energies

Review
Temperature, Ageing and Thermal Management of
Lithium-Ion Batteries
Lena Spitthoff 1 , Paul R. Shearing 1,2 and Odne Stokke Burheim 1, *

1 Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU),
7491 Trondheim, Norway; lena.spitthoff@ntnu.no (L.S.); p.shearing@ucl.ac.uk (P.R.S.)
2 Department of Chemical Engineering, University College London (UCL), London WC1E 6BT, UK
* Correspondence: odne.s.burheim@ntnu.no; Tel.: +47-9170-7856

Abstract: Heat generation and therefore thermal transport plays a critical role in ensuring perfor-
mance, ageing and safety for lithium-ion batteries (LIB). Increased battery temperature is the most
important ageing accelerator. Understanding and managing temperature and ageing for batteries
in operation is thus a multiscale challenge, ranging from the micro/nanoscale within the single
material layers to large, integrated LIB packs. This paper includes an extended literature survey of
experimental studies on commercial cells investigating the capacity and performance degradation
of LIB. It compares the degradation behavior in terms of the influence of operating conditions for
different chemistries and cell sizes. A simple thermal model for linking some of these parameters
together is presented as well. While the temperature appears to have a large impact on ageing
acceleration above room temperature during cycling for all studied cells, the effect of SOC and C rate
appear to be rather cell dependent.Through the application of new simulations, it is shown that



during cell testing, the actual cell temperature can deviate severely from the reported temperature

 depending on the thermal management during testing and C rate. It is shown, that the battery
Citation: Spitthoff, L.; Shearing, P.R.; lifetime reduction at high C rates can be for large parts due to an increase in temperature especially
Burheim, O.S. Temperature, Ageing for high energy cells and poor cooling during cycling studies. Measuring and reporting the actual
and Thermal Management of battery (surface) temperature allow for a proper interpretation of results and transferring results
Lithium-Ion Batteries. Energies 2021, from laboratory experiments to real applications.
14, 1248. https://doi.org/10.3390/
en14051248 Keywords: lithium-ion batteries; battery ageing; degradation; thermal management; temperature
control
Academic Editors: Carlos Miguel
Costa and Seung-Wan Song

Received: 17 December 2020

1. Introduction
Accepted: 22 February 2021
Published: 25 February 2021
The current efforts of transitioning from fossil fuels and traditional energy sources
to renewable energy sources have led to a massive increase in the lithium-ion battery
Publisher’s Note: MDPI stays neutral
(LIB) market. LIBs have become the leading energy storage technology in many sectors
with regard to jurisdictional claims in
due to their high gravimetric and volumetric energy density, high power density, high
published maps and institutional affil- efficiency, low self-discharge property and compatibility with the existing electric infras-
iations. tructure [1]. The transport sector has had a large impact on the increase in the LIB market;
BloombergNEF forecasts in the Electric Vehicle Outlook 2020 [2] that EVs will hit 10% of
the global passenger vehicle sales by 2025 and 58% in 2040, with LIBs being the established
energy storage technology [3].
Copyright: © 2021 by the authors.
However, for the successful application of LIBs in these market segments, high energy,
Licensee MDPI, Basel, Switzerland.
high power and fast charging rates are required; this is typically associated with large
This article is an open access article
amounts of heat being generated and non-uniform current distribution. This in turn leads
distributed under the terms and to safety problems, decreased performance and long term durability challenges, as reaction
conditions of the Creative Commons rates and diffusivity are temperature dependent. Thermal management systems are used to
Attribution (CC BY) license (https:// keep the battery temperature at an optimal range, aiming to enable a uniform temperature
creativecommons.org/licenses/by/ distribution. Apart from reversible heat, generated heat is an indicator of lost work during
4.0/). energy conversion during the charging and discharging process.

Energies 2021, 14, 1248. https://doi.org/10.3390/en14051248 https://www.mdpi.com/journal/energies

Energies 2021, 14, 1248 2 of 30

Many studies in the past three decades have been devoted to improving the un-
derstanding of the thermal behaviour of LIBs at cell and pack level. Experiments and
numerical thermal simulations are the preferred methods in most studies [4–8], and several
cooling methods have been proposed and researched [9–12].
Firstly, a comprehensive literature review of experimental ageing studies is presented
and secondly combined with new thermal modelling. The aim is to illustrate the importance
of the thermal management system and proper temperature monitoring during ageing
studies for comparability and transferability of results from laboratory experiments to real
battery applications. The first section provides a brief, didactic overview of the working
principal of LIB in general, the most common materials used in commercially available
LIB and the development trends, as well as thermal modelling and thermal management
systems. The second section is a review of experimental cycling and ageing studies on
capacity degradation and resistance increase. Those studies are compared in terms of
the effect of operation conditions (temperature, state of charge (SOC) and C rate). The
third section presents the simple thermal model used in this work for an evaluation of
the importance of thermal management during degradation studies. Finally, the results
of the thermal modelling are presented and used for an evaluation of the comparability
of degradation studies and the validity of those when it comes to differentiating between
ageing acceleration due to temperature and C rate increase.

1.1. Working Principle and Geometries

A LIB cell (as schematically shown in Figure 1) utilizes two open-structured materials
as electrodes, where the lithium-ions (Li-ions) intercalate. The positive and negative
electrode are attached to current collectors and separated by an electrolyte filled separator.
The electrolyte-filled separator provides Li-ion transport and prevents electron flow. While
charging, Li-ions from the positive electrode dissolve in the electrolyte solution, forming a
positive ion and an electron in an oxidation reaction [13]. The Li-ions move to the negative
electrode through the electrolyte while the electrons circulate through the external circuit.
The negative electrode consumes the electrons upon intercalation of the Li-ions. During
discharging, the Li-ions and electrons circulate in opposite directions than during charging.
By definition, the electrode that has the oxidation reaction during discharge is the anode
and the reduction reaction during discharge takes place at the cathode [14]. As LIBs are
typically operated outside the electrochemical stability range of the electrolyte, the organic
electrolyte is partially reduced and forms a passivating layer on the anode. This layer is
called the solid electrolyte interphase (SEI) and mostly prevents the further reduction of
electrolyte, however, an unstable SEI layer leads to further consumption of Li-ions and
increase in the impedance of the cell during operational lifetime [15].

Figure 1. Schematic illustration of a lithium-ion battery (LIB) under discharge. The Li-ions are
moving from the anode to the cathode while the electrons circulate through the external circuit.
Energies 2021, 14, 1248 3 of 30

The current collectors are cast with electrode material on both sides. One cell con-
sists of electrode and separator sheets sandwiched with anode/cathode/anode or cath-
ode/anode/cathode. Those cells are stacked to form a full battery. The most common
battery geometries are pouch cell, cylindrical cell, button cell and prismatic cell. To fulfil
energy and voltage requirements, several batteries are connected in series and parallel as
a pack. Different types of spacing are used between the batteries or packs to stop failure
propagation and help with thermal management.

1.2. Currently Used Chemistries and Development Trends

Most commercially available LIBs consist of a carbon-based intercalation anode and a
cathode utilizing mixed lithium transition metal oxides or olivine compounds. The most
widely used cathode materials are the lithium transition metal oxides, lithium cobalt oxide
(LCO), lithium nickel cobalt manganese oxide (NMC), lithium nickel cobalt aluminium
oxide (NCA), and lithium manganese oxide (LMO) and the olivine lithium iron phosphate
(LFP) [16]. These cathode and anode compounds are typically mixed with small quantities
of a polymeric binder (e.g., polyvinylidene fluoride) and conductive agents (e.g., carbon
black) and printed onto a metal current collector (aluminium for the cathode and copper
for the anode).
The requirements on high energy/power density, cost reduction, prolonged lifetime,
and safety are steadily increasing and are major driving forces in the LIB research. The
common strategies on increasing the energy density on the material level are to improve
the specific and volumetric capacities as well as their operating potentials, i.e., maximizing
the cell voltage with cathode materials operating at high electrode potentials and anode
materials operating at low electrode potentials. The most promising trends in the LIB
world are electrodes with a significantly higher theoretical capacity, such as silicon [17],
increasing energy density by using higher cell voltages [18], increasing ionic and electronic
conductivity to allow thicker electrodes and the utilization of solid-state electrolytes to
enable higher charging rates [19] and improved safety [20].

Cathode Materials: LCO, LMO, NMC, and LFP

LiCoO2 (LCO) was introduced by Goodenough in 1980 [21]. By combing the cathode
material with a carbon anode, Sony introduced the first successful commercial LIB on the
market around 1990. Until now, LCO remains one of the most used cathode materials of
commercial available LIBs [22]. It is a layered transition metal oxide: cobalt (Co) and Li are
located in octahedral sites and occupy alternating layers, forming a hexagonal symmetry.
The paths for lithiation and delithiation are planes. The average operation voltage is
3.8 V [16]. Despite a high theoretical capacity of 270 Ah/kg, only around 145 Ah/kg can be
reversibly accessed, due to the risk of structural instability [23]. The main drawback with
LCO is the toxic and expensive Co and poor thermal stability. The poor thermal stability
is caused by an exothermic release of oxygen when an LCO cathode is heated above a
certain point, leading to a thermal runaway reaction [16]. To obtain cheaper materials
and increase Li utilization, new materials are being developed, trying to replace Co with
cheaper transition metals like manganese, nickel, and iron [23].
By substituting Co in LCO cathodes with Manganese (Mn), the cathode material
LiMn2 O4 (LMO) was obtained. It has a spinel structure, with manganese occupying the oc-
tahedral sites and Li predominantly occupying the tetrahedral sites [24]. Here, the paths for
lithiation and delithiation are a three-dimensional network of channels [25]. The average
operating voltage is 4.1 V and the theoretically available specific capacity 148 Ah/kg [16].
The cathode material LiNi0.5 Mn0.5 O2 (NMO) was the result of extensive research efforts
to create a cheaper cathode material. However, to enhance rate capability, Co was added
and resulted in the formulation of LiNix Coy Mnz O2 (NMC). NMC has a similar or higher
achievable specific capacity than LCO, while having lower costs due to a reduced Co
content. Nowadays, the commercially most available form is LiNi1/3 Co1/3 Mn1/3 O2 , with
an average voltage of 3.7 V and theoretically available specific capacity of 280 Ah/kg [16].
Energies 2021, 14, 1248 4 of 30

