Journal of Energy Storage 55 (2022) 105747

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Journal of Energy Storage

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Research Papers

Thermodynamic and kinetic limits of Li-ion battery operation

Ewelina Rudnicka *, Pawel Jakobczyk, Andrzej Lewandowski
Faculty of Chemical Technology, Poznan University of Technology, PL-60 965 Poznan, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: Capacity of graphene|electrolyte|Li laboratory cell was tested at different currents with the use of galvanostatic
Lithium-ion battery discharging. Impedance of Li4Ti5O12|electrolyte|Li laboratory and commercial Li-ion cells were measured with
Anode material EIS method. Literature data describing Li-ion batteries such as cathode and anode material capacity, battery
Cathode material
polarization, heat dissipation, volume changes, capacity under non-equilibrium conditions, pseudocapacitive
Batteries
Capacity
behavior, and battery safety were discussed. All these factors, both thermodynamic and kinetic, determine
overall practical battery efficiency. It was shown that different manners of electrode capacity expression are
commonly used. The phenomenon of dependence of battery capacity on current was discussed. Practical capacity
of electrode materials measured at non-equilibrium conditions (I > 0) are reported to depend on current. It was
shown, that battery polarization shortens the time necessary to obtain the cutoff voltage. Therefore the mea­
surement is stopped at a voltage before the system is fully discharged and hence, determined capacity value
apparently decreases with current. Moreover battery efficiency is also limited by other necessary but electro­
chemically inactive parts of the device.

1. Introduction
Rechargeable Li-ion batteries have become dominant power sources
for portable electronic devices. Therefore, a growing body of research
has focused on new electrode materials and the development of existing
systems [1–6]. The ability of the Li-ion battery to store energy is char­
acterized by its capacity q, expressed in coulombs (C) or usually amp
hours (Ah). However, the concept of capacity and its practical deter­
mination are somewhat ambiguous.
Numerous attempts have been made to find new electrode materials
of possibly high capacity [7,8]. However, the maximum amount of en­
ergy exchanged by a battery as work (Wmax), is determined not only by
the capacity of both electrodes, but also the difference of their electric
potentials Δϕ:
Wmax = qΔϕ(for I = 0)
In the case of lithium and lithium-ion systems their theoretical ca­
pacity is inversely proportional to the molar mass M of electrode active
material:
q = nFM − 1 (for I = 0)
where F is the Faraday constant.
In this work, for the first time, different points of view and reference
states are compared.
2. Experimental
Commercial LP501226 Li-ion battery was obtained from B&K, China.
Li4Ti5O12 (Aldrich), LiPF6 (Aldrich), lithium foil (0.75-mm thick,
Aldrich), vinylene carbonate (VC, Aldrich), lithium bis(tri­
fluoromethanesulfonyl)imide (LiNTf2, Fluka), single-layer graphene (G,
obtained by reducing graphene oxide prepared by Hummer's method,
specific surface 570 m2 g− 1 (in micropores), average particle size 2.28
μm, ACS Material, USA), carbon black (CB, Alfa Aesar), poly(vinylidene
fluoride) (PVdF, Fluka) and N-methyl-2-pyrrolidinone (NMP, Fluka)
were used as received from suppliers. N-methyl-N-propylpyrroldinium
bromide (MPPyrBr) was obtained by reacting N-methylpyrrolidinium
(1)
(Aldrich) with bromopropane (Aldrich) in acetone. Precipitated white
MPPyrBr crystals were decanted, washed 5 times with n-hexane and
dried under vacuum at 40 ◦ C. N-methyl-N-propylpyrrolidinium bis(tri­
fluoromethanesulfonyl)imide (MPPyrNTf2) was obtained from MPPyrBr
and LiNTf2 solution in an aqueous medium. The ionic liquid phase was
(2) separated from the aqueous LiBr solution, washed three times with
water and finally dried by evaporation in a vacuum at 50 ◦ C for 10 h. The
solid LiNTf2 salt was dissolved in the liquid salt MPPyrNTf2 (0.7 M

* Corresponding author.
E-mail address: ewelina.rudnicka@put.poznan.pl (E. Rudnicka).

