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\begin{document}

\title{Failure Analysis of Lead-acid Batteries at Extreme Operating
Temperatures}



\author[1]{Umesh Prasad}%
\author[2]{Jyoti Prakash}%
\author[3]{Venkat Kamavaram}%
\author[3]{Ganesh Arumugam}%
\author[2]{Arunachala Nadar Mada Kannan}%
\affil[1]{Affiliation not available}%
\affil[2]{Arizona State University - Polytechnic Campus}%
\affil[3]{Oceanit Laboratories Inc}%


\vspace{-1em}



  
  \date{May 20, 2024}


\begingroup
\let\center\flushleft
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\selectlanguage{english}
\begin{abstract}
Lead-acid battery system is designed to perform optimally at ambient
temperature (25 \selectlanguage{ngerman}°C) in terms of capacity and cyclability. However,
varying climate zones enforce harsher conditions on the automotive lead
acid batteries. Hence, they age faster and exhibit low performance when
operated at either extremity of the optimum ambient conditions. In this
work, a systematic study was conducted to analyze the effect of varying
temperatures (-10, 0, 25 and 40 °C) on the sealed lead acid. Enersys®
Cyclon (2V, 5Ah) cells were cycled at C/10 rate using battery testing
system. The environmental aging results in shorter cycle life due to the
degradation of electrode, and grid materials at higher temperature (25
and 40 °C), while at lower temperature (-10 and 0 °C) negligible
degradation was observed due to slower kinetics and reduced available
capacity. Electrochemical impedance spectroscopy, X-ray diffraction and
Energy-dispersive X-ray spectroscopy analysis were used to evaluate the
degradation mechanism, chemical and morphological changes.%
\end{abstract}\selectlanguage{ngerman}%



\sloppy


\textbf{Failure Analysis of Lead-acid Batteries at Extreme Operating
Temperatures}

U. Prasad\textsuperscript{1}, J. Prakash\textsuperscript{1}, A. M.
Kannan11*Corresponding author amk@asu.edu*, V.
Kamavaram\textsuperscript{2} and G. K. Arumugam\textsuperscript{2}

\textsuperscript{1}Arizona State University, 7171 E Sonoran Arroyo Mall,
Mesa, AZ 85212, USA

\textsuperscript{2}Oceanit Laboratories, 828 Fort Street Mall, Ste 600,
Honolulu, HI 96813, USA

\textbf{Abstract}

Lead-acid battery system is designed to perform optimally at ambient
temperature (25 \selectlanguage{ngerman}°C) in terms of capacity and cyclability. However,
varying climate zones enforce harsher conditions on the automotive lead
acid batteries. Hence, they age faster and exhibit low performance when
operated at either extremity of the optimum ambient conditions. In this
work, a systematic study was conducted to analyze the effect of varying
temperatures (-10, 0, 25 and 40 °C) on the sealed lead acid. Enersys®
Cyclon (2V, 5Ah) cells were cycled at C/10 rate using battery testing
system. The environmental aging results in shorter cycle life due to the
degradation of electrode, and grid materials at higher temperature (25
and 40 °C), while at lower temperature (-10 and 0 °C) negligible
degradation was observed due to slower kinetics and reduced available
capacity. Electrochemical impedance spectroscopy, X-ray diffraction and
Energy-dispersive X-ray spectroscopy analysis were used to evaluate the
degradation mechanism, chemical and morphological changes.



\textbf{Introduction}

The ever-growing energy demand with the increasing population and rise
in the economy has led to a rapid increase in the total energy demand
globally.\textsuperscript{1,2} More than 80 \% of the energy supplies
come from carbon-rich non-renewable energy sources in the current
situation.\textsuperscript{3} Battery technologies are being established
rapidly due to its increasing demand in portable devices, stationary
frameworks, and electric vehicles.\textsuperscript{4,5} Among present
various battery technologies, Lead-Acid (PbA), Nickel-Metal Hydride
(NiMH), Nickel-Cadmium (NiCd) and Lithium-ion (Li-ion) are the major
chemistries towards different applications due to their specific
characteristics related to energy density, power density, durability,
and economic feasibility.\textsuperscript{6--8} Even though the growing
popularity of Li-ion and NiMH batteries, the demand for PbA batteries
grows proportionately due to their ease in availability, manufacturing,
maintenance, reliability, recycling and cost.\textsuperscript{9} Lead
acid battery demand is higher in large-scale applications such as
renewable energy storage system, e.g., wind and solar technologies
despite having lower energy density (\textless{} 50 Wh/kg). Lead acid
battery market share is the largest for stationary energy storage system
due to the development of innovative grid with Ca and Ti additives and
electrodes with functioning carbon,
Ga\textsubscript{2}O\textsubscript{3} and
Bi\textsubscript{2}O\textsubscript{3}
additives.\textsuperscript{10,11}In the current scenario, leak-proof and
maintenance-free Sealed Lead Acid batteries (SLAs) are used in multiple
applications such as motorcycles, ATVs, home alarm systems, toys, backup
systems, workout equipment and generators.\textsuperscript{12--14}