However, compositions with increased nickel (Ni) content (LiNix Coy Mnz O2 with x > 0.6)
have recently received an increase in interest, as they provide larger specific capacities
and energy densities and lower the costs due to the higher capacity and lower costs of
Ni compared to Co [26–33]. The common abbreviation NMC is added with numbers
indicating the decimals of each element (e.g., NMC523: LiNi0.5 Co0.2 Mn0.3 O2 ). Ni is as-
sociated with higher capacity, cobalt with better rate capability and manganese with
improved safety/stability [29]. One of the major drawbacks with nickel rich NMC is the
decreased thermal stability. Some EVs of the current generation already employ NMC with
a Ni:Co:Ma ratio of 5:3:2 [29], which was shown to have so far the optimized composition,
offering a reasonably good thermal stability and high capacity due to a well-balanced ratio
of Ni content to Mn and Co contents [34]. The main problems with Ni-rich NMC cathode,
summarized by Schipper et al. [29], are the large amount of highly reactive Ni4+ at high
SoC that lead to undesired side reactions with the electrolyte solution and the poor thermal
stability resulting in serious safety concerns. In addition, it leads to Li and Ni cation lattice
substitution and corresponding spinel formation on the electrode particle crystal surface
which eventually results in inactive Fm(-)3m phase and capacity fade. Additionally, the
composition in a ratio of 8:1:1 during cycling will lead to cracks in the secondary particle
along the grain boundaries which result in increased surface area and thus more active
sites for parasitic reactions [30]. Research is therefore focused on ensuring stability while
increasing the nickel content. Increased Ni content can also result in increased cation
mixing and increased parasitic reactions at the valence of surface Ni increases towards
highly reactive Ni+ . Additionally, to maintain a layered structure, excessive Li is used for
Ni rich NMC cathodes. Side reactions with water vapour and CO2 in air can lead to the
formation of LiOH and Li2 CO3 on the surface that thickens when cycled [35]. Research is
mainly focused on creating artificial cathode-electrolyte interphases, either by introducing
functional groups on the surface [30], electrolyte additives [32] or surface coating [36].
LiFePO4 (LFP) was first reported by Goodenough in 1996 [21]. It has an olivine
structure, with covalently bonded PO4 groups forming the PO4 tetrahedron together with
a chemically stable Fe2+ /Fe3+ couple within the FeO6 octahedron. During charging and
discharging, the Li-ions are respectively extracted from and inserted into LiFePO4 , while
the central iron ions are oxidized and reduced. The main advantages of this material are
the use of inexpensive and environmentally benign Fe as well as the very good safety
characteristics due to the structure and voltage plateau at 3.4 V which suppresses electrolyte
degradation. The main disadvantage is the low volumetric energy density with a theoretical
available capacity of 170 Ah/kg [16].

Anode Materials: Hard Carbon, Graphite and Silicon

Anode materials are commonly divided into three main categories, depending on
their LIB performances and reaction mechanisms. These are intercalation anodes which
are mostly carbon-based, alloy anodes like silicon, and germanium and conversion anodes
using transition metal compounds like oxides, phosphides, sulphides, and nitrides [37].
Currently, the most common commercial anode materials are based on carbon. Car-
bon is cheap, has a low delithiation potential vs. Li/Li+ , high Li diffusivity, high elec-
trical conductivity and relatively low volume changes during lithiation and delithiation.
Carbon anode materials can be divided into graphitic carbons and hard carbons [16].
Graphite is a three-dimensional ordered crystal with large graphite grains and a density
of 2.26 g/cm3 [38]. It is a very stable allotrope of carbon. During battery operation, a
Li atom is intercalated between the graphite layers to form an intercalation compound
(i.e., LiC6 ). The surface most exposed to the electrolyte is the basal plane, but the Li-ions
predominantly intercalate into the graphene layers through the edge planes which are
normal to the graphene layers [39,40]. During the intercalation of Li, the graphitic particles
undergo uniaxial strain along the edge planes [41]. Hard carbon or “non-graphitized car-
bon” consists of two dimensional “ordered” graphene sheets, which are randomly stacked.
The structure of both hard carbon and graphite are schematically shown in Figure 2. Its
Energies 2021, 14, 1248 5 of 30

density is between 1.4 and 1.8 g/cm3 and is smaller than graphite [38]. The SEI layer that is
formed on the carbon anode depends on the properties of the carbon/graphite. Important
factors are the degree of crystallinity, basal-to-edge-plane ratio, particle and pore size, and
surface chemical composition. A high degree of graphite crystallinity is preferred for high
energy LIB anodes [40], but the strains during the intercalation of Li in the graphitic particle
may damage the SEI and reduce the cell’s cycle life. On the other hand, SEI on hard carbon
is thicker, due to the accumulation of electrolyte-reduction products in surface voids [39].
Moreover, hard carbon has a higher fraction of exposed edge planes and therefore an
increased quantity of SEI formed in the first cycles [16].

Figure 2. Structure of hard carbon (left) and graphite (right).

Vast amounts of research have been focused in recent years on increasing the capacity
of the anode by using silicon [42]. Silicon anodes offer an up to 10 times higher gravimetric
capacity, and a higher potential (∼0.4 V vs. Li/Li+ ) than currently used carbon anodes [17].
However, silicon anodes show poor cycling stability due to large volume expansion and
contraction (300–400%) and subsequent cracking during the lithiation and delithiation.
During the volume changes, the SEI layer is damaged and new SEI is constantly formed
and consumes Li-ions. Therefore, so far, only small amounts of silicon particles combined
with silicon dioxide and graphite are used for commercial LIBs.
To be able to increase the amount of silicon in the anode while maintaining long-term
capacity retention, different strategies are currently explored. A large focus is on using
nanostructured silicon to overcome surface cracking and particle fractures as Liu et al. [43]
found that the critical particle size is 150 nm. Nanomaterials and structures like nanoparti-
cle, nanowires, nanotubes and nanoporous networks have shown superior electrochemical
properties [44–47], but industrial applications are still challenging, as their fabrication is
not yet cost-effective [37]. Other efforts are focused on finding new binder materials [48,49],
new electrolytes and electrolyte additives (e.g., fluoroethylene carbonate) that stabilize
the electrolyte/electrode interphase [48,50] or surface modification like molecular layer
deposition [48]. Other considered options are the coating of Si particle with graphene [51],
increasing the porosity [52] and using composite anodes, e.g., formed by silicon, Li and
highly electronically conductive materials such as TiC/C [45,53]. Moreover, applying
special cycling procedures that use for example limited potential windows [54,55] or pre-
lithiation of the anode by introducing an alternative Li source [56–59] are considered.
Prelithiation leads to a high initial Coulombic efficiency and prevents the Li in the cathode
from being consumed during the initial SEI formation. One approach is to bring a Li foil
in contact with an electrolyte-wetted anode in a temporary cell to realize electrochemical
prelithiation.

Separator, Electrolyte and Additives

The purpose of the separator is preventing direct electrical contact between the cathode
and the anode and thus avoiding short-circuiting. Commercially used separators utilize
mostly polyolefin-based microporous membranes like polyethylene (PE), polypropylene
(PP) or PE/PP composite membranes. They have good mechanical properties, chemical
stability and are economically viable. However, their low porosity, insufficient electrolyte
wettability, and low melting point can affect the electrochemical properties and safety
Energies 2021, 14, 1248 6 of 30

of LIBs [60]. In recent years, research was focused on improving the performance of
polyolefin-based separators by coating common membranes. These coated separators
showed improved thermal stability [61]. However, this method reduces the porosity, and
more recent approaches have been focusing on using electrospinning to obtain microporous
nanofiber membranes with high porosity and enhanced wetting properties [62–64].
The electrolyte interacts with all components in the battery and is therefore important
for power density, cycling stability and safety of the battery. The most important criteria
for a good electrolyte is good ionic conductivity, whilst being electronically insulating,
a wide electrochemical stability window to prevent electrolyte degradation, being inert
to other components, as well as low costs, non-toxicity, and sustainability. Most of the
electrolytes used in commercially available LIBs are non-aqueous solutions utilizing lithium
hexafluorophosphate (LiPF6 ) salt, dissolved in organic carbonates, mostly mixtures of
ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), diethyl
carbonate (DEC) and ethyl methyl carbonate (EMC) [65]. Electrolyte additives are used to
improve the performance of LIBs. The amount is usually no more than 5%. Additives are
mostly utilized to improve the SEI formation, protect the cathode, stabilize the LiPF6 salt
and increase safety [66].
Solid-state electrolytes (SSE) have attracted great attention as the key components for
all-solid-state LIBs, allowing high safety and increased energy density due to improved
stacking. By replacing the organic liquid electrolytes and separator with an inorganic solid
electrolyte, it is possible to use higher potential cathode materials due to an improved
electrochemical stability. As SSE are inorganic they are not flammable. Additionally, they
are reported to enable higher charging rates as, in contrast to liquid electrolytes, no con-
centration gradient is built up during charging and discharging at high rates [19]. The
major downside with SSE is about 10 times lower ionic conductivity compared to liquid
electrolytes resulting in high resistance and therefore high losses at high rates [20]. Further-
more, achieving simultaneous electron and ion transport at the interface is challenging [67].
Different electrolytes are currently investigated, with NASICON-, garnet- and perovskite-
type solid electrolytes being the most promising ones for application in all-solid-state LIBs.
However, Zheng et al. [20] concluded in their extensive review that further improvement
is necessary for the compatibility between solid electrolytes and electrodes.