https://doi.org/10.1016/j.est.2022.105747
Received 29 March 2022; Received in revised form 12 July 2022; Accepted 21 September 2022
Available online 27 September 2022
2352-152X/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
E. Rudnicka et al. Journal of Energy Storage 55 (2022) 105747

solution of LiNTf2 in MPPyrNTf2) to give the Li+ containing ionic liquid Table 1
[Li+]m[MPPyr]n[NTf2]z. The water content in the [Li+]m[MP­ Capacity q of different Li or Li-ion battery anodes [mAh g− 1], calculated ac­
Pyr]n[NTf2]z electrolyte, analyzed with a standard Karl-Fischer titrant cording to eq. (2) versus the mass of the host material (qhost) or total anode mass
(Aldrich), was below 0.4 mg H2O L− 1. Vinylene carbonate was stored at (qt) [9–19].
a max temperature of 8 ◦ C to prevent its spontaneous polymerization. Versus host material mass Versus total anode mass
Electrolytes containing VC as a solid electrolyte interface (SEI)-forming Molecular M qhost Molecular M qt
additive (10 wt%) were prepared in a dry argon atmosphere in a glove 1 1 1 1
Formula g mol− mAh g− Formula g mol− mAh g−
box. Tested electrodes were prepared on a copper foil (Hohsen, Japan)
by the casting technique, from a slurry of graphene (G) or Li4Ti5O12, Li 6.9 3860
C6 72.1 371.9 LiC6 79.0 339.2
carbon black (CB) and PVdF in NMP. The ratio of components was
Si 28.1 4198.8 Li4.4Si 58.6215 2011.7
70:10:20 (by weight) respectively. After NMP evaporation at 120 ◦ C in a Ge 72.6 1384.4 Li3.75Ge 394.7 254.6
vacuum, electrode contained the active material, electronic conductor Ge 72.6 1624.3 Li4.4Ge 515.9 228.6
(CB) and the binder (PVdF). The electrode contained typically ca. 0.8 mg Sn 118.7 993.4 Li4.4Sn 149.2 790.1
of the graphene and 3 mg of the Li4Ti5O12. A round-shaped metal­ SnO 134.7 875.5 Li4.4Sn/Li2O 179.0 658.6
SnO2 150.7 782.5 Li4.4Sn/2Li2O 208.8 564.7
lic‑lithium counter electrode was cut off from the metallic lithium foil Pb 207.2 569.1 Li4.4Pb 237.7 496.0
(surface area of 1 cm2). Mg 24.3 3307.7 Li3Mg 45.1 1781.7
Graphene|electrolyte|Li and Li4Ti5O12|electrolyte|Li cells were Al 27.0 993.3 LiAl 33.9 790.1
assembled in a dry argon atmosphere in a glove box. Anodes and lithium TiO2 79.9 335.6 LiTiO2 86.8 308.8
Li4Ti5O12 459.1 175.1 Li7Ti5O12 479.9 167.5
electrodes were separated by a glass microfibre separator (GF/A,
Whatman) soaked with electrolytes. Systems were placed in an adapted
0.5′′ Swagelok® connecting tube. Electrochemical properties of cells [10]:
were characterized using electrochemical impedance spectroscopy (EIS)
and galvanostatic charge-discharge tests. The electrochemical exami­ SnO2 + 2Li+ + 2e− = SnO + Li2 O (4)
nation of the graphene|Li was performed at different galvanostatic
charging rates and times. Impedance spectra were obtained using a SnO + 2Li+ + 2e− = Sn + Li2 O (5)
frequency response analyser at a frequency range of 100 kHz–10 mHz, at
Sn + xLi+ + xe− = Lix Sn + (0 ≤ × ≤ 4.4) (6)
the open circuit potential and amplitude of 10 mV (G750 System Gamry,
USA). The cycling tests on cells were performed between 0.001 and 3 V Therefore, the theoretical specific capacity may be expressed versus
with the use of the Gamry G1000 multichannel electrochemical system not only Sn but also SnO [11], SnO2 [12,13] or Li4.4Sn [11], Li4.4Sn/Li2O
(Gamry, USA). [11] or Li4.4Sn/2Li2O [11]. This leads to a relatively inconsistent set of
data and hence, in each case it should be mentioned if the specific ca­
