 95 26 66 254 14 51 364
H3 3790 3770 99 25 19 76 13 13 100
Cell ID QRT QLT QLT /QRT RRT RLT RLT /RRT |Z|RT |Z|LT |Z|LT /|Z|RT
[mAh] [mAh] [%] [mΩ] [mΩ] [%] [mΩ] [mΩ] [%]
L1 3900 3400 87 27 92 341 16 18 113
L2 4000 3520 88 27 92 341 17 19 112
L3 4120 3580 87 26 88 338 17 19 112
After ageing cycling, the batteries kept at HT and LT were allowed to reach RT again and a final
characterisation test was performed. Hence, variations in battery parameter’s due to temperature’s
effect could be controlled for.
The parameter data are summarised in Table 4.2. Subscript B indicates measurement prior to
ageing cycling, and E indicates measurements after ageing cycling. The normalised change is
presented with respect to the initial value at RT at beginning of cycling. The initial capacity QB
varies by up to 9 % (340 mAh) between individual cells. According to Pastor-Fernández et al. [19],
it has previously been shown that the variation in initial capacity between individual cells of the
same battery type can reach approximately 9 %. The initial magnitude of the impedance measured
at 980 Hz ranges between 12 mΩ and 17 mΩ. According to the manufacturer specification [44],
the initial impedance at 100 % SOC measures maximum 12 mΩ. The deviation could be due to
increased series resistance from the welding of connectors.
Table 4.2. Battery parameters measured at RT (21 ◦ C) for individual cells, at beginning of
cycling (subscript B) or end of cycling (subscript E). Battery parameters are obtained at 100
% SOC.
Cell ID QB QE QE /QB RB RE RE /RB |Z|B |Z|E |Z|E /|Z|B

[mAh] [mAh] [%] [mΩ] [mΩ] [%] [mΩ] [mΩ] [%]
H1 4130 2700 65 22 79 359 12 14 116
H2 3780 1- - 26 - - 14 - -
H3 3790 1- - 25 - - 13 - -
R1 3820 3150 82 26 76 292 15 60 400

R2 3950 3320 84 23 28 122 12 13 108
R3 4050 3420 84 22 28 127 12 13 108
L12 3900 2500 64 27 35 130 16 17 106

L2 4000 1900 48 27 44 163 17 21 124
L3 4120 1400 34 26 55 212 17 24 141
Neither of the batteries kept at RT passed the EOL limit of 80 % retaining capacity. H1 and all
batteries kept at LT had by far passed the EOL limit, with the greatest decrease observed for the
batteries cycled at LT.
The resistance increase and impedance increase do not consistently reflect the degree of capacity
fade. For instance, battery L1 had only 64 % of its initial capacity left after 200 ageing cycles,
while the resistance rose to 130 % of the initial value. Recall that an EOL limit of 160 % increase
compared to that of the initial value was adopted for impedance and resistance in this study. Note
also for H1 the major relative increase in resistance compared to that of the impedance after ageing.
4.6 Battery disassembly

In order to visually investigate ageing induced changes to the electrodes and separators, batteries
were disassembled post-cycling; one HT cycled battery, one LT cycled battery and two RT cycled
batteries, out of which one was the deviating battery R1. Two non-cycled batteries were disassem-
bled to use as a reference. Each battery was discharged to 2.5 V, including a CV-step with cutoff
at a current of 0.2 A (C/20-rate) to ensure full discharge. However, the OCV of the battery cycled
at LT rose to 3.6 V despite two attempts of discharge.
1
No data due to CID activation and contact loss.
2
Ageing terminated after 200 ageing cycles due to time constraints.
The cathode (NMC) of the RT cycled batteries (R1 and R2) showed no visual changes compared
to that of the reference. No changes were seen on the graphite anode either. For the HT cycled
battery (H1), the NMC cathode cracked more easily upon disassembly, exposing the aluminum
current collector. Otherwise, no visual changes could be observed on the surface. See a picture of
the NMC electrode of the HT cycled battery and that of the reference in Figure 4.11.
Figure 4.11. Surface of NMC cathode post cycling at 52 ◦ C (left), and of

that of a non-cycled battery (right).
In contrary, clear visual changes were observed on the graphite anode of the HT cycled battery
compared to that of the reference. Grainy deposits could be observed on the surface and the coating
came loose on several places, exposing the copper current collector beneath. Figure 4.12 shows a
picture of the graphite electrode post HT cycling and that of the reference.
Figure 4.12. Surface of graphite anode post cycling at 52 ◦ C