1.3. Thermal Modelling

Numerical simulations can simulate the thermal behaviour of the whole batteries
and can be fitted to different conditions and geometries by alternating model parame-
ters. The models can be classified into two major categories according to the underlying
mathematical model. A first category is a multiphysics approach where a thermal model
is mostly coupled with an electrical model (based on an equivalent circuit) [68,69] or an
electrochemical model [70,71]. The second category is a purely thermal model based on
solving the energy balance and heat generation equation with the respective boundary con-
ditions. Bernardi et al. [72] presented one of the first thermal models by deriving a general
energy balance for battery systems with heat generation due to phase changes, enthalpy
of mixing and enthalpy of reaction consisting of heat due to overpotential, ohmic heating
and entropic heat. They showed that a simplified form, where the heat generation due to
phase changes and enthalpy of mixing is neglected, is valid for most systems. The heat
is transferred inside the battery by conduction and therefore determined by the thermal
conductivities of all components.

1.4. Thermal Management

The primary aim of a battery thermal management system (BTMS) is to maintain the
batteries within the optimum operating temperature range with a uniform temperature
distribution inside the cell and the pack. It is of utmost importance to enable a uniform
temperature distribution on both cell and pack level, as uneven temperature distribution
leads to non-uniform and accelerated degradation [73]. An unbalanced system restricts the
Energies 2021, 14, 1248 7 of 30

optimum performance and decreases the lifetime of a battery severely [74]. The magnitude
of the overall heat generation of the battery under load dictates the size and design of the
cooling system needed [75].
Generally, BTMS can be categorized into internal and external systems and according
to the used cooling medium. External systems remove the generated heat from the battery
surface in different forms and geometries [9,10,76]. External BTMS using air cooling is
the most traditional approach, studied intensively, and is widely adopted in commercial
applications. The efficiency of external systems is limited, as the maximum temperature
of a battery is located at the internal portion of the cell. Therefore, increasing the ve-
locity of the cooling medium in the external BTMS increases the difference within the
cell—enhancing non-uniformity [73]. To enable a BTMS that contributes to a uniform
temperature distribution while removing heat, several internal cooling systems have been
proposed. Mohammadian et al. [11] embedded microchannels into the electrode area using
an electrolyte as a coolant. They concluded that at the same pumping power internal
cooling decreases the internal bulk temperature more than external cooling with a more
uniform temperature distribution. Shah et al. [12] proposed using an annular channel
through the axis of a cylindrical 26650 cell. They concluded that airflow, heat pipe insertion
and using a thin metal rod result in sufficient cooling.
BTMS can also be categorized based on the cooling medium used. Air cooling and
liquid cooling are frequently used, but also phase change (liquid to gas) cooling, phase
change (solid to liquid) cooling and combinations of them are obtaining increased atten-
tion [10]. As already mentioned, although air-cooling has the advantages of low cost,
simple structure and abundant source of coolant materials, it lacks efficiency. It can be
differentiated in natural air-cooling and forced air-cooling using fans to drive an airflow.
Liquid-cooling is also frequently used with high cooling efficiency. It has been used in
commercial EVs like General Motors Volt and Tesla Model S [10]. It generally allows
a better battery temperature control than air-cooling, especially at higher charging and
discharging rates. Direct liquid cooling the cells or battery pack is stored in a fluid envi-
ronment, whereas in an indirect liquid-cooling system, the coolant is circulated between
the battery pack and a heat sink [77]. The efficiency is mostly influenced by fluid flow rate,
fluid temperature, flow channel structure and cooling medium. The main disadvantage of
this liquid cooling methods is the increase in weight and space consumption, due to extra
components like pumps, valves and cooling channels. It also increases the parasitic power
costs and therefore decreases cooling efficiency [10].
To enable an efficient thermal management system without adding motive compo-
nents, research has been focused on utilizing phase change materials (PCM). The generated
heat can be absorbed by PCMs during the phase change process. Often, thermal conductiv-
ity enhanced materials like graphite sheets, metal foam or carbon fibre are added to allow a
rapid transfer of heat to the PCM. Huang et al. [78] proposed the use of flexible form-stable
composite PCM embedded in battery packs to lower the thermal contact resistance and
improve the thermal control performance. Another option is the utilization of the liquid to
gas phase change. This is often done in combination with exploiting the heat pipe effect.
The generated heat vaporises the working fluid which flows up to the condenser due to
the energy density difference and is condensed there. After being transformed into a liquid
state, it moves back to the evaporator under the effect of capillary force [79]. Fang et al. [10]
proposed thermal management for a tube-shell LIB pack using water evaporation, using a
sodium alginate film with high water content coupled with forced air cooling.
Chen et al. [80] compared cooling methods for a LIB pack for electric drive vehicles.
Their results show that an air-cooling system needs 2 to 3 times more energy compared to
fin cooling and direct and indirect liquid cooling to keep the same average temperature.
An indirect liquid cooling system was found to have the lowest maximum temperature rise
and a fin cooling system adds the most weight (about 40% extra weight of cell). Indirect
liquid cooling (cooling of fins) is a more practical form than direct liquid cooling, though it
has a slightly lower cooling performance.
Energies 2021, 14, 1248 8 of 30

2. Comparing Ageing and Degradation Studies

In the following, a review of experimental cycling and calendar ageing studies is
presented, focusing on capacity degradation and resistance increase. The reviewed studies
are compared in terms of the effect of operation conditions on the ageing rates.

2.1. Ageing Mechanism

The performance of a LIB deteriorates over time, which includes both losses of avail-
able energy and power. This results from a capacity degradation and a resistance increase.
This degradation is caused by different ageing mechanisms and is frequently studied for
different cell chemistries. Battery degradation is known to be a result of several simultane-
ous physicochemical processes: these processes lead to loss of Li inventory (LLI), loss of
active materials (LAM), and impedance increase due to reaction kinetics degradation [81].
LLI is mainly caused by the growth and decomposition of the SEI layer, electrolyte decom-
position, and Li plating and dendrite formation. LAM can be introduced by the dissolution
of material, structural degradation, particle isolation, corrosion of current collector, loss
of electric contact and electrode delamination. Increased impedance is a result of the for-
mation of passive films at the active particle surfaces, pore-clogging, as well as electrolyte
conductivity losses and loss of electric contact [4]. The increase in internal resistance causes
an earlier termination of the charging or discharging process. These degradation mecha-
nisms are influenced by time, (ambient) temperature, current load, voltage, accumulated
ampere-hour throughput, and mechanical stress [4–8].
The ageing, underlying mechanisms, and influencing factors are investigated in differ-
ent ways. Dubarry et al. [4] categorized the ageing investigation methods into experimental,
modelling, post mortem and electrochemical voltage spectroscopy. Experimental ageing
studies on different commercially available chemistries will be compared in terms of
capacity degradation and internal resistance increase in the following.

2.2. Definitions and Calculations

Traditionally, capacity degradation was used to describe the ageing behavior of a
battery. In recent years, changes in internal resistance have received more attention as
an ageing characteristic as well. When considering ageing in connection with internal
temperature, ohmic resistance plays a significant role. As the resistance increases, the
ohmic heat generation increases and the available energy is reduced as power is lost to
ohmic heating. This is especially significant for high C rates.
Capacity degradation can be presented in different ways. One way of evaluating
the battery degradation is relating the cell coulombic capacity at a specific point to the
initial cell capacity. This relative cell capacity is frequently used in ageing studies [6,7]
and generally referred to as the state of health (SOH) [82], normalized capacity [8] and
relative, remaining or relative discharge capacity [5,83,84]. Another way of evaluating
battery degradation is by presenting the accumulated capacity loss normalized to initial
conditions using the terms maximum available capacity degradation [85] and degradation
percentage [86]. Moreover, it is common to measure the capacity at a given C rate to allow
for comparison between different test regimes. The available capacity varies; C rate as the
charge at the lowest SOC is less available at higher currents.
The resistance of a battery depends on SOC, current, temperature, pulse duration
and frequency. In ageing tests, several resistance measuring methods can be used to
characterize ageing, where most studies use pulse resistance [6,7,81,85,87]. Resistance
values by the pulse measurements are calculated using the voltage step method, based
on Ohm’s law. Here, a current pulse is applied to the cell at equilibrium voltage. The
internal resistance can be derived from the overvoltage due to the current pulse that
immediately occurs. Therefore, the difference in voltage before and at the end of the pulse
is divided by the currents at the respective points. Depending on the length of the current
pulse, different impedance effects are included in the measured resistance. While at low
frequency or short current pulses (around 1 ms), only purely ohmic resistance is included, at
Energies 2021, 14, 1248 9 of 30