3. Thermodynamic limits pacity is referred to the mass of (i) the host, (ii) active material or (iii)
the total mass of the electrode [14–19].
3.1. Anodes
3.2. Cathodes
From this point of view, lithium as an anode material is characterized
by the highest capacity (MLi ≈ 7 g mol− 1, d = 0.535 g/cm3, q (Li) =
Elements of groups 7 and 6, like F, Cl, O and S, or their compounds,
13,783C/g = 3830 mAh/g) and it determines the highest anodic limit. In
are the most promising candidates as cathode materials in high energy
addition, it is characterized by practically the lowest electric potential in
lithium or lithium-ion batteries (Table 2). Oxygen can be accessed from
nonaqueous organic electrolytes, in comparison to other materials.
the air, similarly as in classical combustion engines, which reduces the
However, metallic‑lithium anodes are not used in practical present-day
mass of active materials only to the anode. Consequently, O2 determines
Li-ion systems, due to the volume change during its transfer to the
the limit of the cathodic active material. During the discharging process
electrolyte after oxidation to Li+ ions. Commercial batteries are based on
oxygen can be reduced to Li2O [20]:
carbon host materials which are lithiated to form a LiC6 system. This
anode, as well as others in the charged form are lithiated and are 2Li + 1 2 O2 →Li2 O
/
(7)
oxidized during the discharging process, which may be represented by
equilibrium (3):
Table 2
Lim Rn →m Li+ + n R + m e− (3) Capacity q of different Li or Li-ion battery cathodes [mAh g− 1], calculated ac­
However, in contrast to the specific capacity of metallic‑lithium, cording to eq. (2) versus the mass of the delithiated qdelith or lithiated qlith
which is referred to the mass of the electrochemically active material cathode material [17,20,21,23–27].
(Li), in the case of carbon anodes its value is calculated versus the mass Delithiated cathode material Lithiated cathode material
of only the host material (in this case (q(C6) = 372 mAh g− 1), which Molecular M qdelith Molecular M qlith
cannot act by itself as an anode. The same applies to a very high specific − 1 − 1 − 1 1
Formula g mol mAh g Formula g mol mAh g−
capacity of the silicon anode, which when calculated in respect to an
inactive host material (Si) is characterized by the highest value of 4200 O2 27.8 3861.9 2Li2O 59.8 1793.9
MnO 70.9 755.6 Li2O + Mn 84.7 632.6
mAh g− 1 [9]. However, if calculated taking into account the total mass NiO 74.7 717.6 Li2O + Ni 88.5 605.7
of the anode (both the inactive host material Si and the active compo­ S 32 1675.1 Li2S 45.8 1170.4
nent Li: Li22Si5 or Li4.4Si), the specific capacity drops to approximately CF0.73 25.9 756.3 0.73LiF + C 30.9 632.5
2000 mAh g− 1 (Table 1). The problem is even more ambiguous in the CF0.83 27.8 801.1 0.83LiF + C 33.5 663.5
CuF2 101.5 527.9 2LiF + Cu 115.4 464.4
case of Sn. Theoretical capacity referred versus the host material (Sn) is
NiF2 96.7 554.4 2LiF + Ni 110.6 484.8
ca. 993 mAh g− 1 while taking into account the composition of the MnF3 111.9 718.3 3LiF + Mn 132.8 605.7
lithiated anode (Li4,4Sn) it drops to 790 mAh g− 1 (Table 1). Again, due to LixFePO4 150.8 177.8 LiFePO4 157.8 169.9
the high volume changes the host material can be rather used in the form LixMn2O4 173.8 154.2 LiMn2O4 180.8 148.2
of tin dioxide. The delithiation process undergoes a multistep process LixCoO2 91 294.6 LiCoO2 97.9 273.8
LixNiO2 90.7 295.4 LiNiO2 97.6 274.5