(left), and of that of a non-cycled battery (right).
Clear visual changes could also be observed on the separator of the HT cycled battery. While
the separator of the reference appeared white colored with no traces of electrode material, the
separator of the HT cycled battery had turned to a dull brown color with clear traces of deposits,
see Figure 4.13. The deposits are believed to be adhered coating from the graphite anode.
Figure 4.13. Surface of separator post cycling at 52 ◦ C

(left), and of that of a non-cycled battery (right).
Upon disassembly, the reference cell contained plenty of electrolyte. The batteries kept at RT
during ageing only had small traces of electrolyte left, and the batteries kept at HT was completely
dry upon disassembly.
Interestingly, upon disassembly of the battery cycled at LT (L3), a thermal runaway was immedi-
ately initiated. The cell burst open at the negative terminal and a fire broke out. See a picture of
the battery after the thermal runaway event in Figure 4.14.
A summary of the observations of the disassembled batteries is presented in Table 4.3.
Figure 4.14. Picture of battery L3 after thermal runaway. The negative

terminal burst open, exposing melted aluminum from the current collector.
Table 4.3. Summary of observations upon visual inspection of disassembled batteries.

Comparisons are made with respect to non-cycled reference batteries.
Cell ID OCV [V] Cathode (NMC) Anode (Graphite) Separator
R1, R2 3 No changes No changes No changes
H1 3 Cracking Deposition and cracking Color change and deposits
L3 3.6 -3 - -
3
Immediate initiation of thermal runaway upon opening of cell.
4.7 X-ray diffraction analysis