medium length pulses a combination of ohmic resistance and charge-transfer resistance are
measured. Impedance effects due to solid-state diffusion processes are only included when
the current pulse is long enough. Electrochemical impedance spectroscopy (EIS) is often
used to differentiate between the impedance distributions. The ohmic resistance of a cell is
typically caused by the electrolyte resistance and the contact resistance of current collector
and active mass. The electrolyte resistance depends on the ionic conductivity, which
changes with the concentration of the conductive salt. As this concentration is changing
with ageing, ohmic resistance is often used to identify electrolyte degradation [88]. The
measured internal resistances compared in this study are using 10 to 20 s pulses.
Ageing studies can generally be divided into cycle life and storage (shelf, calendar) life
studies. Storage life studies look at battery degradation versus the time that a battery was
stored under specific conditions. For this, the presently reviewed calendar ageing studies
performed characterization tests before storing and periodically after storing at the defined
SOC and temperature for specific time intervals. The characterization tests mostly consist
of capacity measurements using 1 to 3 cycles and IR (ohmic potential) measurements at
room temperature (defined either at 20 ◦ C or 25 ◦ C). Schmitt et al. [84] showed that the
degradation due to this electrochemical testing plays a significant role when looking at the
relatively small degradation rates during storage. They showed that the resistance increase
after 186 days, for a storage test with intermediate characterization tests can be more than
3 times the resistance increase for a storage test without intermediate characterization tests.
Therefore, the frequency of the characterization tests has to be considered carefully when
discussing and comparing calendar ageing studies.
Cycle life studies look at battery degradation when continuously cycled. For the
evaluation, the amount of cycling is quantified in different ways. Some studies look
at the number of cycles defined as one charge and one discharge until specified cut-off
voltages [81,85,86] or the degradation to the time that the battery is cycled [8,82]. Other
studies relate the current cycle capacity to the original cell capacity. This method is
applied using the terms normalized cycles [5], full equivalent cycles [7] or equivalent full
cycles [81]. This method will be referred to as full equivalent cycles (FEC) in the following.
To compare ageing data from different studies, the cycling time and the number of cycles
were calculated to FEC. The cycling time was converted to FEC by multiplying with half
of the C rate as the C rate is the rate at which a battery is discharged relative to its initial
capacity (a C rate of 1C means that the discharge current is equivalent to that of discharging
a battery from 100% to 0% SOC in 1 hour, e.g., from 70–20% SOC in half an hour). The
number of cycles was converted to FEC by multiplying the cycle number with the depth
of discharge (e.g., 80% in case of a SOC window of 10–90%) and integrating the capacity
loss over the number of cycles using a linear regression between two measurement points.
When evaluating degradation characteristics batteries are cycled in different SOC windows
(e.g., 20% to 80% SOC) or stored at a specific SOC. Some studies use the term Depth of
Discharge (DOD) instead of SOC. The DOD can either be given from 100% SOC, so that
e.g., 60% DOD is equal to a SOC window of 40% to 100%, or DOD can be given around
50% SOC, so that e.g., 60% DOD around 50% is equal to a SOC window of 20% to 80% SOC
(as one utilises 60% around a reference SOC at 50%) [7].

2.3. Cycling: Capacity Fade and Resistance Increase as a Function of Temperature, C Rate and
SOC Window
Capacity fade and resistance increase and the effect of different parameter on those
are compared for cycling ageing for different chemistries and studies.

2.3.1. Capacity Fade

The capacity degradation as a function of FEC from different reviewed cycle life
studies are presented in Figure 3. All presented studies use commercial LIB and cycle
with a C rate (charging/discharging) of 1 C/1 C, within a SOC window of 0–100% and
a temperature of 25 ◦ C unless specified otherwise in the legend. The cathode and anode
material are specified in the figure legend, more details are presented in Table 1. The
Energies 2021, 14, 1248 10 of 30

studied batteries are numbered to simplify referencing. All studies use a climate chamber
for temperature regulation (except [89]) without further specifying the cooling strategy. It
is noticeable that three studies report a significantly slower degradation of the observed
batteries (3, 8, 11) than all others (1, 7, 13–16). The slower degrading batteries are those
using a NMC cathode and a carbon anode without silicon and LFP/graphite. A SOH of
80% and thus the defined end of life for automotive applications was reached after nearly
3150 FEC for LFP/graphite (3) and 4000 FEC for NMC/hard carbon (8). The NMC/graphite
(11) reached more than 8800 FEC, but it has to be noted that this battery was cycled with a
reduced DOD of 80%. The NMC/hard carbon (8) shows a drop in SOH around 500 FEC
and a further steady decrease in SOH afterwards. The SOH of the LFP/graphite (3) drops
to around 3000 FEC. The other study on an LFP/graphite (1) presented in the figure shows
a significantly faster capacity degradation. A SOH of 80% is already reached after 600. Both
studied batteries are cylindrical but the better performing battery (3) has 2.3 Ah, while the
other only has 1 Ah. Although, the most significant difference is the ambient temperature
during operation. The faster degrading battery was operated at 45 ◦ C, while the other
was operated at 30 ◦ C. The other batteries with significantly larger degradation rate are
NMC/LMO blend with carbon anode (7), NMC with Si/C (13, 14) and the LCO/graphite
(15, 16). The NMC/LMO blend with carbon anode (7) has a slow degradation rate for the
first 500 FEC before the capacity starts decreasing quickly, reaching a SOH of 80% around
800 FEC.

Figure 3. State of health (SOH) as a function of full equivalent cycles (FEC). If not specified differently
in the legend, all batteries were cycled under the same conditions (charging/ discharging rate of
1 C/1 C, SOC window of 0–100% and a temperature of 25 ◦ ). Numbers are specified in Table 1. Linear
segments that connect data points for visual orientation.

Both NMC batteries with a Si/C anode (13,14) degrade significantly faster than the
NMC batteries with carbon-based anodes without silicon (8, 11). The capacity of battery
14 decreases extremely fast; a SOH of 90% is already reached after less than 100 FEC. Battery
13 reaches a SOH of 90% after around 400 FEC. (For comparison: the NMC batteries with
silicon free anodes reach this after around 1900 FEC (8) and 3800 FEC (11)). Both studied
batteries are cylindrical but the better performing battery (13) has 1.3 Ah while the battery
14 has 3.45 Ah. While battery 13 is cycled at 45 ◦ C with 1 C, battery 14 is cycled only at
25 ◦ C and 0.5 C. While the NMC type was not specified for battery 13, battery 14 has a
Ni-rich NMC cathode.
The SOH of both LCO/graphite batteries starts decreasing quickly from the start,
reaching a SOH of 80% already around 500 FEC for battery 15. The study on LCO/graphite
Energies 2021, 14, 1248 11 of 30

16 is not as extensive. However, the capacity degradation is a little slower. Battery 15 is

cylindrical and has capacity of 2.4 Ah while battery 16 is prismatic and has a capacity of
1.35 Ah. The charging current in the study of battery 16 is only 0.5 C.
It must be addressed that not only the anode and cathode chemistry differ between the
batteries in the reviewed studies, but also other factors like electrolyte composition, size and
geometry. While the electrolyte composition is not communicated, size and geometry are in
most studies. Table 1 shows that the nominal capacity of the batteries vary between 1 and
40 Ah. It is noticeable that the two largest batteries (11, 13) belong to the three batteries
that are degrading the slowest. Unfortunately, it is not possible to draw any conclusion
from this, as no comparable study with smaller NMC batteries was found in literature. In
general, it appears that the battery size does not impact the degradation behavior as much
as electrode material composition or operating condition. While for LFP/graphite (1, 3),
the smaller battery showed a faster degradation, for the studies with NMC/SiC (13, 14)
and LCO/graphite (15, 16), the larger battery showed a faster degradation. In all cases,
either the temperature, cathode composition or C rate varied between the studies as well.

Table 1. Battery specifications from reviewed studies.

Nominal
Nr. Cathode Anode Geometry Study Type Ref.
Capacity
1 LFP graphite 1 Ah cylindrical (18,650) cycling [90]
2 LFP graphite 1.1 Ah cylindrical (18,650) storage [91]
3 LFP graphite 2.3 Ah cylindrical (26,650) cycling, storage [6,7]
4 LFP graphite 15 Ah cylindrical (N/S) storage [92]
5 LFP carbon 2.2 Ah cylindrical (26,650) cycling [8]
6 LFP carbon 3 Ah cylindrical (26,650) storage [83]
graphite and
7 NMC/ LMO 1.5 Ah cylindrical (18,650) cycling [82]
carbon particle
8 NMC hard carbon 17.5 Ah pouch (23 × 15 × 0.5 cm) cycling and storage [5]
9 NMC graphite 2.05 Ah cylindrical (18,650) storage [91]
10 NMC graphite 2.15 Ah cylindrical (18,650) storage [84]
11 NMC graphite 40 Ah (N/S) cycling [89]
12 NMC graphite 8 Ah pouch (N/S) cycling [81]
13 NMC Si/C 1.3 Ah cylindrical (18,650) cycling [90]
14 NMC (Ni rich) Si/C 3.45 Ah cylindrical (18,650) cycling [27]
15 LCO graphite 2.4 Ah cylindrical (18,650) cycling [85]
16 LCO graphite 1.35 Ah prismatic (6.6 × 33.8 × 50 mm) cycling [86]

Figure 4 shows the FEC relative to the number of cycles at 25 ◦ C (18 ◦ C for LFP/Graphite)
at constant SOH as a function of temperature. For example; the lighter green line compares
NMC/LMO at 80% SOH. When cycling this battery at 60 ◦ C, one only achieves around
40% of the cycle compared to that of 25 ◦ C. The figure therefore illustrates the accelerating
effect of increased temperature on batteries using NMC/LMO blend, NMC, LCO, and
LFP as the cathode material and a carbon-based anode. Although NMC/Hard carbon and
LFP/Graphite age slowest, it appears that they are more temperature-sensitive compared
to LCO and NMC/LMO. When considering a temperature increase from 25 ◦ C to 55 ◦ C for
the NMC battery, the SOH of 80% is already reached after only 5% of the FEC. It is also
striking that except for a SOH of 95%, the temperature dependency is nearly linear and
very similar for different SOH, which is important for temperature accelerated ageing tests.
The capacity degradation of the battery with NMC/LMO shows a lower but still significant
temperature dependency with a decreasing impact with ageing. The lowest impact can be
observed for the battery with the LCO cathode. Increasing the temperature from 25 ◦ C to
55 ◦ C results into a 60% decrease of FEC at a SOH of 95%. The battery with LFP cathode
shows a decrease in capacity, with temperature similar to the battery with NMC cathode.
It is also noticeable that NMC, LCO, LFP have the largest temperature dependency in a
Energies 2021, 14, 1248 12 of 30

temperature interval between 25 ◦ C and 40 ◦ C. A further increase in temperature has a

declining effect on capacity degradation. The temperature dependency of the NMC/LMO
shows the same trend for a SOH of 95%, but appears to be most sensitive to temperature
changes in a temperature interval of 50 ◦ C to 60 ◦ C for further cycling.

Figure 4. Capacity fade during cycling as a function of temperature. NMC/Hard carbon (8) [5] and
NMC/LMO- Graphite & carbon [82] relate to 25 ◦ C, charging and discharging rate of 1 C and 100%
DOD. LCO/Graphite (16) [86] similarly, but with a charging rate of 0.5 C. LFP/Graphite (3) [8] relates
to 15 ◦ C, discharge rate 0.5 C and data summarized for DOD of 10 to 90%. Linear segments that
connect data points for visual orientation.