Temperature plays a key role in the battery operation as it affects the
cycle life, performance, and available capacity. The PbA battery system
are designed to perform optimally at ambient temperature (25 °C) for
performance, capacity and cyclability. However, they degrade faster when
operated at higher than ambient conditions leading to shorter cycle life
due to the degradation of electrode and grid
materials.\textsuperscript{6} The oxidation and reduction rates increase
significantly at both Pb anode and PbO\textsubscript{2} cathode, leading
to higher discharge capacity at elevated
temperatures.\textsuperscript{7,12} Besides having a deleterious impact
on the cycle life at elevated temperatures, several other impacts
include self-discharge reactions, loss of electrolyte, active material
shedding, grid corrosion, and loss of mechanical strength of the
positive electrode
(PbO\textsubscript{2}).\textsuperscript{15--17}Shedding or loss of
positive active mass particles into the electrolyte could also increase
corrosion and macro defects on the lugs of the negative
electrode.\textsuperscript{16,17} While operating at lower temperature,
low electrolyte conductivity and active material results in reduced
available capacity.\textsuperscript{6} To reduce the corrosion or
degradation rate of the PbA battery, limiting the internal temperature
to \textless{} 60 °C could minimize the electrolyte
vaporization.\textsuperscript{18} The cell internal pressure should be
in acceptable range for long term optimum performances. However, it was
reported that charging efficiency and cyclability were improved under
high internal pressure with the favorable crystal structure of the
electrodes.\textsuperscript{16} Performance evaluation of the batteries
at elevated temperatures and near-freezing temperature is critical for
using these batteries for outdoor energy storage applications in hot and
cold conditions.\textsuperscript{6}

The adverse effect of temperature also includes reduced discharge
capacity, increased internal resistance and self-discharge with
increased duration at extreme temperatures. Typical PbA batteries
undergo many charge/discharge cycles during their life
time.\textsuperscript{10} Hence it is necessary to understand the
complete cycling behavior of PbA battery in various operating
conditions, including incomplete charging, slow discharging, extreme
conditions such as temperature fluctuations, and vibrations that cause
degradation of internal components leading to failure of the battery.

In this work, a systematic study was conducted to analyze the 2V/5Ah
Enersys® Cyclon sealed lead-acid (SLA) cells cycled at -10, 0, 25 and 40
°C, to minimize the experimentation duration as these conditions are
practical for vehicles used or stored in frozen tundra and arid desert
climates. To evaluate these condition, electrochemical impedance
spectroscopy (EIS) was carried out to evaluate internal resistance
(ohmic and charge transfer) to explain the degradation mechanism of the
battery. Further, electrode materials were extracted post cycling
analysis for morphology characterization using X-ray diffraction (XRD),
and Energy-dispersive X-ray spectroscopy analysis (EDX). SLA batteries
were observed to degrade faster at higher temperatures (25 and 40°C).
However, the degradation is minimal at lower temperatures (0 and -10 °C)
due to less active material and slower kinetics. The impedance values,
x-axis intercept of Nyquist plot was observed to increase with cycling
at all the temperatures.