Seeing that no visual changes were observed on the cathode of the batteries cycled at RT, and
that R1 deviated with respect to impedance and resistance during ageing cycling, the project was
motivated to investigate possible ageing related changes of the crystal structure of the NMC cathode
through XRD measurements. Battery R2 and a non-cycled one were used as references. The NMC
cathode of HT cycled battery H1 was investigated as well. The spectra are fitted using Fityk 1.3.1
software, see more details in Appendix C.
Figure 4.15 (a) presents the diffraction pattern of the NMC cathode extracted from R1, R2 and one
non-cycled (pristine) as a reference. Peaks of interest between 64◦ and 66◦ are marked, and an
expanded view of the marked peaks are shown in (b). For visualisation purposes, the diffraction
patterns of R1 and R2 are shifted towards higher intensities in order to present them in the same
plot, and the intensity is given in arbitrary units. In order to estimate the direction of peak shift,
the position of the sharpest peaks at ∼36 ◦ were used as reference since the position of these peaks
seemed to remain constant post cycling. In (b), a peak splitting of (1 0 8) and (1 1 0) is observed.
For peak shift estimation in (b), the position of the leftmost peak with highest intensity was adopted.
(a) (b)
Figure 4.15. (a) XRD spectra of the NMC cathode from one non-cycled battery and two batteries
cycled at 21 ◦ C (1R and 2R). (b) Expanded view of the diffraction peaks marked in (a). The
intensity is given in arbitrary units (a.u.).
For R2, peak (1 0 8) shifted by 0.14◦ towards lower degrees, and (1 1 0) shifted toward higher
degrees by 0.15◦ , compared to the peak positions of the pristine electrode. For R1, (1 0 8) shifted
by 0.19◦ towards lower degrees, and (1 1 0) shifted by 0.10◦ towards higher degrees. For the
pristine electrode, the distance between the peaks measured 0.56◦ , and for R1 and R2, the distance
measured 0.85◦ , corresponding to a ∼50 % increase in peak separation compared to that of the
pristine electrode.
Figure 4.16 shows the expanded view of the diffraction spectra of the NMC cathode of H1 and
that of a pristine cathode. For better visualisation of differences, the intensity of diffraction pattern
corresponding to H1 is shifted towards higher intensities. (a) shows the reference peaks at ∼36◦ ,
and (b) shows an expanded view of peaks (1 0 8) and (1 1 0). A peak splitting of (1 0 8) and (1 1 0)
is observed. For peak shift estimation in (b), the position of the leftmost peak with highest intensity
is adopted.
(a) (b)
Figure 4.16. XRD spectra of NMC cathode for a battery cycled at 52 ◦ C (H1) and that of a
non-cycled reference. Expanded view of (a) reference peaks and (b) peaks (1 0 8) and (1 1 0).
The intensity is given in arbitrary units (a.u.).
Likewise, the sharpest observed peaks at ∼36 ◦ were used as reference, as the position of this peak
appeared to be unaffected by ageing. Peak (1 0 8) of H1 shifted by 0.18◦ towards lower degrees and
by 0.08◦ towards higher degrees. The distance between (1 0 8) and (1 1 0) measured 0.52◦ for the
pristine and 0.78◦ for H1; corresponding to a 50 % increase in peak separation for H1 compared
to that of the pristine.
Daemi et al. [50] report that a simultaneous separation and shift in 2θ of (1 0 8) and (1 1 0) cor-
responds to a decrease in a and b direction of the unit cell, and an increase along the c direction.
According to Buchberger et al. [52], such a structural change is a sign of a changed lithium content
in an aged NMC electrode. In this case, peak (1 0 8) was shifted towards lower 2θ and peak (1 1 0)
was shifted towards higher 2θ, for both R1, R2 and H1. The absolute distance between the peaks
of interest increased by 50 % for R1, R2 and H1 compared to of that of the pristine. This slightly
increased separation could indicate that a change in crystal structure of the NMC electrode have
occurred for R1, R2 and H1.
Chapter 5
Discussion
In this chapter, the results of the battery cycling ageing are discussed. The sections are arranged
according to each investigated battery parameter, and the chapter ends with a discussion of the
limitations of the current study as well as potential outlooks for future studies.
5.1 Capacity
Compared to RT cycled batteries, the capacity fade was accelerated at HT and LT, with a major fade
seen at LT. The major capacity fade could be due to lithium plating and accelerated SEI-layer forma-
tion, ageing phenomena which according to previous studies are accelerated at temperatures below
0 ◦ C [19]. A rapid capacity drop was observed for LT cycled batteries between 200–250 ageing
cycles. Burns et al. [53] described this phenomenon as rollover failure, occurring due to a build up
of kinetic hindrance. The rollover failure observed for the LT cycled batteries could have occurred
due a combination of the kinetic resistance of the growing SEI-layer and the low temperature con-
ditions. However, the impedance and resistance were still below the EOL limit at 200 cycles. The
potential onset of rollover-failure may therefore have gone unnoticed by looking at the impedance
and resistance increase only. Nevertheless, there were not enough data-points to confirm whether
the onset could have been detected.
A higher initial charge capacity was observed after 50 ageing cycles for HT cycled batteries, com-
pared to that of RT cycled batteries. This could be an effect of faster reaction rates and increased
ionic conductivity, phenomena which are favored at higher temperatures [16]. A similar effect was
observed on commercial NMC/graphite batteries by Jalkanen et al. [20]. In contrast, a lower initial
charge and discharge capacity was observed for LT cycled batteries, seeing that low-temperature
conditions slow down reaction rates and limit mass transport.
The ICA revealed changes in peak characteristics associated with capacity fade and resistance
increase. Some suggested degradation mechanisms that may have caused the capacity fade are
lithium plating, electrolyte decomposition and transition metal dissolution [19] [34]. However,
45
46 CHAPTER 5. DISCUSSION
more information is required in order to tell the exact cause for the capacity loss in each case.
Nevertheless, a major decrease in peak heights with simultaneous peak shifts were observed after
cycling at LT (c). This indicates a massive LLI, possibly due to lithium plating which occurs due to
