Journal of Energy Storage 85 (2024) 110907

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Journal of Energy Storage

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Research Papers

Hydrogen releasing law and in situ computed tomography investigation of

structural damage of waded lithium-ion batteries
Dongqi Li , Qingsong Zhang *
College of Safety Science and Engineering, Civil Aviation University of China, Tianjin 300300, PR China

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

Keywords: Wading event of new energy electric vehicles occurs frequently, and wading safety of lithium-ion batteries has
Lithium-ion battery been increasingly paid great attention. Here, hydrogen releasing kinetics of waded lithium-ion battery packs are
Wading corrosion systematically studied. Structural damage of waded lithium-ion batteries are carefully investigated in real time
Computed tomography
by in-situ computed tomography, and its thermal runaway and explosion limit is further analyzed. The results
Structural damage
demonstrate that wading corrosion leads to a significant releasing of hydrogen gas, and hydrogen producing rate
Hydrogen evolution
Explosion limit is positively correlated with total dissolved solids and the terminal voltage of the battery pack in different water
bodies, such as tap water, river water and lake water. Wading corrosion can cause issues such as falling off and
displacement of connection nickel plate, thinning of anode metal cap, perforation and failure of the safety valve.
Thermal runaway characteristics of Li-ion batteries are obviously affected by wading events, and excessive
wading corrosion of anode metal cap causes the battery to lose its explosive characteristic. This research has
important theoretical and practical value in solving the wading safety problem of lithium-ion battery and electric
vehicle design.

1. Introduction a brief period of vibration, but its DC resistance increases significantly,

Lithium-ion battery with unique characteristics, such as small size,
high energy storage ratio, and long cycle life, are extensively used in
transportation, power electronics and daily life [1,2]. The “National
Lithium Battery Blueprint 2021-2030” [3] released by the American
Advanced Battery Federation predicts a significant increase in demand
for lithium-ion batteries in the future. The current commercial market
includes passenger electric vehicles, stationary energy storage and
aviation. Global electric vehicle battery manufacturing capacity was
747 GWh in 2020, and it is expected to increase to 2492 GWh, an in­
crease of 70 % by 2025. The stationary energy storage market is pro­
jected to increase its value by 80.8 % by 2025. With the advent of new
air traffic concepts [4–6], vertical takeoff and landing aircraft are ex­
pected to develop rapidly in civil aviation applications, relying on the
current lithium battery technology. With the widespread use of lithium-
ion batteries, safety issues have become a crucial focus worldwide,
particularly the influence of the application scenario on the electrical
characteristics and safety of these batteries. Vibration is a common
environmental condition in transportation and aerospace applications
[7]. It reveals that the battery structure does not alter significantly after
with a significant effect along the Z-axis (vertical) direction of batteries
[8]. Vibration causes the removal of the selectively-formed surface film
created during a cell’s first cycles, which is replaced with the surface
film from electrolyte decomposition. The surface films formed under
vibration are composed of much higher concentrations of organic elec­
trolyte decomposition products. This leads to a higher level of damage to
the battery, resulting in capacity attenuation and increased impedance
[9]. Brand [10] found that when the battery is subjected to vibration
along the Z-axis (vertical) for an extended period, the internal mandrel
of the battery may hit the current collector, leading damage to the
negative pole piece that connecting the mandrel and the battery hous­
ing. In high-altitude region, lithium-ion batteries may experience low-
pressure states, which can weaken the combustion intensity of thermal
runaway and the surface temperature of the battery, thereby increasing
the effective emergent response time [11]. However, studies show that
the released gas amount and the explosion limit range of battery ex­
plosions will obviously expand with ambient pressure decreasing [12],
which means that lithium batteries produce more toxic and asphyxiating
gases at low pressure. Usually, lithium-ion batteries are always suffering
varying temperature, magnetic field, and aging during operation. The

* Corresponding author.
E-mail address: nkzqsong@126.com (Q. Zhang).