2
E. Rudnicka et al. Journal of Energy Storage 55 (2022) 105747

Theoretical specific capacity of oxygen, determined from eq. (2), is
therefore: q(O2) = 2 F (16 g mol− 1)− 1 = 12,060C g− 1 = 3350 mAh g− 1. If
drawn from the air, the q(O2) value may be approximated by infinity.
However, a lithium-air battery must contain a porous system (carbon)
with a catalyst reducing oxygen and as a container for lithium oxides. If
the theoretic capacity is calculated versus the molar mass of a lithium
oxide contained in the cathodic compartment, the theoretic capacity is q
(Li2O) = 2 F (30 g mol− 1)− 1 = 6432C g− 1 (ca. 1790 mAh g− 1). This value
seems to be the maximum limit of the cathode. Again, various capacity
values can be calculated taking into account different reference states
describing the cathode.
However, most cathode materials do not show high practical ability
for recharging, instead they may rather be applied in primary systems.
Fluorine can be used in the form of fluorinated graphite CFx (x close to 1)
[21]. Maximum theoretical electric work which may be delivered by a
Li/CFx battery is ca. ΔG = 2.81 MJ/kg [21]. This system cannot be
recharged with satisfactory efficiency and can work only at low current
densities. The poor power of a CFx cathode is due to the very low ex­
change current density (ca. 10− 4 mA/cm2) [22].
Another group 7 element, chlorine, is used in the form of SOCl2 as a
liquid cathode, again in primary batteries [23], with ΔG = 3.84 MJ/kg.
24252627.
3.3. Capacity at non-equilibrium conditions
The capacity under non-equilibrium conditions q(I) is usually
determined from galvanostatic discharging Δϕ = f(τ) curves as the
product of the constant current I and time t after which the cutoff voltage
is obtained and the discharging process is stopped:
q(I) = I⋅t (8)
Capacity defined in such a way is not a thermodynamic value, as it
also reflects all kinetic limits depending on the discharging rate (current
I). However, the internal energy (or enthalpy) difference between two
states (charged and discharged) is a function of state and its value does
not depend on the process path. Let us consider battery discharging in
two variants: with current I1 and current I2 = 2I1. In the absence of
polarization processes (being quasi-reversible processes), the same
charge q is necessary to convert electrode materials from the ‘charged’ to
‘discharged’ state, but in a twice shorter time (t1 = 2 t2). However, the
overvoltage η increases with an increasing current and voltage measured
by the equipment is now:
Δϕ(I) = Δϕ + η(I) (9)
Battery polarization shortens the time t necessary to obtain the cutoff
voltage and the measurement is stopped at the voltage Δϕ + η(I) before
the system is fully discharged (t2 < t1/2) and hence, the I•t value de­
creases. This is equivalent to the statement that the overpotential
changes with current and not capacity. Consequences of both thermo­
dynamic and kinetic limits are seen together and generally reported as
an experimentally determined dependence of capacity on the dis­
experimentally determined discharging capacity calculated from eq. (8)
and represented in Fig. 1 by points Δ, strongly depends on the rate: it
changes by ca. 50 %. However, if the first process, conducted at different
rates, was followed by a relaxation under open circuit conditions and
followed by the further discharging process at a low rate (C/10), the sum
of capacities determined in both steps was constant (represented by
points o) [33].
3.4. Pseudocapacitive systems
Usually Li-ion systems work at an approximately constant voltage
(the plateau in Fig. 2a). However, in some cases, especially when the
active material consists of nano-particles, the system behaves in a
pseudocapacitive way, as the potential changes linearly with time
(Fig. 2b). MnO2 deposited on carbon nano-tubes [34] can serve here as
an example. In such a case, capacity cannot be expressed in coulombs (or
Ah) but in farads, similarly as in the case of capacitors (usually denoted
as C). Therefore, no direct comparison of capacities of Li-ion systems
working at a constant or linearly changing voltage is possible. In the
pseudocapacitive system a change of free energy/enthalpy during dis­
charging is described by the following equation (adopted from the
classical capacitor theory):
/
ΔG = 1 2C(Δϕ)2 (11)
In the theory of classical capacitors, capacitance C is a proportion­
ality constant between the charge separated Δq and voltage Δϕ:
Δq/Δϕ = const. = C (12)
The capacity value can be calculated from a galvanostatic dis­
charging experiment [35]:
( )− 1
Δϕ
C=I for I ≈ 0 (13)
Δt
where I is the constant current and Δϕ/Δt stands for the discharging
curve slope.
Classical capacitors consist of two electron conductors separated by
an insulator, while Li-ion systems comprise two electrodes separated by
an ionic conductor (electrolyte). It can be expected that these two
different systems can behave differently and therefore, equations
describing classical capacitors may not be valid in the case of systems
based on faradaic processes. Again, the behavior of the electrochemical
system is influenced by overvoltage η. Hence, the slope of charging and
discharging curves is not Δϕ/Δt but disturbed by the overvoltage.
Consequently, capacity C calculated for various currents (discharging
rates) is again apparently a variable:
1.2
c/6+c/10 c/5+c/10 c/3+c/10 c/2+c/10 1c+c/10
1.0
I·t (C)

c/6
charging rate [3,28–32]. However, when for example 1 mol of the LiC6 0.8 c/5
anode is fully discharged to C6, the capacity equals the charge of 1 mol of
elementary electrons (F = 96,485C mol− 1), which is constant. This c/3
0.6
suggests that capacity, not only of the 1-mol system, but also of its c/2
multiple, thermodynamically cannot depend on the discharging rate. 1c
Therefore, the product of current I and time t after which the cutoff 0.4
0 1 2 3 4 5 6
voltage is measured does not indicate equilibrium thermodynamic ca­
Cycle number
pacity q:
I t(I) ≤ q(I = 0) (10) Fig. 1. Product I•t recorded during delithiation of the LiFePO4 cathode (2.3
mg). Counter electrode: metallic lithium (23 mg), electrolyte: 1 M LiPF6 in EC
In point of fact, it was shown experimentally that capacity, which + DMC (1:1). The process was run in two ways: (Δ) one step with different rates
indicates the amount of energy accumulated, is constant [33]. The Li| (q = I1•t1) and (o) the first step followed by 10 min relaxation under open
LiFePO4 laboratory cell was galvanostatically cycled between cutoff circuit potential and further delithiation at a low c/10 rate (q = I1•t1 + I2•t2).
voltages of 3.3 V and 4.3 V with different rates (C/6 – 1C). The Cutoff voltage between 3.3 V and 4.3 V [33].