Figure 5 illustrates the accelerated capacity fading due to an increased charging rate.
Moreover, the y-axis represents how many cycles one can expect at a given C rate relative
to 1 C, with all other conditions unchanged. Generally, the chemistries with the poorest
ageing properties are also the ones most sensitive to rate changes. When increasing the
charging rate from 0.5 C to 1.5 C for the LCO battery, a SOH of 85% is reached after only
30% of the FEC. However, initial accelerated ageing for a C rate of 0.5 C as a 95% SOH is
already reached 20% faster. The accelerating effect of the C rate on degradation is even
more significant at the beginning of cycling. For the battery with the NMC cathode, the
effect of the charging rate increases with ageing. Only around 50% of the FEC can be
realized before reaching a SOH of 80% when increasing the charging rate from 0.5 C to
1.5 C. It is noticeable that while dependency on charging rate for NMC seems to be linear,
the dependency for the LCO is higher when charging rates of 1 C and higher are reached.
For the battery with LFP cathode, an increase of the C rate from 1 C to 2 C seems to have
nearly no effect.
Figure 6 shows the amount of FEC for different SOC windows around a SOC of 50%
relative to a SOC window of 0–100%, which was the only common point of reference. The
batteries with NMC cathode benefits from decreasing the SOC window. When decreasing
the SOC window from 0–100% to 20–80%, a SOH of 95% is only reached after nearly 2 times
the amount of FEC. A further decrease to 40–60% seems to bring no further improvement.
The battery with the LFP cathode shows a complex relationship between SOC window
and capacity degradation with plateaus between the DOD of 100% to 60% and 50% to 10%.
Decreasing the SOC window from 0–100% to 25–75% bisects the amount of FEC that can
be realized until a specific SOH. A further decrease in the SOC window until 45–55% has
no additional effect. The voltage window of a LFP cathode is more narrow than other
cathodes. It never reaches as high a voltage as NMC etc., which are especially critical for
the stability. This explains why a decrease in the SOC window is not beneficial.
Energies 2021, 14, 1248 13 of 30

Figure 5. Capacity fade during cycling as a function of the charging rate. NMC/Hard carbon (8) [5]
and LCO/Graphite (15) [85] at 25 ◦ C and fixed discharging rate at 1 C, LFP/Graphite (3) [7] 30 ◦ C,
the discharge rate is similar to charging rate. Linear segments that connect data points for visual
orientation.

Figure 6. Capacity fade during cycling as a function of DOD around 50% SOC e.g., 60% DOD is equal
to a SOC window of 20% to 80%. NMC/Graphite (12) [81] at 25 ◦ C and 6 C charging and discharging
rate, NMC/Hard carbon (8) [5] at 25 ◦ C and 2 C charging and discharging rate and LFP/Graphite
(3) [7] at 30 ◦ C and 1 C charging and discharging rate. Linear segments that connect data points for
visual orientation.

One can summarize that NMC and LFP with a carbon-based anode perform the
best at a constant and moderate temperature, as they are very sensitive to an increase in
temperature beyond room temperature. Temperature has the largest impact on the ageing
behaviour for all the chemistries. Only LCO/graphite appears to be aged more aggressively
by charging rate in comparison to ambient temperature. Increasing the charging rate from
0.5 C to 1 C has a similar effect on the capacity as increasing the ambient temperature from
25 ◦ C to 35 ◦ C.
The effect of an increased C rate and SOC window seem to be in the same order
of magnitude for the battery with NMC and carbon based anode, with the effect of the
SOC window being smaller for the study using a larger variation in SOC window and
a graphite anode instead of hard carbon. This leaves an unanswered question about if
a further reduction of the SOC window is accelerating ageing more or if it is the anode
Energies 2021, 14, 1248 14 of 30

material that is responsible for the change in behaviour? The LFP/graphite seems to be
most sensitive to an increase in temperature, followed by the variation in SOC window
and showing nearly no effect when changing the charging rate.

2.3.2. Resistance Increase from Cycling Rate

Most studies only communicate the relative changes of the resistance during cycling.
However, when looking at the few reported values, it stands out that the internal resistance
of LCO appears to be significantly larger than for NMC. Gao et al. [85] report a 1 s resistance
of approx. 33 mΩ at the beginning of life (BOL) for the LCO battery they evaluate, while
Richter et al. [93] and Gao et al. [81] report an internal resistance of around 2–3 mΩ for NMC
batteries. All evaluated studies [81,85,87] that examine the effect of cycling on the internal
resistance show that, apart from an initial decrease in resistance for certain conditions,
cycling increases the resistance of a LIB.
The elevated operating temperature has the largest impact on the rate of resistance
increase, followed by an increased C rate over 1 C [85,87]. Some studies show that by
reducing the SOC window the effect on the C rate increase can be reduced [87]. The effect
of the SOC window is inconclusive when comparing different studies. Wikner et al. [87]
show that the resistance increase is most pronounced at higher SOC windows in their study
with an NMC/LMO cathode and surface-treated natural graphite anode. On the other
hand, Gao at al. [81] show that the resistance increase in their study with an NMC cathode
and graphite anode is most pronounced at low SOC windows.

2.4. Calendar Ageing: Capacity Fade as a Function of SOC and Temperature

2.4.1. Capacity Fade
When comparing the results from calendar life studies for the cathode materials
NMC and LFP stored at 100% SOC and a temperature between 20 and 30 ◦ C, the study
by Schmitt et al. [84] with a NMC-graphite battery and two studies with LFP-graphite
batteries by Grolleau et al. [92] and Naumann et al. [83] show a similar behavior in capacity
degradation over time. However, the study by Richter et al. [5] with a battery with NMC
cathode and hard carbon anode has the largest decrease in SOH with time. It can be
observed that the capacity decrease slows down with time. In literature, this is often
modeled as square root dependency and explained with the growth rate of the SEI. The
increased SEI thickness results in a reduction of the solvent diffusion rate and consequently
to a slowing down of SEI growth and capacity loss [83]. As expected, the battery stored
at 20 ◦ C loses capacity slower than the one stored at 25 ◦ C. However, the capacity of the
LFP battery stored at 25 ◦ C in the study by Naumann et al. [83] fades slightly slower than
the capacity of the LFP battery stored at 30 ◦ C in the study by Grolleau et al. [92]. Figure 7
shows that increasing the temperature has an accelerating effect on the capacity degradation
of an LFP battery, even though this effect is not very severe. This is similar for all compared
studies [6,83,92], although the study by Grolleau et al. appears to be the least affected by
temperature. It is only possible to speculate what the reason for this behavior is. One
reason can be different testing schedules with more frequent characterization cycling and
temperature change in the studies with faster fading or slightly different cell chemistries
(e.g., electrolyte additives, crystallinity of the graphite) that were not communicated, or
different battery sizes (e.g., 3 Ah in Naumann et al., 15 Ah in Grolleau et al.).
Figure 7 shows the storage time relative to a temperature between 40 and 45 ◦ C for
batteries with an NMC cathode and a hard carbon anode and LFP cathode and a graphite
anode. The effect of increasing the temperature from room temperature is more severe
for the NMC battery and increases with ageing. When increasing the storage temperature
from 25 ◦ C to 42.5 ◦ C, a SOH of 85% is reached 6 times faster and 15 times faster when
increasing the storage temperature to 55 ◦ C. All three studies on batteries with LFP cathode
show that the capacity degradation is increasing with temperature as well, however less
significant than for the NMC battery. When increasing the storage temperature from 25 ◦ C
Energies 2021, 14, 1248 15 of 30

to 40 ◦ C, a SOH of 90% is reached 1.3 times faster and 5 times faster when increasing the
storage temperature further to 60 ◦ C.

Figure 7. Capacity fade during storage as a function of temperature. Series marked with * are
related to 42.5 ◦ C [5] instead of 40 ◦ C and series marked with ** are related to 45 ◦ C [92] instead of
40 ◦ C [6,83]. The NMC/ Hard carbon (8) battery was stored at 80%, LFP/Graphie (3) [6] (purple)
at 90% and LFP/Graphite (6) [83] (blue) and LFP/Graphite (4) [92] (green) at 100% SOC. Linear
segments that connect data points for visual orientation.

In Figure 8, the storage time relative to a SOC 90 or 100% for batteries with NMC
cathode and hard carbon anode and LFP cathode and graphite anode is presented. The
effect of an increased SOC during storage is more severe for the NMC/hard carbon battery
and is increasing with ageing. The effect of an increased SOC appears to be linear in the
SOC window from 60% to 90% before it reaches a plateau for a further increase until 100%.
When storing an NMC/hard carbon battery at 100% instead of 60%, a SOH of 90% is
reached 7 times faster. The effect of an increased SOC during storage is accelerating the
capacity degradation less severe for batteries with LFP/graphite battery.
In summary, both increased SOC and temperature during storage are accelerating
capacity degradation with the temperature being more damaging. These trends appear
the same for both batteries with an NMC cathode with a hard carbon anode and an LFP
cathode with graphite anode but are more severe for the NMC battery with a hard carbon
anode. While the NMC/hard carbon battery performed best when evaluating the cycling,
the LFP/graphite batteries are more stable in terms of calendar ageing. A SOH of 90%
was reached for an LFP/graphite battery after 260 days at 40 ◦ C and a SOC of 90% in [6],
after around 220 days at a SOC of 100% (25 ◦ C: 660 days) in [83] and around 100 days at
a SOC of 100% and a temperature of 45 ◦ C in [92]. The same SOH was already reached
after around 70 days for an NMC/hard carbon battery in [5], after storage at 80% SOC and
42.3 ◦ C (25 ◦ C: 360 days).
Energies 2021, 14, 1248 16 of 30

Figure 8. Capacity fade during storage as a function of SOC. Series marked with * are related to
90% SOC instead of 100% SOC. ‘NMC [5]’: 25 ◦ C, ‘LFP [6]’, ‘LFP [84]’: 40 ◦ C. Linear segments that
connect data points for visual orientation.