https://doi.org/10.1016/j.est.2024.110907
Received 5 May 2023; Received in revised form 23 December 2023; Accepted 8 February 2024
Available online 24 February 2024
2352-152X/© 2024 Elsevier Ltd. All rights reserved.
D. Li and Q. Zhang
normal working environment temperature of lithium-ion batteries is
limited to 15–35 ◦ C, then low temperature can decrease ion conductivity
and increase charge transfer resistance, resulting in a decrease in per­
formance, while high temperatures can accelerate the aging rate of the
battery, shorten its life, and cause rapid performance decline [13]. Se­
vere heat accumulation due to abnormal conditions can result in thermal
runaway [14]. The influence of magnetic fields on lithium battery ap­
plications is currently believed to be generally conducive [15,16].
Lithium batteries in magnetic fields produce a magneto hydrodynamic
(MHD) effect that promotes the uniform distribution of lithium ions and
inhibits the growth of dendrites. This leads to a more uniform and dense
deposition of lithium, resulting in better electrical characteristics [17].
As magnetic induction intensity increases, discharge capacity, charging
capacity, discharge energy, and charging energy also increases signifi­
cantly [18]. In addition to external factors, self-aging during the appli­
cation of lithium batteries is also another factor affecting safety. The
electrochemical reaction in the battery plays a major role, including
intercalation/deintercalation, lithium plating, the formation of a solid
electrolyte interphase (SEI) layer, cracks, expansion, and overheating
[19]. This process is accompanied by complex mechanisms such as ca­
pacity attenuation, battery impedance increase, and power attenuation
[20]. Lithium batteries reflect different thermal runaway characteristics
depending on the aging path. For example, electrolyte consumption can
reduce the heat generation of lithium batteries during thermal runaway,
while lithium deposition leads to a deterioration of battery thermal
runaway performance [21,22]. Even in a static non-working state,
lithium batteries can exhibit performance aging attenuation phenomena
[23–25].
Most of current researches have generally focused on environmental
factors of lithium-ion batteries mainly including vibration, magnetic
field, temperature, pressure, and aging. Few scholars have conducted in-
depth research on the water-related corrosion phenomenon of lithium
batteries. However, since the 21st century, the global climate has
changed drastically, resulting in frequent floods that have caused huge
losses of life and property [26]. The irregularity, suddenness, and
destructiveness of floods has particularly affected coastal areas, where
large-scale seawater irrigation has caused various electronic devices that
including new energy vehicles, civil electric bicycles and household
appliances, suffering varying degrees of wading corrosion. Therefore,
safety issue of secondary use of batteries after wading corrosion has
attracted great attention. Nowadays, lithium-ion batteries are widely
used in new energy ships and marine equipment [27–29] and may suffer
from long-term seawater and salt spray erosion in practical applications,
resulting in structural changes in batteries and production of some
dangerous gases [30], which poses great hidden dangers to application
of lithium-ion batteries. The American Advanced Battery Alliance
Electrochemical Storage System Abuse Test Procedure provides re­
quirements for the lithium battery immersion test [31]. According to the
procedure, the lithium-ion battery should be immersed in seawater at
25 ◦ C for at least 2 h, the experimental phenomenon should be observed,
and the hazards during wading should be evaluated. However, the test
did not set a specific wading concentration gradient and lacked a safety
assessment method for waded batteries.
In this work, structure damage evolution and hydrogen releasing
mechanism of Li-ion batteries during wading process is investigated in
real time by in-situ computed tomography. The law of hydrogen
releasing of waded lithium-ion battery is revealed and the kinetic
equation of hydrogen producing is proposed. Moreover, explosion limit
of waded lithium ion battery is examined via thermal runaway test.
2. Experimental
2.1. Water sample
To authentically simulate wading scenarios, the experiment carried
out trials in three distinct domestic water sources characterized by
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Journal of Energy Storage 85 (2024) 110907
varying ion concentrations, including tap water, river water, and lake
water (as shown in Table 1).
2.2. Materials and equipment
The experimental battery used here is 18650 type lithium-ion battery