3
E. Rudnicka et al. Journal of Energy Storage 55 (2022) 105747

3.5. The fraction of active materials in the total battery mass

a
The anodic and cathodic active material mass is only a fraction of the
Δɸ

total mass of a battery, which consists of both electrodes, their leads, a

b
separator, electrolyte, the case, the top cover, a gasket, insulators and
usually safety systems. In addition, electrodes consist of current collec­
tors covered with active electrode materials, a polymer binder and an
electronic conductor (e.g. carbon black). This significantly reduces the
amount of active materials (which take part in the electrochemical redox
reaction) and therefore available specific energy expressed versus the
mass of the whole device.
t Table 3 shows the mass distribution of two 18,650 Li-ion batteries by
Sony and Sanyo [39]. It can be seen that the mass of active electrode
Fig. 2. Two types of discharging curves: a) at constant potential (capacitance materials is close to 60 % of the total mass of batteries. In addition, the
expressed in coulombs or ampere-hours) and b) pseudocapacitive (capacitance mass of can in these devices is comparable to the mass of anodes.
expressed in farads).

( )− 1
Δϕ + η(I)
I ≤C (14)
Δt Table 3
Mass distribution of 18,650 Li-ion batteries by Sony and Sanyo [39].
Fig. 3a shows the dependence of C = [Δϕ + η(I)]/Δt on current.
However, while in the case classical dielectric capacitors knowledge of Supllier: Sony Sanyo
only one value (C) describes the behavior of the device for all currents. Total battery weight: 39.4 g 37.7 g
The concept of varying capacity leads to a number of C(I) values. Fig. 3b
wt%
presents a fitting curve of C(I) = f(I) values as polynomial C(I) = a – bI +
Cathode 39.4 34.7
cI2. This procedure compresses the number of constants necessary to
Anode 23.1 29.5
describe capacity at all currents to only three constants (a, b and c). Electrolyte 5.5 9.8
In some cases the pseudocapacitive faradaic systems are described by Separator 4.4 5.0
capacity expressed in mAh g− 1 for the sake of convenience [36–38]. Header 3.4 2.9
Generally, the method to determine such a value and its physical Can 24.2 18.1
Total 100 100
meaning are not clear.

a) 1800
1600
0.05 A g-1

1400 0.1 A g-1

1200
I/Δϕ/Δt / F g-1

1000 0.2 A g-1

800
600 0.5 A g-1
400 0.6 A g-1
1 A g-1
200
0
0 10 20 30 40 50 60 70
Cycle number
1800
b)
1500 y=1649-3622x+2191x2
I/Δϕ/Δt / F g-1

1200

900

600

300

0
0 0.2 0.4 0.6 0.8 1
Current / A g-1

Fig. 3. a) Capacity of the graphene anode in 0.7 M LiNTf2 in MPPyrNTf2 + 10 wt% VC for different currents, b) a fitting curve of C(I) = f(I) values. Graphene mass is
0.8 mg