\textbf{Experiments Setup}

Sealed lead acid cells 2 V, 5 Ah (Cyclon Enersys®) were tested in this
study at -10, 0, 25 and 40 °C (Figure 1a). Studies on these temperature
margins are sufficient to provide better understanding of SLA cell
performance. The thermal chamber (ESPEC, BTU-433) was used for testing
cells in a controlled environment (Figure 1b). A programmable battery
tester (Arbin Instruments, BT-1) was used for charge/discharge cycling
studies. The charge and discharge cut-off potential were kept at 2.45
and 1.85 V, with a constant charging and discharging rate of C/10 (0.5
A) and a 5 min rest period between charging and discharging cycles. The
discharge rate was taken to study the slow charge discharge phenomena.
Discharge capacities were calculated for each cycle from the charge and
discharge profiles. EIS spectra were recorded after 20/25
charge-discharge cycles in fully charged state at room temperature using
a potentiostat/galvanostat (PARSTAT 2273, Princeton Applied Research)
with a frequency range of 10 Hz to 1 kHz.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image1/image1}

\end{center}
\end{figure}

\emph{Figure 1: (a) Cyclon cell 2V and 5 Ah (b) temperature controlled
environmental chamber.}

Post cycling analysis, electrode materials were extracted in charged and
discharged states for chemical and morphological characterization
(Figure 2). The extracted material was thoroughly ground, rinsed with
water profusely to remove remnant acid, and dried overnight at 80 \selectlanguage{ngerman}°C.
Phase and crystal structure of pristine and degraded electrodes were
examined using XRD (PANalytical X'Pert PRO MRD; Cu K\selectlanguage{greek}α \selectlanguage{english}radiation; 0.006
degrees/sec). Phases of the materials were validated after rinsing and
drying process during material extraction process. EDX spectral mapping
analysis (25 kV) was performed for estimating the chemical composition
of electrodes post degradation.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image2/image2}

\end{center}
\end{figure}

\emph{Figure 2: Cell disassembling process after cycling studies to
extract active electrode materials for XRD characterization.}

\textbf{Result and Discussion:}

The charge-discharge profiles at different operating temperatures,
electrochemical impedance spectra studies, chemical and morphological
analysis are discussed in the following sections.

\emph{Charge-Discharge Cycling Studies:}

The discharge profiles of the cycled cells at -10, 0, 25 and 40 \selectlanguage{ngerman}°C are
shown in Figure 3a-d. It was observed that during the initial cycles the
total discharge duration at 40 and 25 °C is about 2X as compared to that
at 0 and -10 °C, which is due to slower kinetics and lower electrolyte
conductivity. Moreover, the discharge duration are 2, 2.5, 3.8 and 1.5 h
after 120 cycles for 40, 25, 0 and -10 °C, respectively. This suggests
that ageing of PbA battery is faster at elevated temperature (40 and 25
°C) than at sub-ambient temperatures (0 and -10 °C). For cell discharged
at 0 °C, the total discharging duration remains unchanged throughout the
cycling studies. Whereas for cell discharged at -10 °C the discharge
duration decreases from 3.5 to 1.5h, which is relatively faster ageing
despite low active materials utilization due to reduced initial
available capacity.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image3/image3}

\end{center}
\end{figure}

\selectlanguage{ngerman}\emph{Figure 3: Discharge curves at C/10 rate for (a) -10 °C, (b) 0 °C,
(c) 25 °C and (d) 40 °C}

Figure 4a-d illustrates the charging pattern of the cells at -10, 0, 25
and 40 °C. Similar to discharging profiles, during the initial cycles it
was observed that total charging duration is higher for cells discharged
at 40 and 25 °C, as compared to that at 0 °C and -10 °C. The charge
durations are 2, 2.5, 4 and 1.5 h after 120 cycles for 40, 25, 0 and -10
°C, respectively. Similar charging and discharging patterns corroborate
the observed capacity degradation process.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image4/image4}

\end{center}
\end{figure}

\emph{Figure 4: Charge curves at C/10 rate for (a} \selectlanguage{ngerman}\emph{) -10 °C, (b) 0
°C, (c) 25 °C and (d) 40 °C}