mass transport limitations at temperatures below 0 ◦ C [27]. It is possible that the thermal runaway
initiation of L3 occurred due to plated metallic lithium reacting with water in the atmosphere upon
opening of the cell, initiating an exothermic reaction and fire outbreak [54]. This event further
highlights the safety risks of operating Li-ion batteries at lower temperatures, and in applications
where there is a risk of mechanical damage to the batteries.
The presence of the fourth peak suggests that the NMC electrode of this battery contains a high
relative amount of nickel, such as that of an NMC811 electrode. Previous studies on nickel-rich
electrodes have shown a high susceptibility for transition metal dissolution and associated capacity
fade due to LAM, particularly at high SOC [12]. In this project, the batteries were cycled between
100 % and 0 % SOC, mimicking a military application where the full discharge capacity at rated
discharge is required. Repeated charging to the recommended upper voltage limit could have con-
tributed to an increased risk of transition metal dissolution, hence accelerated capacity fade [12].
Nickel-rich NMC-electrodes are particularly susceptible to operating voltages above 4.0 V due to
the H2 −→ H3 crystal phase transition [33], and the ICA in this study revealed what is believed to
be such a phase transition at 4.1 V and possibly LAM at the NMC electrode.
Regular tracking of the capacity showed many signs of degradation arising from both LLI and
LAM. From an application point of view, it should however be stressed that a full capacity mea-
surement at C/2 rate corresponds to at least four hours of charging and discharging the battery,
hence, as suggested by several authors [19][28], the accuracy comes at the expense of the dispos-
able time.
5.2 Resistance
Investigation of the resistance through HPPC-tests showed an increasing resistance upon ageing at
each investigated temperature. An increase in resistance with ageing has previously been reported
to occur due to a combination of several degradation phenomena, such as degradation of current
collectors, active material and SEI-layer build up; the latter being associated with impeding charge
transfer of Li-ions during the intercalation and de-intercalation reactions [19][39]. The increase in
resistance was accelerated at HT, indicating an accelerated degradation. For LT cycled batteries,
the changes in resistance were inconsistent between individual cells between 100 and 200 cycles. It
is yet unknown whether this behavior could be an ageing phenomenon or an effect of temperature
fluctuations.
Solely changing the temperature at beginning of cycling had a major effect on the resistance. In-
creasing the temperature to 52 ◦ C resulted in a resistance decrease of approximately 20 %. This
effect could be due to the increasing temperature’s enhancing effect on kinetic phenomena in the
electrodes, which is a part of the total resistance obtained from pulse power tests [41]. In contrary,
decreasing the temperature to −15 ◦ C slowed down the kinetics, which is closely associated with
CHAPTER 5. DISCUSSION 47
resistance due to kinetic limitations in the electrodes and electrolyte [16]. In this study, an almost
threefold resistance increase was observed solely by decreasing the temperature to −15 ◦ C. A sim-
ilar effect was reported for LFP batteries, for which the resistance increase was threefold when the
batteries were cooled from 20 ◦ C down to −20 ◦ C [15]. This is crucial information if the resis-
tance is to be used accurately for SOH estimation, since a temperature decrease could mistakenly
be interpreted as battery ageing.
Changes in resistance upon ageing showed to depend not only on temperature, but also on the
battery’s SOC. The results from the resistance measurements revealed a notable SOC dependence,
for HT cycled batteries in particular. For instance, the HT cycled batteries reached their EOL with
respect to resistance increase between 150–200 cycles; however, only at 100 % SOC. At 80 % and
50 % SOC, the resistance remained below the EOL limit. This clearly indicates the importance of
considering the battery’s SOC when adopting the resistance for SOH estimation.
For LT cycled batteries, an initial decrease in resistance was observed at each SOC. Similarly,
this phenomenon was seen for R2 and R3 at 50 % SOC and most prominently for the deviating
battery H2. This phenomenon was also observed by Groot [29] on Li-ion batteries exposed to
cycling ageing, and was suggested to occur due to an initial decrease in charge transfer resistance.
According to Groot [29], it could possibly be an early sign of fast ageing.
5.3 Impedance
Impedance measurements at 980 Hz were not affected by the selected SOCs, and during the ini-
tial 150 cycles, only small differences were observed between the investigated temperatures. The
possibility that impedance measurements at 980 Hz mainly captured the purely ohmic contribution
to the impedance motivated the investigation of electrochemical phenomena using Nyquist plots.
The Nyquist plots showed an increasing charge transfer resistance RCT with cycling ageing, an
ageing phenomenon which apparently was not captured at 980 Hz. Furthermore, the impedance
varied with increasing SOC upon ageing, in particular for the HT cycled batteries.
The shift along the real axis in a Nyquist plot occurs due to an increase in ohmic resistance (R0 ),
indicating an increasing resistance due to purely ohmic phenomena, such as contact resistance in
current collectors and electrode material [37][19]. The greatest increase in both R0 and RCT was
observed for the LT cycled batteries cycled to 250 ageing cycles. Interestingly, the charge transfer
resistance increased immensely between 200 and 250 cycles at LT. According to [19], this could
be a sign of LLI, such as lithium plating and SEI-layer formation.
The appearance of the semi-circle during the initial cycles at HT could result from an increasing
charge transfer resistance due to SEI-layer build up and electrolyte decomposition [19]. A high tem-
perature study by Jalkanen et al. [20] showed a similar phenomenon in commercial NMC/graphite
batteries, and the growing semicircle was attributed to the SEI-layer on the graphite electrode. As
discussed, the Nyquist plots revealed signs of several important electrochemical degradation phe-
nomena with ageing, which may not have been identified solely tracking the impedance at 980 Hz.
48 CHAPTER 5. DISCUSSION
5.4 Surface temperature