2.4.2. Resistance Increase during Storage

All evaluated studies [5–7,81,83–85,87,88] show a clear increase in resistance during
storage and cycling. The resistance generally increases between 30% and 100% from BOL
(beginning of life) with 100% SOH to EOL (80% SOH).
During storage, an approximately linear increase of resistance with storage time can
be observed. Some studies show an initial decrease until a SOH around 95% in resistance
before finally increasing [83,87,93]. This appears to be independent of the cathode and
anode material. An increased storage temperature accelerates the resistance increase
rate significantly. The influence of the SOC (or SOC window) appears to be different for
different chemistries—especially for LFP. For NMC and NCA, the rate is increasing with
SOC [5,88]. The resistance increase for LFP is by far the lowest and the impact of SOC is
fairly small [83,88]. The largest resistance increase is observed when storing at 50% SOC,
smaller impact towards 0% and 100% SOC, lowest for 0% [83].
The increase of internal resistance during calendar ageing is often explained with
increased ionic resistance due to the formation of surface layers (e.g., SEI). This would
agree with different observation and behaviour for LFP.

2.5. Discussion
The degradation mechanisms of LIBs are manifold and strongly linked to many
interactive factors, such as battery materials, types and operating conditions. There are
large variations between the LIB cells in different literature studies, of which some are
reported like anode and cathode material, capacity and geometry and others are not like
electrolyte composition and fabrication parameter. Others are partially reported, like the
cooling strategy and cycling schedule. Those external factors are known to have an impact
on the different degradation mechanisms inside LIB which are categorized into LLI, LAM
and impedance increase. Sections 2.3 and 2.4 showed that the studied LFP/graphite,
NMC/hard carbon and NMC/graphite had the longest cycle life and longest when cycled
and stored at moderate temperatures. The studied batteries NMC/LMO with graphite
and carbon particle, NMC/Si-C and LCO/graphite had a significant shorter cycle life.
It appears that apart from the batteries using anodes with silicon, the type of cathode
material has the largest impact on the length of the cycle life. It appeared that the rate
of capacity degradation during cycling was most significantly increased by an increased
ambient temperature for all compared studies, with the batteries utilizing LFP or NMC and
Energies 2021, 14, 1248 17 of 30

a carbon-based anode being the most sensitive. It was noticeable that the LCO/graphite
battery (15) was significantly more sensitive to a C rate increase than any other compared
battery. Due to a lack of data, only LFP/graphite and NMC/hard carbon were compared
in terms of storage lifetime. While they show a similar capacity degradation when stored
at moderate temperatures, NMC/hard carbon appeared to be significantly more effected
by larger storage temperatures and storing at high SOC.
In present electrolyte solutions with LiPF6 , traces of HF are often inevitable and this
leads to the dissolution of transition metal ions from the cathode. This results in a reduction
in active material and passivation of the negative carbon electrode due to redeposition
of these transition metal compounds. This leads to increased thermal resistance and is
accelerated with increased temperature. Aurbach et al. [94] showed that this degrada-
tion mechanism is more important for LCO and LFP than other chemistries, and that
LiMn1.5 Ni0.5 O4 and LiMn0.5 Ni0.5 O2 have better stability in this respect, and attributed it to
the unique surface chemistry due to the presence of nickel ions in the lattice.
The main ageing mechanisms in NMC- and Ni-rich NMC cathodes are the cracking
of secondary particle due to expansion and contraction of crystal lattices during cycling,
surface reconstructions resulting an inhibition of Li+ insertion and desertion. At high
SOC high-valence, ions can trigger side reactions like the decomposition of electrolyte
often resulting in dissolution of NMC materials. Transition metals, especially Mn2+ from
dissolved NMC, can cause significant capacity loss due to massive damage to the SEI
layer [35]. Naumann et al. [83] showed that the loss of active material on the anode when
using an LFP cathode at elevated temperatures was a result of Fe deposition on the anode.
The main ageing mechanism on carbon-based anodes is the development of the
SEI layer over time which consumes Li-ions and increases the resistance. This is more
severe at a higher SOC (>80%) and accelerated with temperature [82]. A high SOC results
in a lowered anode potential which causes electrochemical instability on the electrolyte
components [7]. A further expansion of the SEI layer can be triggered during storage at
high cell voltage (low anode reduction potential). Solvent interaction with graphite after
diffusion of solvent components through the SEI layer, can induce graphite exfoliation and
gas creation leads to the cracking of the SEI layer which again leads to further SEI growth.
This is in agreement with the degradation acceleration by the SOC for all chemistries,
except LFP, as the voltage window of an LFP chemistry is smaller. Additional Li-ions are
consumed due to side reactions on the anode [95]. High temperatures can furthermore lead
to a dissolving of the SEI and creation of Li salts less permeable to Li-ions which results
in an increased anode ohmic impedance. At low temperatures (<∼5 ◦ C), a decrease of
Li diffusivity within SEI and the carbon anode can lead to plating of metallic Li outside
the SEI/anode material and subsequent reaction with the electrolyte, leading to loss of
cyclable Li. The temperature at which plating of Li happens depends on the polarization
potential vs. Li/Li+ , and is, therefore, material dependent [82]. As for graphite anodes,
further degradation occurs due to the cracking of layered graphitic structures [35].
Studies [27,42,96] showed that even with 5% of silicon added in a carbon anode, the
extreme expansion and contraction of silicon upon lithiation and delithiation have massive
effects on the degradation. Particle cracking leading to contact loss and thickening of the
SEI layer contribute to an impedance rise and loss of cyclable Li.
For all reviewed and compared studies, there was no obvious correlation of the size
and geometry and the battery lifetime and sensitivity towards operation condition. As
the amount of comparable literature data is relatively small, it is not possible to draw a
detailed conclusion. Although, it is possible to say that the cathode and anode material
appear to have a more significant impact.
In addition to the discussed, other factors like fabrication parameter, electrolyte com-
position and thermal management strategy have been shown to have an impact on both
the performance and degradation of LIB. The fabrication process parameter determine the
mesostructure of the electrode materials which is characterized by the spatial location of
the active material particles, carbon additive and binder, contact between electrode material
Energies 2021, 14, 1248 18 of 30

and current collector etc. Fabrication process parameters that have been among others
shown to have a large impact on the performance are coating of active particle [97], slurry
composition [98], calendaring of electrodes [99]. Electrolyte additives are used to improve
the performance and lifetime of LIB. Additives are mostly utilized to improve the SEI for-
mation, protect the cathode, stabilize the LiPF6 salt and therefore have a significant impact
on the degradation behavior [100–102]. As all reviewed studies have been conducted with
commercial cells, details on fabrication parameter and the electrolyte composition were not
disclosed and therefore outside the scope of this review. While all reviewed studies report
the type of climate chamber used for the study, settings like fan speed are not specified. To
elude more on the importance of the cooling strategy for the comparability of the ageing
studies, simple thermal simulations have been conducted and used for further evaluation
of the reviewed literature data.
From the review, it is concluded that temperature has the largest impact on the ageing
behaviour in terms of capacity degradation and resistance increase for all the chemistries,
both in operation and during storage. Only LCO appears to be aged more aggressively by
charging rate in comparison to ambient temperature.

3. Modelling Battery Temperature

In the following, a sufficiently simplified thermal battery model and the studies
conducted to allow a further evaluation of the reviewed ageing studies are presented.

3.1. Thermal Model

To indicate the impact of the SOC and C rate on the battery temperature, simulations
based on a simple thermal model are performed. The 1D stationary solution of the energy
balance is used. This simplification does not allow one to model the transient temperature
change when starting to discharge a resting cell, but rather models a steady-state once a
balance between heat generation and external heat transfer is reached. This is representative
for batteries continuously cycled at constant rate, with heat sources averaged over the SOC
window. This allows to assess the external temperature difference; the difference between
the average battery temperature and the ambient air temperature which is reported in
most experimental studies. For internal temperature gradients, Equation (1) describes this
model.
∂  ∂T 
0= λx +Q (1)
∂x ∂x
where λ x is the thermal conductivity in the through-plane direction and Q is the volumetric
heat generation. The thermal conductivity in through-plane direction is calculated by
normalising the electrodes and the separator by their thickness di :

dtotal
λx = di
(2)
∑ λi

Heat generation due to activation overpotentials, ohmic heating and entropic heat is
considered [103]. While the entropic heat is reversible, the overpotential and ohmic heating
are lost work. All heat sources depend on the current density j:
1. heat due to the resistances to the electrochemical reactions, expressed in the overpo-
tential, ηj,
2. the ohmic heat, rω j2 , due to the paths of the charge carrier (the ion transport in the
electrolyte, and the electron transport in the solid-state materials and metals.
3. heat due to rearrangement in the electrode, expressed as entropy change, T∆S F j, which
is reversible and acts as a heat source during discharge and heat sink during charge.
The total heat generation during charge and discharge for a full LIB can be described
as follows:
T∆S
q=± j + rω j2 + ηj (3)
F
Energies 2021, 14, 1248 19 of 30

For simplification, the center of the battery is set at x = 0. The volumetric heat
generation for half a LIB with n cells during charge and discharge becomes:
q n
Q= ∗ (4)
dtotal 2

As a stack of several single cells is modeled, it is fair to assume the maximum tem-
perature in the center of the battery. The heat transfer due to convection is assumed to
dominate and the heat transfer coefficient h to describe the heat transfer from the surface
of the battery to the ambient is used. The heat transfer coefficient is the proportionality
constant between the heat flux and the thermodynamic driving force for the flow of heat
(i.e., the temperature difference). The boundary conditions therefore become:

dT q
= 0, T ( x = dtotal /2) = + Tamb (5)
dx x =0 h

where Ttotal the ambient temperature.