(model: 22FM, Samsung) with a capacity of 2200 mAh, a maximum
voltage of 4.2 V, a nominal voltage of 3.6 V, and a cut-off voltage of 2.75
V. The FKT-MK-CO hydrogen sensor from Shenzhen Fuquette Technol­
ogy Co., Ltd. is used to detect hydrogen, with an accuracy of 1 ppm in
range of 0–40,000 ppm and. The battery charge and discharge test
equipment used is the CT3001C charge and discharge performance
tester from Wuhan Blue Electric Electronics Co., Ltd. The temperature,
pressure and voltage data is recorded using a SIN-R6000D data logger
from Hangzhou United Test Automation Technology Co., Ltd. A nano­
Voxel micro CT device from Tianjin Sanying Instrument is used to
investigate structural damage, which can obtain detailed image infor­
mation of three-dimensional internal structure of the lithium battery in a
non-destructive manner, and can detect structural changes in key
interface areas of the battery after being immersed in water.
2.3. Wading test
Here, the series connection method of the battery pack with 2, 3, 4,
and 5 cells respectively is chosen to explore the relationship between the
terminal voltage of the battery pack and wading corrosion. The battery’s
state of charge (SOC) was required to reach 100 % before wading test.
The charging process involved an initial discharge to the battery cut-off
voltage of 2.75 V at a constant current of 0.5 C. After a 10-minute rest,
the battery was charged to 4.2 V with a constant current of 1 C, followed
by a constant voltage charge for 10 min until the charging current
dropped below 50 mA. Subsequently, the battery was left to stand for 1 h
post-charging before welding.
The wading test equipment is depicted in Fig. 1. The battery pack
was positioned at the center of the 2 L transparent test chamber bottom,
and 0.4 L of the collected water samples were poured into the chamber,
fully submerging the battery pack with a distance of about 5 cm from the
water surface. Then the chamber was capped using a cylindrical cup
with a rubber sealing ring, and a hydrogen sensor installed at the upper
surface of the cap was used to monitor hydrogen concentration. After
wading test, the corrosion products in the solution were gathered via
centrifugation and drying process for phase analysis. Meanwhile，a
computed tomography (CT) equipment, a non-destructive detection
device [32–34], was used to observe structural damage of the battery
during the wading process in real time.
2.4. Thermal runaway test of waded batteries
Subsequently, a thermal runaway experiment is conducted to
determine the battery’s thermal safety and stability through the analysis
of thermal runaway characteristic parameters. The experiment is con­
ducted using self-built equipment (Fig. 2 and Supplementary Fig. S1),
which consists of several components, including a thermal runaway
chamber, a gas ignition chamber, a battery heating part, a K-type
Table 1
Water samples information.
Water sample Location Total Characteristics
dissolved
solids
Sample1: Tap 117◦ 21′33.091″ E, 69 mg/L Purified water for
water 39◦ 6′43.766″ N domestic use
Sample2: 117◦ 21′18.247″ E, 295 mg/L Flowing water body
River water 39◦ 3′34.656″ N
Sample3: Lake 117◦ 21′38.944″ E, 613 mg/L Still water body
water 39◦ 6′39.206″ N
D. Li and Q. Zhang
Fig. 1. Schematic diagram of wading experimental device.
Fig. 2. Schematic diagram of the explosion device: (a) gas ignition chamber;
(b) thermal runaway chamber.
thermocouple, ignition equipment, an exhaust device, and a tempera­
ture control device. The experimental cabin is made of stainless steel and
has a 3 L dish structure with an air pipe and pump for intake and exhaust
functions. The battery is fixed on a heating seat, and a K-type thermo­
couple is attached to the surface to measure the temperature change on
the battery’s surface. The battery is placed at the center of the explosion
chamber, and a pressure sensor is fixed on the top of the thermal
runaway chamber to measure pressure changes. A high-energy igniter is
used for the secondary ignition of the incoming thermal runaway gas in
the gas explosion chamber. Thermocouples and pressure sensors are also
set up in the gas explosion area to measure the change of gas ignition
parameters. The experimental cabin is connected to various equipment,
including a data recorder, gas exhaust device, and heating power supply.
Following the experiment’s initiation, external heating (40 W) was
applied to induce thermal runaway of the waded lithium-ion battery,
with concurrent recording of parameters throughout the explosion
process. After thermal runaway, the gas produced during thermal
runaway was directed into the gas ignition chamber, where the mixture