Discharge capacity of the cells calculated from the discharge profiles
is illustrated in Figure 5a. It was observed that discharge capacity is
close to the theoretical capacity (5Ah) for 25 °C and 40 °C, while the
initial discharge capacity at -10 °C is higher than the result at 0°C,
the discharge capacity drop is much significant in -10 °C because lower
temperature increases the internal resistance and reduces the
capacity.\textsuperscript{19} Steep slope confirms that degradation is
higher at 40 °C due to enhanced ageing of the electrodes from faster
reaction kinetics at elevated temperature. The capacity degradation
after 130 cycles are 92, 74, 69 and 17\% for 40, -10, 25 and 0 °C,
respectively. Moreover, the cell degradation is insignificant at 0 °C
even though the total discharge capacity is low. The state of health
(SOH) is a measurement that reflects the general condition and ability
to deliver the specified performance compared to that of a fresh
battery. SOH takes into consideration factors such as charge acceptance,
internal resistance, voltage, and
self-discharge.\textsuperscript{4,20,21} It is a measure of the
battery's long-term capability and available lifetime energy throughput.
Health of the battery tends to deteriorate gradually due to irreversible
physical and chemical changes, hence SOH is estimated by multiple
methods including impedance, conductance and discharge capacity
(current/actual).\textsuperscript{4,20} SOH was calculated using instant
discharge capacity and initial capacity (after
1\textsuperscript{st}cycle) as illustrated in Figure 5b. SOH was
observed to be highest for 0 °C ranging from 95\% (1\textsuperscript{st}
cycle) to 89\% (130\textsuperscript{th} cycle). However, the SOH
decreased sharply for cells discharged at -10 °C (78\% to 46\%), 25 °C
(67 to 28\%), and 40 °C (73 to 10\%). Significant SOH loss was observed
for 40 °C confirming major degradation.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image5/image5}

\end{center}
\end{figure}

\emph{Figure 5: (a) Discharge capacities and (b) SOH of the cells at
-10, 0, 25 and 40 .}

\emph{Electrochemical Impedance Spectroscopy Studies:}

Electrochemical impedance spectroscopy (EIS) was measured after every
20/25 charge-discharge cycles at room temperature and in fully charged
state. EIS is essential for evaluating the power loss due to cycling and
analyzing the failure mechanism. The Nyquist plots of the cells
discharged at different temperatures are illustrated in Figure 6 a-d.
All the cells initial showed similar impedance values (0.05 -- 0.06 )
prior to cycling. However, after 130 cycles the impedance values are
significantly higher: 0.41, 0.20, 0.13, and 0.38  at -10, 0, 25, and 40
\selectlanguage{ngerman}°C, respectively. The increase in impedance is consistent with capacity
degradation after 130 cycles as shown in Figure 5a.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image6/image6}

\end{center}
\end{figure}

\emph{Figure 6: Electrochemical impedance spectroscopy at (a) -10, (b)
0, (c) 25 and (d) 40 .}

According to the standard equivalent circuit model, the measured
impedance data were analyzed by using a complex non-linear least squares
(CNLS) fitting method (Figure 7). EIS studies the system response to the
application of a periodic small amplitude AC
signal.\textsuperscript{5,10} Analysis of the system response contains
information about the interface, its structure and reactions taking
place at the interfaces e.g.,
electrolyte-electrodes.\textsuperscript{20}\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image7/image7}

\end{center}
\end{figure}

\emph{Figure 7: Equivalent circuit model representing lead-acid
battery.} \textsuperscript{20}

The impedance value, x-intercept from the Nyquist plot (Figure 6 a-d),
is observed to increases gradually with cycling for all the temperatures
(Figure 8a). However, the increase is higher at low temperatures (-10 \&
0 \selectlanguage{ngerman}°C) than at higher temperatures (25 \& 40 °C) even though the total
active material availability and utilization is significantly reduced at
the lower temperatures. The lower real impedance at higher temperatures
(25 and 40 °C) essentially means that battery activity is improved
despite higher degradation.

The ohmic and charge transfer resistance were calculated by fitting the
EIS data to equivalent circuit model using \emph{ZSimpWin} software. The
ohmic resistance and charge transfer resistances exhibited similar
behavior as impedance values (Figure 8b and 8c). However, it is reported
that charge transfer resistance is critical in representing the
degradation mechanism as it reflects the reaction mechanism at
electrodes.\textsuperscript{10,20,22} The voltage at 50\% discharge
cycle (V\textsubscript{dis,50\%}) was analyzed to further evaluate the
capacity degradation with cycling (Figure 8d). These values increase
with cycles at all temperatures, however, more rapidly at 25 and 40 °C
than at 0 and -10 °C. Higher battery degradation correlates to higher
slope of the V\textsubscript{dis,50\%} vs cycle profiles, which
essentially shows that the cell discharge capacity and SOH are
decreasing with cycling.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image8/image8}

\end{center}
\end{figure}

\selectlanguage{ngerman}\emph{Figure 8: (a) Impedance, (b) ohmic resistance, (c) charge transfer
resistance and (d) V\textsubscript{dis,50\%} with cycle numbers for -10,
0, 25 and 40 °C.}