The entropy change ∆S highly depends on the SOC and chemistry [104,105].
Calculation of the overpotential is based on Tafel equation valid for current densities
significantly larger than the exchange current density. Burheim et al. [106] showed no
significant difference in the Tafel behaviour with SOC within the SOC range of 20% to
100%.
η = a + b log| j| (6)
where a = −b log j0 , b is the observed Tafel slope, j and j0 are the effective current density
and exchange current density.

3.2. Modelling Cases and Parameterisation

The parameters used for all the modelled cases are presented in Table 2. A 1 D
simulation for a battery cell consisting of 24 unit cells is conducted. Simulations are
conducted for three different studies presented in the following. These allow one to
evaluate the benefit of an efficient thermal management and the effect of a temperature
increase during operation on the lifetime of a cell.
Study 1: Heat transfer from the battery surface to the surroundings. The average temper-
ature increase of a LIB is modelled for different C rate and heat transfer coefficients at
the BOL and with an average entropy change in the range of most common chemistries
(e.g., NMC and LFP). The increase in battery temperature is modeled in comparison to
the ambient temperature depending on the heat transfer from the surface of the battery
to the ambient, which is described using the heat transfer coefficient. Typical values for
the heat transfer coefficient range from 7 W/m2 K for natural air convection [107] and
gradually increase with air velocity. Commonly forced air convection is starting in the
range of 25 W/m2 K [108]. Natural water cooling starts around 30 W/m2 K and can increase
up to 8000 W/m2 K with increasing water velocity [109].
Study 2: LCO battery. The LCO battery appeared to be most sensitive to increased
C rates among the chemistries reviewed, and more sensitive to C rates than temperature
increase, as shown in Section 2.3. The potential effect of of the cathode chemistry on the
temperature increase is evaluated. It is noted that the internal resistance of the studied
LCO battery was about 10 times larger than the reviewed NMC chemistry and the LCO
chemistry has an about 3–4 times larger average entropy change compared to LFP-G and
NMC-G [105]. Both have an effect on the battery heat generation.
Study 3: Ageing. The temperature increase of an aged cell with a cell at the BOL are
compared. Section 2.4.2 showed that the internal resistance generally increases between
30% and 100% from BOL to EOL. Additionally, the internal heat transport depends on the
thermal conductivity of the battery materials. Richter et al. [93] showed that the thermal
conductivity decreases with ageing and a decrease in amount of electrolyte.
Energies 2021, 14, 1248 20 of 30

Table 2. Input parameter for the thermal model.

Parameter Value Ref.

Number of single cells 24
Ambient temperature 290 K
1 C rate 35 mA2
Anode thickness 74 µm
Separator thickness 12.1 µm
Cathode thickness 67 µm
Current collector thickness 20 µm
Thermal conductivity, anode, new and soaked 1.11 WK−1 m−1 [5]
Thermal conductivity, separator, new and soaked 0.31 WK−1 m−1 [5]
Thermal conductivity, cathode, new and soaked 0.33 WK−1 m−1 [5]
Thermal conductivity, anode, aged and dry 0.32 WK−1 m−1 [5]
Thermal conductivity, separator, aged and dry 0.10 WK−1 m−1 [5]
Thermal conductivity, cathode, aged and dry 0.13 WK−1 m−1 [5]
Average entropy change over 0–100% SOC range, LFP-G 12.5 J mol−1 K−1 [105]
Average entropy change over 0–100% SOC range, NMC-G 10 J mol−1 K−1 [105]
Average entropy change over 0–100% SOC range, LCO-G 37 J mol−1 K−1 [105]
Internal resistance, NMC 2 mΩ [93]
Internal resistance, LCO 33 mΩ [85]
Tafel parameter a −0.039 V [106]
Tafel parameter b 0.068 V decade−1 [106]

4. Results and Discussion

In the following, the results from the thermal modelling are presented and the im-
portance of an efficient thermal management system for different C rates, by estimating
the maximum internal temperature, the increase during discharge compared to the ambi-
ent temperature is evaluated and discussed. Prospects of chemistry-dependent changes
and ageing are presented. The results are discussed in light of temperature and C rate
dependent ageing rates, presented in Section 2.3.
Study 1: Heat transfer from the battery surface to the surroundings. Figure 9 shows the
difference between the battery temperature and the ambient temperature as a function of
the heat transfer coefficient compared for different C rates (while discharging). All results
present a steady-state temperature difference between the ambient and the temperature
in the battery midplane (at x = 0). The figure also indicates which cooling strategies
correspond to the heat transfer coefficients (discussed in Section 3.2). The heat transfer
coefficient has a large impact on the temperature increase, especially for high C rates.
When considering only natural air convection (h = 7.17 W/m2 K) for the removal of heat,
higher C rates can cause a significant temperature increase of up to 40 K for 8 C and 13 K
for 4 C. For lower discharging rates of 0.5 C to 1 C, the generated heat only leads to a
temperature increase of up to 2 K above the ambient temperature. With an effective thermal
management system instead of natural air convection and therefore significantly larger
heat transfer coefficient, it is possible to reduce the battery temperature by up to 35 K
for 8 C and 11 K for 4 C (compared to h = 7.17 W/m2 K). The maximum temperature is
proportional to the inverse of the heat transfer coefficient.
Energies 2021, 14, 1248 21 of 30

Figure 9. Difference between battery and ambient temperature depending on the heat transfer from
the battery surface to the ambient for different C rates.

Comparing these modelling results with the conclusion from the review in Section 2.3
allows us to better understand the benefit of a thermal management system. As discussed
in Section 2.3 both a temperature increase in this order, as well as an increased C rate, have
a serious effect on the capacity decrease and resistance increase. When assuming that the
acceleration effect of a high C rate is superimposed from the increased temperature and the
actual C rate effect, it allows us to estimate the benefit of the thermal management system
for the battery lifetime. When having C rates of around 4 to 8 C a significant difference
between the battery and ambient temperature of around 13 K to 40 K, respectively, can be
observed. This is when no active thermal management system is applied. The study on
temperature-dependent cycling ageing showed that an increase of around 30 K to 35 K can
lead to a decrease in the battery life of around 65% to 95% depending on the chemistry. This
is for a constant C rate, only considering the increase in degradation due to temperature
increase. When changing the cooling strategy from non-active air cooling (h = 7.17 W/m2 K)
to forced air cooling (h = 50 W/m2 K), the temperature difference can be decreased to 3 K
to 8 K (for 4 and 8 C, respectively). This can lead to a temperature-induced decrease in
the battery lifetime of up to 55%. The cooling can be further enhanced when changing the
cooling medium to water, resulting in a difference of battery and ambient temperature
of 2 K to 4 K (for 4 and 8 C, respectively), reducing the temperature-induced decrease of
battery life to around 1% to 20%, but as previously stated—water cooling is complicated.
All mentioned numbers only consider the temperature effect of a high C rate, but not the
effect of a C rate increase itself.
Study 2: LCO battery. In the literature review (Section 2.3), the LCO battery appeared
to be most sensitive to increased C rates among the chemistries reviewed. The battery
temperature for the reviewed LCO and NMC chemistry with the internal resistance being
about 10 times larger and about 3–4 times larger average entropy change of the reviewed
LCO chemistry compared to the NMC chemistries (cf. Table 2) are modelled and compared.
Figure 10 shows the results for discharging rates of 0.5 C, 1 C and 2 C and a heat transfer
coefficient from 7 to 50 W/m2 K. The higher internal resistance and entropy change result
in a significant larger temperature increase. The additional temperature increase is already
significant for small C rates of up to 2 C. In the extreme case of only considering heat
removal from the battery due to natural convection, the internal temperature of an LCO
Energies 2021, 14, 1248 22 of 30

battery at a C rate of 2 C can have an up to 23 K larger temperature increase compared to

NMC—28 K in total.

Figure 10. Difference between internal and ambient temperature as a function of heat transfer
coefficient—impact of a larger internal resistance and average entropy change for LCO-G.

It was shown in Section 2.3 that a temperature increase of around 25 to 30 K can

lead to a temperature-induced decrease in the battery lifetime of up to 50% for an LCO
battery. This compares to a lifetime reduction of around 20% for an 5 K increase for
NMC. In experimental studies, studies investigating the effect of temperature and C rate
on capacity loss are separated. The cooling management during those studies is rarely
communicated. When considering capacity loss to be comprised of capacity loss due to
increased temperature and C rate, it is possible to evaluate the actual effect of increased
C rates on degradation. Table 3 summarizes and compares the results for the discussed
studies for the LCO battery and NMC battery for a C rate increase from 0.5 C to 1.5 C
and estimates the actual C rate effect. The lifetime reduction due to a C rate increase from
0.5 C to 1.5 C was found to be 80% for LCO and 30% for NMC in the presented studies,
see Figure 5. Considering only heat removal from the battery due to natural convection
for both, the modelling results (Figure 10) show that this C rate increase can lead to a
temperature rise of 14.5 K and 2.3 K, respectively. Based on the data presented in Figure 4,
and using linear interpolation, it is possible to estimate the lifetime reduction purely due to
this temperature increase to be 43% for LCO and 11% for NMC, which results in an actual
C rate effect of 36% and 19%. This shows that even though LCO appears to be far more
sensitive to an increased C rate than other chemistries, a considerable proportion is actually
due to an increased heat generation rate.

Table 3. Comparing and evaluating temperature increase and FEC reduction of LCO and NMC for a
C rate increase from 0.5 C to 1.5 C.

LCO NMC
Temperature increase 14.5 K 2.3 K
Temperature induced FEC reduction (Figure 4) 43% 11 ± 1.2%
“C rate induced” FEC reduction (Figure 5) 79.5 ± 0.6% 30 ± 6%
Revised C rate induced FEC reduction 36% 19%
Energies 2021, 14, 1248 23 of 30

Study 3: Ageing. Figure 11 shows how an increase in resistance of 100% and a decrease
in thermal conductivity due to ageing effects the temperature increase. While the affect
is insignificant for low C rates (0.5 and 1 C), it becomes significant for larger C rates. It
results in an additional temperature increase of up to 2.5 K at 2 C and 8 K at 4 C when
considering no active cooling. The increase is more significant for higher C rates, as the
ohmic heat is proportional to the current density squared. While the resistance increase
contributes mostly to the external temperature gradient, the thermal conductivity affects
only the internal heat transport. The combination of increased ohmic resistance and
lowered internal thermal heat transfer can result in even more severe accelerated ageing
towards the EOL of a battery.