With regard to maximum surface temperature, no consistent trend with ageing could be observed,
apart from an increase in surface temperature for LT cycled batteries. This temperature increase
could be due to heat generation associated with the increased resistance, which increased rapidly
after 150 cycles. This phenomenon was more pronounced at 10 A discharge, particularly for battery
L3 which showed both a higher surface temperature increase and resistance increase.
Interestingly, the CID was activated on two HT cycled batteries (H2 and H3) before the ageing
protocol had ended. According to the battery manufacturer specification [44], the surface temper-
ature should not be allowed to exceed 80 ◦ C during discharge. However, the surface temperature
occasionally reached a maximum of 77 ◦ C for H3 and 92 ◦ C for H2, for a short period of time
during the 10 A discharge cycles. This is crucial information, seeing that a previous study on this
particular battery model reported activation of the CID around 100 ◦ C during ARC-experiments
[25]. This could indicate that the internal temperature could potentially reach up to 100 ◦ C during
10 A discharge at elevated temperatures, even though the surface temperature is lower. Hence, the
importance of monitoring surface temperature is highlighted, as well as taking into account the
internal temperature rise at various C-rates.
The rise in surface temperature of battery H2 and the LT-cycled batteries correlated with the in-
crease in resistance along ageing. This could be a sign of growing heat generation due to increased
ohmic resistance of the electrolyte and electrodes, as well as an increased charge transfer resistance
of the SEI-layer [16]. However, solely monitoring a temperature rise may be insufficient informa-
tion for SOH estimation. For instance, the maximum surface temperature of batteries H1 and H3
did not increase with ageing, yet the resistance increased with ageing, eventually reaching the EOL
limit (at 100 % SOC) after 150–200 cycles. Furthermore, the CID of battery H3 was activated,
indicating a substantial degree of degradation in terms of gas evolution. In addition, ambient tem-
perature fluctuations may affect the surface temperature readings. More information may therefore
be required to accurately estimate the battery’s SOH using the surface temperature.
5.5 Deviating batteries