\emph{Chemical and Morphological Analysis:}

Two cells were cycled at each temperature for data reliability and XRD
analysis. The anode and cathode materials obtained from the fresh and
cycled cells in charged and discharged states were analyzed using XRD
(Figure 9).\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image9/image9}

\end{center}
\end{figure}

\selectlanguage{ngerman}\emph{Figure 9: (a) Anode, and (b) cathode in fully charged condition
after 130 cycles, (c) anode and (d) cathode in discharged condition
after 130 cycles for cells cycled at -10, 0, 25 and 40°C.}

The XRD pattern of anode after 130 cycles in charged condition contained
Pb (cubic) and PbSO\textsubscript{4} (anglesite) peaks, like that for
the fresh cells (Figure 9a). Along with Pb and PbSO\textsubscript{4},
there were PbO, Pb\textsubscript{3}O\textsubscript{4} peaks for the
cycled cell at different temperatures (Figures 9 a-d). Pb peaks
intensity was higher and sharper in the new cell than the cycled cells,
which confirmed that the PbSO\textsubscript{4} was completely converting
into Pb through reduction reaction. However, there was a permanent
deposition of PbSO\textsubscript{4} in the cycled cells after 130 cycles
due to surface hardening. The intensity of PbSO\textsubscript{4} peaks
was more intense at 40 °C compared to 25 °C and new cell, which could be
attributed to poor reversibility with a higher amount of
PbSO\textsubscript{4} at the anode in the charge condition (Figure 9a).

The cathode in charged condition contained PbO\textsubscript{2} and
PbSO\textsubscript{4} peaks, like that of the fresh cells (Figure 9b).
The cell after 130 cycles also showed Pb, PbO, and
Pb\textsubscript{3}O\textsubscript{4} peaks. The
PbO\textsubscript{2}peaks intensity was higher and sharper in the fresh
cell than the cycled cell after 130 cycles. PbSO\textsubscript{4}
detected due to permanent deposits (surface hardening) through
charge/discharge cycling, leading to capacity loss. The
PbSO\textsubscript{4} peaks was more intense at 40 °C compared to those
cycled at 25 °C and fresh cell due to accelerated kinetics at higher
temperature leading to irreversibility. However, there was not much
difference observed in the cells at 0 °C in charged (Figure 9a) than
cell in discharged state (Figure 9c). This could be because at 0 °C only
half of the cell capacity was used, discharge capacity is 4.1 Ah at 25
°C and 2.15 Ah at 0 °C due to the change in kinetics at 0 °C
temperature. Similarly, at -10 °C the cathode for the cell after 130
cycles in charged and discharged condition contained
PbO\textsubscript{2}, Pb\textsubscript{3}O\textsubscript{4} and
PbSO\textsubscript{4} peaks (Figure 9b \& d). However, at 0 °C, the
anode both in charged and discharged conditions contained Pb (cubic),
PbO and PbSO\textsubscript{4} (anglesite) peaks (Figure 9a \& c).

The anode in discharged condition for the cell after 130 cycles
contained the Pb (cubic) and PbSO4 (anglesite) peaks, like that of the
fresh cells (Figure 9c). Along with Pb and PbSO\textsubscript{4}, there
were Pb\textsubscript{3}O\textsubscript{2}SO\textsubscript{4},
PbSO\textsubscript{3}, PbO, and
Pb\textsubscript{3}O\textsubscript{4}peaks in the cell after 130 cycles.
The PbO, PbSO\textsubscript{4}, and
Pb\textsubscript{3}O\textsubscript{4} peaks were identified in Figures
9c \& 9d. \textbackslash{}soutThe
Pb\textsubscript{3}O\textsubscript{2}SO\textsubscript{4} peaks were not
detected in XRD, but they do exist in charging condition. The
PbSO\textsubscript{4} peaks intensity was higher and sharper in the
fresh cell compared to the cell after 130 cycles, mostly agglomerated
and surface hardened active materials, which confirmed that the Pb was
completely converting into PbSO\textsubscript{4} through an oxidation
reaction in the fresh cell.\textsuperscript{6,17,18,23} Some of the
PbSO\textsubscript{4} peaks such as 26.6°, 29.8° and 36° are relatively
higher in the cycled cell compared to the fresh cells. However, the main
peak intensity at 44.4° is more intense in the fresh cell than cycled
cells. This discrepancy observed could be attributed to the
compositional difference on the electrode surface and in the bulk. The
Pb peaks were more intense at 40 °C compared to that at 25 °C and fresh
cell, this is probably due to higher deposition of Pb at anode in the
charged condition.\textsuperscript{6,23}