4
E. Rudnicka et al.
3.6. Heat dissipation
Energy can be exchanged with the surrounding environment (during
charging and discharging) not only as work W but also heat Q:
ΔU = W + Q (15)
The reversible heats (Qrev) of charging and discharging have the
same absolute value, but an opposite sign and they are proportional to
the entropy change, ΔSrev, associated with the lithiation and delithiation
of electrode materials. The irreversible heat generated during charging
and discharging, Qirr, is always exothermic (Qirr < 0) and its absolute
value |Qirr| increases with the charging/discharging rate in the second
power of the current I. The total heat flow Q during battery charging or
discharging is a sum of both irreversible and reversible heats:
Q = Qrev + Qirr = TΔSrev − I 2 Rs t (16)
where Rs indicates series resistance of the system.
Total reversible entropy change during battery charging and further
discharging equals zero, as the system returns to the initial state.
However, the irreversible heat indicates energy dissipation, hence the
minus on the right side of eq. 16. Let us assume that the battery is
charged and discharged at constant voltage Δϕ (Fig. 2a) at the same rate.
In such a case, the ratio of dissipated heat Qdis to the useful electrical
work W is described by the following equation:
Qdis I 2 tRs IRs
| |= = (17)
W ItΔϕ Δϕ
This indicates that the amount of energy dissipated as heat depends
on the discharging rate and hence, battery efficiency decreases with
increasing current.
For example, a Panasonic 1.2 Ah battery discharged at a 1C rate with
a voltage of ca. 3.6 V (Fig. 4 shows EIS of the charged battery [33]), is
characterized by a low value of |Qdis/W| = (1.2Ax0.06 Ω)/3.7 V ≈ 0.02
(ca. 2 % of energy dissipated). However, if the battery is discharged with
the maximum discharging current of 2.4 A, the ratio increases twice but
is still low: |Qdis/W| = 0.039 (ca. 4 % of energy dissipated). This means
that the most important factor in terms of battery efficiency and thermal
safety is its low series resistance, which can be obtained by an increase of
electrodes geometrical surface (at fixed other parameters).
3.7. Overheating risk limits
In addition to the application of Li-ion batteries (LIBs) in portable
electronics, they have been considered as electric energy accumulators
for electric and hybrid vehicles. High-energy batteries with organic
electrolytes pose a fire hazard. The natural flammability of standard
0.15
0.1
0.05
Z'' (Ω)
0
-0.05
-0.1
-0.15
0 0.1 0.2 0.3 0.4
Z' (Ω)
Fig. 4. Impedance spectrum of the 1200 mAh Panasonic US453759 battery.
Nominal Voltage: 3.7 V. Maximum Discharge Current: 2400 mA. Weight: 22.0
g [33].
5
Journal of Energy Storage 55 (2022) 105747
carbonate based electrolytes generates a fire risk, which may arise under
abnormal conditions. These conditions often result in the thermal
runaway: an increase of temperature causes its further increase finally
leading to destructive results. Moreover, when battery size increases, the
ratio of the cooling area to the heat generating volume decreases, which
is associated with an increased runaway risk and imposes limits on
battery size. From this point of view the total heat generating power PQ
is important:
⃒
⃒TΔSrev
⃒
⃒
PQ = ⃒⃒ − I 2 Rs ⃒⃒ (18)
t
Therefore, knowledge of the reversible entropy change during bat­
tery operation is of great importance. The reversible entropy change was
measured for a number of Li-ion systems. They were typically calculated
from temperature coefficients dϕ/dT of open circuit voltage Δϕ of cells
composed of the active electrode material and a lithium counter-
electrode, both kept at the same temperature (isothermal cell). The
open circuit voltage of isothermal cells, consisting of various cathodes
and a metallic lithium counter electrode is defined as a difference of
potentials of both electrodes:
Δϕ = ϕi –ϕLi (19)
Consequently, the derivative of the open circuit voltage Δϕ in respect
to temperature is given by the following equation:
dϕ/dT = dϕi /dT − dϕLi /dT (20)
It has been shown that ΔSrev values for such batteries are strongly
associated with the state of charge (SOC) and possible overcharge
[40–49]. Determined reversible entropy changes were between ca. 25 J
mol− 1 K− 1and − 25 J mol− 1 K− 1. This is equivalent to heat values in the
range of ca. 7.5 kJ mol− 1 and − 7.5 kJ mol− 1. For a given system the
reversible heat can be positive and change to negative, or reverse,
depending on the state of charge.
Usually potentials of various Li-ion battery electrodes (at constant
temperature) are expressed against the potential of metallic lithium,
assuming that it equals zero. In the case of potential temperature co­
efficients (dϕ/dT), and hence entropies, no similar assumption can be
applied, as it is against the third principle of thermodynamics. However,
single electrode potential temperature coefficients can be estimated
using the ‘negligible thermal diffusion potential assumption’. The
dependence of open circuit voltage (Δϕi) on temperature T, for a number
of Li-ion battery electrodes was measured in non-isothermal symmetri­
cal cells (both electrodes had the same composition but were kept at
different temperatures) [50]. Using literature data, values of entropy
change for other single electrode reactions were calculated. All single
electrode entropies were positive for a different state of charge and
ranged between ca. 70 J mol− 1 K− 1 and 120 J mol− 1 K− 1. The effect of a
small entropy change for full cells is due to comparable ΔSi values for
individual electrodes. Entropy changes of individual electrodes were
measured with the use of a non-isothermal cell.
4. Kinetic limits
4.1. Series resistance
As it was mentioned before, series resistance (Rs) of the battery
(usually measured by impedance technique). It can be responsible for
heat dissipation. In addition, it contributes to the IR drop between two
current collectors. In the case of the 1200 mAh Panasonic US453759
battery (EIS shown in Fig. 4) a very low resistance of ca. 0.06 Ω leads to
the IR drop as low as 1.2 A × 0.06 Ω = 72 mV. Such a low series
resistance is due to high electrodes surface. Note that resistance higher
by one order of magnitude would lead to the IR drop as high as ca. 0.7 V.
Again, the low value of Rs, especially of its electrolyte depending
component, is a very important issue [51]. Fig. 5 shows comparison of
E. Rudnicka et al. Journal of Energy Storage 55 (2022) 105747

30 Table 4
a) Exchange current densities jo for different electrode materials together with their
BET specific surface area SBET [60–65].