Two batteries (R1 and H2) deviated with regard to impedance and resistance measurements. Inter-
estingly, H2 deviated also with regard to capacity fade and surface temperature; the capacity fade
was more rapid whereas the surface temperature rise correlated with the resistance increase. These
signs of accelerated ageing could possibly indicate battery defects.
The visual inspection of the electrode material of R1 showed no deviation with respect to R2 or
reference, neither did the XRD-results show variations which could explain the deviating behavior.
For R1, deviations were only observed with respect to resistance and impedance at 980 Hz. This
could point at an increasing ohmic resistance at the connections. Hence, it is possible that devia-
tions observed for R1 could be an effect of external factors such as the welding of the connections
rather than internal defects or ageing phenomena.
CHAPTER 5. DISCUSSION 49
5.6 Limitations and future outlook

The results from this study showed that, solely changing the temperature, both capacity and resis-
tance were greatly affected. This is crucial information not only for accurate estimation of SOH
but also for overall battery performance. However, for more accurate estimation of temperature’s
effect on battery parameters for SOH estimation, more temperature intervals between −30 ◦ C and
52 ◦ C should be investigated, with better control with regard to temperature fluctuations.
Real life applications may vary substantially with respect to time and external conditions such as
temperature. Therefore, the methodology of this study aimed to mimic an application where the
battery parameters are measured not only under one specific condition, but under various temper-
atures, SOCs and under time constraints. Nevertheless, this study was restricted to intermittent
parameter tracking due to the time limitations of this project, and a selection of ambient temper-
atures and SOCs were investigated. SOH estimation through parameter tracking should however
optimally be based on more information.
Impedance measured at 980 Hz showed to be the most stable battery parameter with respect to
temperature and SOC, and increased with cycling ageing due to ageing phenomena related to the
ohmic resistance. Hence, it could serve as a feasible battery parameter for SOH estimation at sit-
uations requiring high degree of flexibility seeing that it is non-invasive, quick and implementable
in a BMS [9]. Yet, the results from this study showed that impedance measured at a single fre-
quency of 980 Hz omits information of electrochemical and kinetic degradation phenomena, such
as increasing charge transfer resistance due to SEI-layer growth. Such degradation phenomena are
likely better reflected on changes in capacity and resistance, which on the other hand proved to
change substantially with temperature. Future studies could therefore involve investigating single-
frequency impedance at other frequencies suitable for detection of electrochemical ageing phe-
nomena, which remain stable over several increments of SOC and temperature. Another approach
could be to investigate the optimal EOL limit for single-frequency impedance, using capacity fade
at various temperatures as a reference. Future studies should also include investigation of battery
parameters at temperatures down to −30 ◦ C, temperatures which for practical reason could not be
investigated in this study, but nevertheless are recommended for battery testing in electric vehicle
applications [45][46]. Finally, investigation of SOH parameters should be extended to batteries in
modules to further simulate a real application.
Chapter 6
Conclusions
Impedance measured at a single frequency of 980 Hz was shown to be the most stable SOH param-
eter with respect to variations in SOC and ambient temperature. Therefore, impedance measured
at 980 Hz was regarded most suitable for applications requiring fast and flexible SOH estimation.
Tracking of discharge capacity and resistance was regarded most suitable for applications requir-
ing accurate estimation of battery SOH as they likely reflected electrochemical ageing phenomena
more accurately. Tracking of surface temperature was regarded insufficient for accurate SOH esti-
mation in this study.
Changes in capacity, resistance and impedance were observed by solely increasing or decreasing
the temperature; changes which are likely related to kinetic phenomena rather than battery degrada-
tion. Decreasing the ambient temperature to −15 ◦ C had a major effect on the measured discharge
capacity and resistance, as the battery performance was significantly reduced; the discharge ca-
pacity reduced to close to their EOL limit while the resistance increase was almost threefold. For
accurate SOH estimation in real applications, temperature’s effect should therefore be considered
when tracking these battery parameters.
With respect to capacity, neither of the batteries kept at 21 ◦ C reached their EOL during the 250 cy-
cles ageing protocol. Batteries kept at 52 ◦ C or at −15 ◦ C reached their EOL after 150–200 cycles.
With respect to resistance, only a deviating battery kept at 21 ◦ C reached their EOL after 200 cycles.
All batteries kept at 52 ◦ C reached their EOL after 150–200 cycles, but only when the resistance
was measured at 100 % SOC, hence, a notable variation in resistance was observed with SOC.
Batteries kept at −15 ◦ C reached their EOL between 200–250 cycles.
With respect to impedance measurements at 980 Hz, only a deviating battery kept at 21 ◦ C, and
a deviating battery kept at 52 ◦ C reached their EOL after 200 cycles and 150 cycles, respectively.
Batteries kept at −15 ◦ C reached their EOL between 200–250 cycles.
Future studies on battery parameters for SOH estimation could involve investigation of single-
50
CHAPTER 6. CONCLUSIONS 51
frequency impedance at other frequencies suitable for detection of electrochemical ageing phe-
nomena. Furthermore, future studies should involve investigation at more temperatures, for in-
stance below −15 ◦ C, as well as on batteries in modules.
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Sources 384 (Apr. 2018), pp. 107–124.
Appendix A
Contact Loss Due to CID Activation
Figure A.1. Discharge curve at cycle 219 for one of the batteries
cycled at 52 ◦ C (H2), eventually leading to a drop in OCV due to
activation of the CID.
58
Appendix B
Magnitude of Impedance at 980 Hz
log10|Z| 980 Hz
Figure B.1. A Bode plot, with the measurement point correspond-