gas concentration ratio was adjusted to a standard value by introducing
a specific quantity of air. Simultaneously, a high-energy igniter initiated
a second ignition. By measuring the explosion limit range of the thermal
runaway pyrolysis gas, evaluate the explosion risk of lithium batteries
with different degrees of corrosion.
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Journal of Energy Storage 85 (2024) 110907
3. Results and discussion
3.1. Wading corrosion phenomenon
In the wading test, the series battery pack was submerged in tap
water, river water and lake water respectively, the corrosion phenom­
enon and gas releasing feature of the battery cell was carefully examined
(Fig. 3). It is clearly observed that a large number of highly dense
bubbles generated from the cathode surface of the last cell in the series
group (Fig. 3a1), which ejected perpendicular to the cathode surface,
and gradually converge and move rapidly to the liquid surface to escape.
Meanwhile, the same phenomenon happened at the second cathode
surface, only the number and diameter of bubbles decreased signifi­
cantly. For the first cell in the battery series, this phenomenon is very
weak, just a few very small bubbles emerged and pooled upward into
larger bubbles to escape from the water surface. That is, from the first
cell to the last, the amount of hydrogen gas released from the cathode of
each cell gradually increases. Almost no gas is produced on the surface of
the anode cap, and even if a few bubbles are found, closer inspection
reveals that they originate from the cathode around the cap. The above
phenomenon can be further explained in Fig. 4. For a battery pack
consisting of three cells connected in series, the voltages from anode A to
cathode B, C, D are 4.16 V, 8.32 V, 12.48 V respectively, which result in
that the amount of hydrogen produced by electrolysis is the most at
cathode D and the least at cathode B, and the medium at cathode C. It
can be seen that for the series battery pack, the hydrogen evolution
volume of the cell at the end is large, and the hydrogen evolution speed
is fast. The greater the number of battery series, the greater the total
potential difference at the end, and the greater the hydrogen evolution.
The results obviously show that the hydrogen evolution rate of lithium
batteries in different water bodies is very different. The rate of hydrogen
evolution in descending order is lake water, river water and tap water,
which is corresponding to the order of total dissolved solids (TDS) values
(613 mg/L for lake water, 295 mg/L for river water, and 69 mg/L for tap
water). The increase in total salinity increases the current density on the
cathode surface when the cell wades, causing more hydrogen ions to be
reduced to hydrogen.
Aside from gas production, the corrosion reaction during battery
wading also produces solid substances. It first forms a layer of green
flocculent substance on the surface of the anode metal cap. Due to water
flow affects, the flocculent substance gradually diffuses to the water
body, with some floating on the water surface and gradually changing
from green to brown-red (Fig. 3-a3). When the corrosion reaction con­
tinues to a certain extent, white flocculent substances begin to be pro­
duced in the perforation of the anode metal cap, until the aqueous
solution enters the inside of the battery, causing the battery to fail. At
this point, the reaction phenomenon tends to stop. After removing the
wading corrosion battery pack from the solution for observation (as
showed in Fig. 3-b1, b2), it is found that the connecting piece of the
high-potential part have been seriously corroded, with a large number of
corrosion layers attached to the surface, and the nickel plate having a
brittle fracture. Meanwhile, the corrosion phenomenon at the low po­
tential end was lighter, but still with a small number of brownish-yellow
corrosion spots. In addition, some battery packs have been corroded and
fallen off the connecting nickel plate (Fig. 3-b3). Hence, in practical
applications, if a battery pack cell accidentally experiences wading
problems, the high voltage end is expected to produce a more severe
corrosion phenomenon. The connection piece fracture may cause the
circuit voltage failure, and if the connection piece falls off, the position
may shift, leading to a short circuit of the cell. This occurrence can cause
the battery pack to fail or even induce the risk of thermal runaway.
When the battery pack is waded in water, the cells may be corroded
and lose their structural integrity. The corrosion degree of waded bat­
teries can be divided into five levels according the corrosion results
(Fig. 5). Level 0 means it is not waded and corroded in water, with a