20 Electrode LiMn2O4 LiCoO2 LiFePO4 CFx LiC6

SBET m2 g− 1
2.30 2.05 15.4 93.6 6.0
Z'' / Ω

3 3 2 4 3
jo mA 5.5•10− 9.4•10− 1.0•10− 1.1•10− 7.7•10−
cm− 2
10

mA cm− 2 (LiFePO4) and 1.1•10− 4 mA cm− 2 (CFx). Let us assume that T

0 = 298 K and charge transfer coefficient α = 0.5 (the slope of the Tafel
0 10 20 30 40 50 60 line is 0.514 V) and current density j = 10.0•10− 2 mA cm− 2. Under such
1
Z' / Ω conditions the overvoltage would be between |η| = 0.514 V ln(10− 2/
b) 10− 2)| = 0 V (for LiFePO4) and |η| = |0.514 V ln(1.1•10− 4/10− 2)| = 2.3 V
0.75 in the case of CFx. This shows that a low value of exchange current
0.5 density can be the next limit of efficient electrode operation. Moreover,
Z'' / Ω

it is one of the main reasons for the apparent dependence of electrode or

0.25 battery capacity on the charging/discharging rate (characterized by
0 current density j), discussed before in Section 3.3.). In addition, the
current (or the charging/discharging rate) and finally determined ca­
-0.25
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5
pacity are usually expressed versus the mass of electrode material and
Z' / Ω not against its real surface area.

Fig. 5. Nyquist plot of: a) laboratory Li|Li4Ti5O12 in 1 M LiPF6 (EC:DMC 1:1w/
w) and b) commercial Li-ion battery 100 mAh B&K, China.
Nyquist plots of laboratory Li | Li4Ti5O12 in 1 M LiPF6 (EC: DMC 1:1),
and commercial Li-ion battery 100 mAh B&K, China. It can be seen that
the laboratory cell (Fig. 5a) of small electrodes shows high impedance in
contrast to the commercial battery (Fig. 5b) of much higher surface area.
4.2. Charge transfer kinetics (activation overpotential)
Although Li-ion batteries work under direct current (dc) conditions,
kinetic parameters are usually determined from impedance spectra
taken at different frequencies of alternating current (ac). Fig. 6 shows an
example of an equivalent circuit representing a lithium ion battery.
At high overpotentials (η ≫ RT/F) kinetics of the charge transfer
process can be described by the Tafel equation (for a symmetric electron
transfer):
( )
RT j
η= ± ln (21)
αF jo
where jo is the exchange current density and α charge transfer
coefficient.
Exchange current densities for the lithium red-ox reaction at five
electrodes, obtained from the deconvolution of ac EIS spectroscopy were
reported (with 1 M LiPF6 solution in a mixture of ethylene carbonate and
dimethyl carbonate used as the electrolyte) [52].
It can be seen from the Table 4 that jo values are between 1.0•10− 2
4.3. Formation of a passive layer (SEI)
Li-ion batteries are assembled with graphite in its delithiated state, a
lithiated cathode material and electrolyte. During the first charging
cycle a LiC6 anode is formed electrochemically. Cyclic carbonates,
typically used as components (solvents) of lithium electrolytes, as well
as lithium salt (typically LiPF6) react with the C6Li anode with the for­
mation of Li+ conducting film, called solid electrolyte interphase (SEI)
[53–57], which is responsible for the chemical and electrochemical
stability of the anode. After the first cycle ca. 10 % of the original ca­
pacity is lost due to lithium consumption in the irreversible process of
SEI formation [57]. However, in some cases the irreversible capacity lost
can be as high as ca. 30 % - 50 % [58,59]. In addition, the protective
solid coating separating the electrode material (LiCx) from the liquid
electrolyte increases battery total impedance, which contributes to the
overvoltage.
4.4. Diffusion in electrode solid material
A theoretical and experimental lithium diffusion studies were con­
ducted for a number cathodes and anodes. It was observed that the Li+
diffusion coefficient (DLI+) varied with the electrode voltage. For
LiFePO4, the diffusion coefficient is as low as 10− 14 cm2s− 1 [60] whereas
for LiCoO2 it was from 10− 8 cm2s− 1 to 10− 9 cm2s− 1. Table 4 lists DLI+
values of some popular electrodes. It can be seen that graphite anode is
characterized by similar DLi+ value.
The very low diffusion coefficient value in the solid state electrodes is
the next limit.
6162636465