Figure 11. Difference between internal and ambient temperature as a function of heat transfer
coefficient—impact of ageing.

It has to be mentioned that from a practical point of view, a simple calculation of the
battery temperature is not straight forward. The cell geometry and structure parameter e.g.,
tab size and positions, electrode and separator thickness, have an impact on the temperature
increase during cycling [110–112]. Most parameters were not enclosed by the studies. In
addition, the temperature rise of the battery was simulated steady-state; although this
might hold for low C rates, many experimental studies have shown the transient nature
of the temperature [73,113,114]. This especially becomes clear, when approaching h = 0
(no heat removal), where the temperature would approach infinity. This is not possible in
real batteries due to the heat generation being finite and the batteries capability to store
heat. In the present study we have considered a stationary model for assessing an average
external temperature difference; the difference between the battery temperature and the
ambient air temperature of the testing chamber. Ohmic heating, entropic heating and
Tafel overpotential heating have been considered, as they have been shown to have the
largest contribution to the heat generation of a battery. The internal resistance have been
measured to vary around 20% over the full SOC window [106]. The entropy change varies
significantly over the full SOC window and even changes sign, but only makes up around
10% of the total heat generation at the C rates that we are considering [105]. The entropy
variation with SOC and the ohmic resistance variation do somewhat balance each other
out, so that it is a fair simplification to consider the heat sources constant throughout the
SOC window. Moreover, the Tafel heat appears constant with SOC [106], and when then
considering continuous cycling, we indeed consider a stationary temperature model to be
a sufficiently good approximation for the purpose of discussing temperature deviations
Energies 2021, 14, 1248 24 of 30

between the ambient air and the battery in cycling ageing measurement. The aim was not to
provide specific battery temperatures but rather illustrate the large range of temperatures
possible during ageing studies, the large dependency on different factors and the effect
of this uncertainty with regards to the actual battery temperature during different ageing
studies. In the following, some of the simplifications are discussed in more detail.
It is well established that different battery geometries like cylindrical, pouch or pris-
matic have an impact on the temperature rise and temperature distribution of LIB. This
component was not included in the calculations, as all calculations were done in 1D for the
same cell thickness. This especially becomes important in Study 2, as the simulation results
were used to evaluate and compare the degradation behavior of NMC/hard carbon (8)
and LCO/graphite (15). While the NMC/hard carbon battery (8) was a 17.5 Ah pouch cell,
the LCO/graphite battery (15) was a 2.4 Ah cylindrical 18,560 cell. Here, only the impact
of the different cathode materials and internal resistances on the heat generation, were
included. Waldmann et al. [113] experimentally studied the influence of the cell design
on temperatures in LIB. By comparing the ratio of the maximum surface temperature to
the C rate of small (1.5 Ah) and larger (16 Ah) pouch cells to high-power and high-energy
cylindrical 18,650 cells, they found that the ratio for pouch cells is in between that of
high-energy and high-power 18,650-type cells. The main difference between high-power
and high-energy cells was found to be the smaller radial heat conductivity and higher cell
resistances. The internal resistance of the LCO/graphite battery (15) is in the range of that
of a high-power 18,650-type cell, showing that while neglecting the geometrical differences
between those two cells compared in Study 2, the significantly larger temperature rise
calculated of the LCO/graphite battery (15) compared to the 17.5 Ah pouch cell appears to
be reasonable.
Modelling the cooling of a battery is not straight forward beyond the options of forced
air convection. Cooling strategies should target the use of dry air, to prevent possible
shortings and leaking currents. Cooling by adding metal fins between pouch cells will,
due to expansion during charging cycles, lead to layers of air of up to a millimeter or
more—resulting in a heat transfer coefficient of 25 W/m2 K or less. Moreover, it has to be
noticed that the cooling strategy calculations represent an extreme case, with cooling over
the full surface area and no heating of the cooling media. This (uniform air flow) can be
true for using air as a cooling medium, but is less likely when water channels are used,
which causes a decrease in the area used and an increase in temperature of the cooling
media from the beginning to the end. Still, air temperature will increase as air flows over a
warm battery surface.
It has to be noted that internal resistance is known to be temperature dependent and
decreases with increased temperature. Therefore, the ohmic heating can be assumed to be
reduced once the battery is heated up and does not behave linearly. This might result in a
slight overestimation of the temperature increase, as the temperature dependency of the
resistance was not included in this simple simulation. Additionally, it has to be noted that
inhomogeneities are not considered in the simulations and the actual local temperature
might be significantly larger.
The results illustrate the challenge of comparing different studies on cycling ageing
and transferring study results from laboratory experiments to real battery applications.
The batteries are generally stored in temperature chambers, but it has to be taken into
consideration in what way the chambers are ventilated and thermally controlled. Ageing
studies should communicate the actual battery (surface) temperature to allow comparability
and an actual differentiation between temperature-induced and C rate-induced ageing.
Additionally, this information can be useful to find the most efficient thermal manage-
ment system with the best cost-benefit ratio for the specific battery application. Evaluating
the decrease in a lifetime based on the increased temperature in combination with mod-
elling the internal temperature for different cooling methods helps to find the optimal
thermal management strategy for different battery applications.
Energies 2021, 14, 1248 25 of 30

5. Conclusions
A review of degradation studies with different commercial LIBs was conducted,
covering different anode and cathode materials, geometries and nominal capacities. The
sensitivity of ageing behavior towards operation conditions was examined. As temperature
and charging rates are important, these ageing effects were compared in the light of a
sufficiently simplified thermal battery model.
The following trends were found from reviewing experimental degradation studies:
• In general, it appeared that the size of the nominal capacity and geometry does
not impact the degradation behavior during cycling as much as electrode material
composition, with the cathode material being more important than the anode material
for all anodes without silicon.
• Considering the operation conditions, it was found that temperature has the largest
comparative impact on battery ageing above room temperature. It accelerates both
capacity degradation and resistance increase.
• LIB utilizing LFP as cathode and carbon-based anodes appear to be less affected by
higher cycling rates (up to 2 C) and SOC window changes, then other chemistries.
• The resistance generally increases between 30% and 100% from beginning of life (BOL)
with 100% SOH to end of life (EOL) (80% SOH).
• Both increased SOC window and temperature were shown to accelerate capacity
degradation during storage with the temperature being more damaging.
• LIB utilizing LFP cathode and carbon based anodes are less have a longer storage life
and are less effected by storage temperature and storage SOC then LIB with NMC
cathode and carbon-based anodes.
• During storage, an approximately linear increase (after an initial decrease) of internal
resistance with storage time was observed.
• For cells stored without cycling, the frequency of cell characterisation tests appears to
affect the results, indicating that this type of studies has to be evaluated and compared
carefully.
For a deeper analysis, more comparable data and experimental studies are needed.
The thermal modelling showed that cooling strategy during studies on cycle ageing
have a significant impact on the actual battery temperature. The following trends were
found from evaluating the literature data with the results from the thermal modelling:
• When testing cells, the actual cell temperature can deviate severely from the reported
ambient temperature. Depending on the cooling strategy and C rate, the difference
between cell and ambient temperature can range between only a fraction of a degree,
up to 40 ◦ C.
• The battery lifetime reduction at high C rates can be for large parts (Table 3) due to
an increase in temperature, especially for high energy cells and poor cooling during
cycling studies.
This provides a challenge both when comparing different studies and when transfer-
ring results from laboratory experiments to real applications, as cooling conditions differ.
Therefore, measuring and reporting the actual battery (surface) temperature is crucial to
allow for a proper interpretation of results, and especially when evaluating charging and
discharging at high rates.

Author Contributions: Conceptualization, L.S. and O.S.B.; methodology, L.S. and O.S.B.; formal
analysis, L.S.; investigation, L.S.; writing—original draft preparation, L.S.; writing—review and
editing, L.S., O.S.B. and P.R.S.; visualization, L.S.; supervision, O.S.B. and P.R.S. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was funded by Norges forsknigsråd grant number 281005, Norges Teknisk-
Naturvitenskapelige Universitet grant number 68024013 and Royal Academy of Engineering grant
number CiET1718/59.
Energies 2021, 14, 1248 26 of 30

Institutional Review Board Statement: Not applicable.

Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors LS and OSB are grateful for financial support from the Research
Council of Norway, via the research project BattMarine (project no. 281005), and from Norwegian
University of Science and Technology (NTNU), via the strategic research ENERSENSE (project no.
68024013). PRS acknowledges support from The Royal Academy of Engineering (CiET1718/59).
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:

BOL Beginning of life

BTMS Battery thermal management system
di Thickness of component i
DEC Diethyl carbonate
DMC Dimethyl carbonate
DOD Depth of discharge
∆S Entropy change
EC Ethylene carbonate
EIS Electrochemical impedance spectroscopy
EMC Ethyl methyl carbonate
EOL End of life
η Overpotential
EV Electrical vehicle
FEC Fully equivalent cycle
j Current density
j0 Exchange current density
LAM Loss of active materials
λx Thermal conductivity in the through-plane direction
LCO Lithium cobalt oxide
LFP Lithium iron phosphate
LFP Lithium iron phosphate
LIB Lithium ion battery
LLI Loss of Li inventory
LMO Lithium manganese oxide
n Number of unit cells
NCA Lithium nickel cobalt aluminium oxide
NMC Lithium nickel cobalt manganese oxide
PC Propylene carbonate
PCM Phase change material
PE Polyethylene
PP Polypropylene
q Area specific heat generation
Q Volumetric heat generation
rω Ohmic resistance
Tamb Ambient temperature
SEI Solid electrolyte interphase
SOC State of charge
SOH State of health
SSE Solid-state electrolytes

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