ing to 980 Hz marked, and the corresponding impedance magnitude
marked.
59
Appendix C
X-ray Diffraction Spectra Fitting
XRD spectra were fitted using Fityk 1.3.1 software. Four peaks were fitted to (1 0 8) and (1 1 0)
using Lorentzian function. See Figure C.1 for the fitting of one of the XRD spectra corresponding
to a pristine NMC electrode.
Figure C.1. Peak fitting of NMC electrode from Fityk 1.3.1 software. Green
graph is experimental data, red graphs show peaks fitted to the experimental
data and yellow graph is the resulting Lorentzian function.
60
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DEGREE PROJECT IN CHEMICAL SCIENCE AND ENGINEERING,

SECOND CYCLE, 30 CREDITS

KTH ROYAL INSTITUTE OF TECHNOLOGY

Master in Molecular Science and Engineering

List of Abbreviations viii

3.2.3 Low-temperature (LT) cycling . . . . . . . . . . . . . . . . . . . . . . . 20

A Contact Loss Due to CID Activation 58

B Magnitude of Impedance at 980 Hz 59

C X-ray Diffraction Spectra Fitting 60

2.1 Principle of the Li-ion battery

Negative current collector

Cathode active material Anode active material

Figure 2.1. An illustration of Li-ion intercalation be-

Figure 2.2. A sketch of the step-wise structural changes of graphite as

2.2 Ageing of Li-ion batteries

2.2.2 Capacity and temperature

2.2.3 Resistance increase

2.2.4 Internal heat generation and gas evolution

2.2.5 Lithium plating

2.2.6 Summary of ageing mechanisms in Li-ion batteries

External cause Ageing mechanism Ageing eﬀect Internal cause

Electrode decomposition Precipitation of new phases LAM

2.3 SOH estimation methods

2.3.1 Capacity fade

2.3.2 Incremental capacity analysis

2.3.3 Impedance increase through EIS measurements

Z(ω) = Z0 (cos(ϕ) + jsin(ϕ)) = Zre + Zim (2.4)

Kinetic control Diffusional control

2.3.4 Resistance increase through HPPC-test

∆Vpulse V0s − V10s

Voltage [V] Current [A]

2.3.5 Summary of SOH estimation methods

SOH evaluation method Advantage Limitations

3.1 Investigated Li-ion battery and battery specifications

Table 3.1. Nominal speciﬁcations of Samsung INR21700–40T power optimised

Battery parameters Speciﬁcation

Standard discharge capacity ≥ 4000 mAh

Rated discharge capacity ≥ 3900 mAh

Initial internal impedance ≤ 12 mΩ (at 1 kHz AC and 100 % SOC)

Recommended operating temperature Charge: 0 – 45 ◦ C

Recommended operating temperature Charge: 0 – 50 ◦ C

3.2 Experimental setup

Figure 3.1. A battery connected to the cycling

3.2.1 Room-temperature (RT) cycling

3.2.2 High-temperature (HT) cycling

3.2.3 Low-temperature (LT) cycling

3.3 Experimental procedure

3.3.1 Cycling ageing

Figure 3.2. Cycling ageing sequence, repeated 50 times and followed by

3.3.2 Characterisation test

3.3.2.1 Capacity measurements

3.3.2.2 Impedance measurements through GEIS

3.3.2.3 Resistance measurements through HPPC-test

3.3.2.4 State of charge estimation

Step 1 CC-CV Charge

Full charge and

Figure 3.3. Characterisation test sequence. Step 1 constitutes capacity

3.3.3 Characterisation at beginning of cycling and end of cycling

3.3.4 X-ray diffraction analysis

λ = 2dhkl sinθ (3.2)

3.3.5 Cell disassembly

4.1.1 Charge and discharge capacity

4.1.2 Incremental capacity analysis

(a) RT cycled battery.