The cathode in discharged condition contained PbO\textsubscript{2} and
PbSO\textsubscript{4} peaks for the cycled cells, like that with the
fresh cells (Figure 9d). Moreover, the cell after 130 cycles also showed
Pb\textsubscript{3}O\textsubscript{2}SO\textsubscript{4},
PbSO\textsubscript{3}, Pb, PbO, and
Pb\textsubscript{3}O\textsubscript{4} peaks. The
PbSO\textsubscript{4}peaks intensity were higher and sharper in the new
cell compared to the cell after 130 cycles. The PbO\textsubscript{2}
detected could be due to the inability of the bulk active material not
being able to get reduced during discharge at elevated temperature,
leading to less utilization of active materials and faster capacity
fading/degradation in the cycled cell. Obviously, the
PbO\textsubscript{2} peaks was more intense at 40 than compared to 25 °C
and the fresh cell due to larger deposition of PbO\textsubscript{2} at
the cathode in the charged condition.\textsuperscript{13,14} There was
not much difference observed in the Pb peak intensity in charge
condition for cathode (Figure 9b) and cell at discharge condition
(Figure 9d) at 0 °C. Similar to anode, this could be because at 0\selectlanguage{english}@C only
half of the cell capacity was used due to the slower kinetics at this
temperature. In summary, the XRD analysis concludes that the major/minor
phases in charged and discharged state for electrodes are as illustrated
in Table 1.

Table 1: Summary of phases present in the electrode from XRD analysis.\selectlanguage{english}
\begin{longtable}[]{@{}lll@{}}
\toprule
\begin{minipage}[b]{0.30\columnwidth}\raggedright\strut
\textbf{Electrodes}\strut
\end{minipage} & \begin{minipage}[b]{0.30\columnwidth}\raggedright\strut
\textbf{Status}\strut
\end{minipage} & \begin{minipage}[b]{0.30\columnwidth}\raggedright\strut
\textbf{Phase}\strut
\end{minipage}\tabularnewline
\midrule
\endhead
\begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Anode\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Charged\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Pb (cubic) (Major) (O)PbSO\textsubscript{4}: anglesite (Minor)\strut
\end{minipage}\tabularnewline
\begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Anode\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Discharged\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Pb (cubic) (Minor) (O)PbSO\textsubscript{4}: anglesite (Major)\strut
\end{minipage}\tabularnewline
\begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Cathode\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Charged\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
PbO\textsubscript{2}: plattnerite (Major) (R)PbSO\textsubscript{4}:
anglesite (Minor)\strut
\end{minipage}\tabularnewline
\begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Cathode\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
Discharged\strut
\end{minipage} & \begin{minipage}[t]{0.32\columnwidth}\raggedright\strut
PbO\textsubscript{2}: plattnerite (Minor) (R)PbSO\textsubscript{4}:
anglesite (Major)\strut
\end{minipage}\tabularnewline
\bottomrule
\end{longtable}

Note: O -- oxidation and R -- reduction

The energy-dispersive X-ray spectroscopy (EDS) was conducted on anode
and cathode active materials for examining sulfur content which is
represented as the Pb/S ratio. The Pb/S is the ratio of composition
obtained from the Pb, PbO\textsubscript{2} and
PbSO\textsubscript{4}peaks in EDS spectrum (Table 2). Higher values of
Pb/S means lower SO\textsubscript{4}\textsuperscript{2-} content and
vice versa. The Pb/S ratio indicative of the relative amount of sulfate
(SO\textsubscript{4}\textsuperscript{2-}) getting deposited on anode and
cathode after cycling. Pb/S ratio of the fresh cell is significantly
different due to complete reversibility of PbSO\textsubscript{4} to Pb
as compared to that observed in cycled cells. As indicated from Pb/S
ratio it can be seen that
SO\textsubscript{4}\textsuperscript{2-}deposition and hardening were
higher in anode and cathode in discharged state which eventually led to
reduction in the amount of active materials with cycling (130
cycles).\textsuperscript{21,22,24} It can be seen that
SO\textsubscript{4}\textsuperscript{2-} content increases with
decreasing temperature from 40 to 0 \selectlanguage{ngerman}°C due to slower kinetics and lower
PbSO\textsubscript{4} reversibility to Pb. However, it is lowest at -10
°C as compared to cycled and fresh cells essentially due to reduced
active material (\textasciitilde{}50\%) availability as seen from the
charge-discharge characteristics (Figures 3-5).\textsuperscript{6,18,25}