4.5. Volume changes

One of the most important factors determining applicability of the

Fig. 6. An example of a simple equivalent circuit representing kinetic limits of
a Li-ion battery electrode (series resistance Rs, resistance of SEI layer, RSEI,
charge transfer resistance Rct and Warburg impedance ZW reflecting diffusion).
CPESEI and CPEdl represent constant phase elements describing capacitive
properties of SEI film and electrochemical double layer.
electrode material is its volume expansion or dilatation during lith­
iation/delithiation processes. Again, the volume change is usually
referred versus the volume of the host material (Table 5) [66].
Volume change of metallic‑lithium is usually reported to be 100 %
[66] however, this value is referred against the active material (Li). In
fact, volume change referred versus the ‘delithiated’ state (V = 0) is
infinite in this case. If the anode is based on a host material, volume
changes can be smaller. For example, the volume difference between
delithiated carbon (C) and its lithiated form (LiC6) is only 12 %, which
makes it suitable for application in practical systems. On the other hand,

6
E. Rudnicka et al.
Table 5
Volume changes during lithiation/delithiation of various anodes [66].
Host material – Li4Ti5O12 C Al
Lithiated anode Li Li7Ti5O12 LiC6
Volume change (%) ∞ 1 12
silicon during the lithiation process increases its volume by 420 % [66],
which induces forceful mechanical stress and hence, electrode structure
damage. The high volume change during high capacity anode operation
is a serious limit which prevents its application in practical battery
systems. This problem can be to some extend reduced by development of
hybrid electrodes [5].
5. Conclusions
Metallic lithium as an anode material is characterized by the highest
capacity (3830 mAh g− 1) and it determines the highest anodic limit.
However, it is not used in practical Li-ions batteries due to non-
reversibility of the electrode reaction. Lithium carbon or lithium sili­
con electrodes may be used instead of metallic Li. The Li–Si electrode is
reported to have the highest capacity (4200 mAh g− 1). The capacity of a
silicone anode is usually calculated in respect to an inactive host ma­
terial (Si). However, if calculated taking into account the total mass of
the anode (both inactive host material Si and active component Li:
Li22Si5 or Li4.4Si), the specific capacity drops to 2005 mAh g− 1.
Elements of groups 6 and 7, e.g. O S, F, Cl, or their compounds, are
the most promising candidates as cathode materials. The theoretical
capacity of O2 is (3350 mAh g− 1). Oxygen can be accessed from the air,
similarly as in classical combustion engines, which reduces the mass of
active materials (and may be approximated by infinity). Consequently,
O2 determines the limit of cathodic active material capacity.
Practical capacity of both cathode and anode materials measured at
non-equilibrium conditions (I > 0) is reported to be lower. Battery po­
larization shortens the time t necessary to obtain the cutoff voltage and
the measurement is stopped at the voltage Δϕ + η(I) before the system is
fully discharged and hence, I•t value decreases.
Usually Li-ion systems work at an approximately constant voltage,
but in some cases, especially when the active material consists of nano-
particles, the system behaves in a pseudocapacitive manner (the po­
tential changes linearly with time).
The phenomenon of capacity variation with current was discussed
and explained as a result of overvoltage operation.
The active material mass of electrodes is only a fraction of the total
mass of the battery, which consists of leads, a separator, electrolyte, the
case, the top cover, a gasket, insulators and usually safety systems.
Moreover, a part of energy is dissipated in the form of irreversible
heat. The natural flammability of standard carbonate based electrolytes
generates a fire risk, which may arise under abnormal conditions.
One of the most important factors determining applicability of any
electrode material is its volume expansion or dilatation during lith­
iation/delithiation processes (it is usually referred versus the volume of
the host material). However, a unified solution or idea does not exist due
to the complicity of the system.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
7
Journal of Energy Storage 55 (2022) 105747
Mg Sb Sn Si
LiAl Li3Mg Li3Sb Li4.4Sn Li4.4Si
96 100 200 260 420
Acknowledgement
This work was supported by the Polish Ministry of Education and
Science, grant 0911/SBAD/2202.
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