\emph{Table 2: EDS chemical analysis comparison of the electrodes from
cycled cells (130 cycles) at various temperatures and fresh cells.}\selectlanguage{english}
\begin{longtable}[]{@{}lllllll@{}}
\toprule
\textbf{Electrodes from cycle cells} & \textbf{Electrodes from cycle
cells} & \textbf{Pb/S ratio} & \textbf{Pb/S ratio} & \textbf{Pb/S ratio}
& \textbf{Pb/S ratio} & \textbf{Pb/S ratio}\tabularnewline
& & \textbf{Fresh} & \selectlanguage{ngerman}\textbf{40 °C} & \selectlanguage{ngerman}\textbf{25 °C} & \selectlanguage{ngerman}\textbf{0 °C} &
\selectlanguage{ngerman}\textbf{-10 °C}\tabularnewline
\textbf{Anode} & \textbf{Charged} & 48.5 \selectlanguage{ngerman}± 2.43 & 24.2 \selectlanguage{ngerman}± 1.24 & 26.3 \selectlanguage{ngerman}±
1.31 & 21.3 \selectlanguage{ngerman}± 1.07 & 31.6 \selectlanguage{ngerman}± 1.6\tabularnewline
& \textbf{Discharged} & 23.3 \selectlanguage{ngerman}± 0.012 & 17.8 \selectlanguage{ngerman}± 0.9 & 15.4 \selectlanguage{ngerman}± 0.77 & 15.3 \selectlanguage{ngerman}±
0.77 & 23.8 \selectlanguage{ngerman}± 1.2\tabularnewline
\textbf{Cathode} & \textbf{Charged} & 55.3 \selectlanguage{ngerman}± 2.81 & 24.0 \selectlanguage{ngerman}± 1.25 & 27.0 \selectlanguage{ngerman}±
1.36 & 22.5 \selectlanguage{ngerman}± 1.3 & 32.8 \selectlanguage{ngerman}± 1.65\tabularnewline
& \textbf{Discharged} & 21.6 \selectlanguage{ngerman}± 1.09 & 20.1 \selectlanguage{ngerman}± 1.1 & 16.1 \selectlanguage{ngerman}± 0.83 & 13.1 \selectlanguage{ngerman}±
0.7 & 24.1 \selectlanguage{ngerman}± 1.3\tabularnewline
\bottomrule
\end{longtable}\selectlanguage{ngerman}\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image10/image10}

\end{center}
\end{figure}

\emph{Figure 10: EDS chemical analysis comparison of the electrodes from
cycled cells (130 cycles) at various temperatures and fresh cells.
(Table 2 data is represented as histograms.)}

\textbf{Conclusion:}

The sealed lead acid (SLA) cells were cycled at -10, 0, 25 and 40 \selectlanguage{ngerman}°C to
evaluate the performance and degradation mechanism. Discharge profiles
demonstrated that the ageing is faster at elevated temperature (40 °C)
than at lower temperature (-10, 0, \& 25 °C). However, capacity
degradation is minimal at 0 and -10 °C due to reduced active material
availability. Moreover, EIS analysis revealed that impedance change was
significantly higher at 25 and 40 °C as compared to that at 0 and -10
°C. The charge transfer resistance is relatively more governing factor
than ohmic resistance for indicating the degradation of the cell. XRD
analysis revealed that a permanent deposition of SO\textsubscript{4} due
to surface hardening (usually termed as sulfate hardening) in the cells
after cycling at all the temperatures. However, sulfate hardening is
significantly higher at 25 and 40 °C as compared to that at 0 and -10 °C
as confirmed from Pb/S ratio determined from EDS analysis. The study
demonstrates that temperature of operation plays a crucial role in state
of health prediction of sealed lead -acid batteries.

\textbf{Acknowledgements}

The authors acknowledge financial support from US Army Research Office,
Oceanit and Arizona State University. V. Kamavaram and G. K. Arumugam
acknowledge financial support from US Army Research Office
(W911NF-18-C-0083).

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\selectlanguage{english}
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