structurally well body and no internal or external damage, exhibiting
D. Li and Q. Zhang
Fig. 3. Phenomenon diagram of wading process: (a1) and (a2) hydrogen evolution image; (a3) the product floats and oxidizes to a brownish red color; (b1) and (b2)
corrosion of nickel plate; (b3) nickel plate fall off. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)
Fig. 4. Schematic diagram of three series battery packs.
Fig. 5. Waded batteries with different corrosion degree: Level 0 (s1), Level 1
(s2), Level 2 (s3-1, s3-2), Level 3 (s4) and Level 4 (s5).
reliable charge and discharge functionality; Level 1 refers to serious
corrosion of the anode, but the basic structure is maintained; Level 2
refers to the complete damage of the anode structure; Level 3 means that
the safety valve is seriously corroded, but without perforation; Level 4
indicates battery perforation, allowing the solution to penetrate into the
cell, causing the battery to fail completely.
In order to obtain the internal structural damage evolution infor­
mation of lithium battery, in situ observation during wading process is
carefully performed in real time using CT technology. Here, a salinity of
3.5 ‰ of seawater as a substitute for ordinary bodies of water was used
in the test to speed up the efficiency of observation. Fig. 6 shows a
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Journal of Energy Storage 85 (2024) 110907
comparison chart of the CT images, depicting the entire cylindrical cell
corrosion process during wading. The horizontal axis represents the time
gradient of wading process, reflecting the change of the corrosion state
of the battery, while the vertical axis represents the CT strafing depth of
the battery, indicating the corrosion process of parts in different cell
positions. Fig. 6a shows a cross-sectional image of the anode cap surface
of the cell, which is initially destroyed during wading-induced corro­
sion. At 30 min, it can be seen obvious granular potholes on the surface
of the metal cap, which gradually thin and perforate until the metal cap
disappears completely at 120 min. Fig. 6b shows the side support of
metal cap that begins to corrode after corrosion of the metal cap surface,
corrosion spreading until the side support disappears completely. Fig. 6c
shows a cross-section of the metal cover base, which remains intact only
near the center edge of the battery because the base is embedded in the
lower part of the seal. In Fig. 6d and e, an aluminum safety valve for the
battery is showed. The upper corrosion of the safety valve occurs after
the anode metal cover is broken, and the corrosion starts from the center
and spreads outward, eventually resulting in a large area of perforation
of the safety valve. Subsequently, the bottom of the safety valve also
begins to undergo a corrosion process. Fig. 5f depicts the collector
located under the safety valve. After the safety valve is corroded and
perforated in a large area, the collector begins to corrode. Since the
collector is wrapped in plastic paper, the structure before and after
corrosion is relatively complete. Fig. 6g shows that there is no noticeable
change in the battery jelly roll in the early stages of wading corrosion.
However, in the later stages, the center mandrel of the battery is
corroded, resulting in some small notches. The last line of the chart is a
longitudinal cross-section of the battery, indicating the position of the
CT section at different depths. This reflects the evolution of the wading
corrosion process from the outside to the inside at the positive electrode
of the battery.
3.2. Analysis of corrosion products
The phenomenon of anode cap corrosion was observed. Firstly, a
large amount of dark green flocculent substances precipitated on the
surface of the positive stainless steel metal cap, which floated in the
solution. The contact part of the water surface and air turned into a
yellow-brown flocculent precipitation, indicating that the positive
stainless steel metal cap initially produced Fe2+ ions when in contact
with water, and reacted with OH− to generate Fe(OH)2. Under the joint
action of the anode potential and dissolved oxygen in solution, Fe(OH)2
further oxidized to reddish-brown Fe(OH)3. As corrosion continued to
deepen, the anode cap corroded and broke, causing the internal
aluminum safety valve to also corrode, producing a small amount of
white precipitate. The overall reaction equation is as following:
4Fe + 3O2 + 6H2 O = 4Fe(OH)3 ↓ (1)
Al − 3e− + 3OH− = Al(OH)3 ↓ (2)
D. Li and Q. Zhang Journal of Energy Storage 85 (2024) 110907

Fig. 6. CT images of the cross-sectional of the tested battery. (a) top surface of the metal cap; (b) side support of metal cap; (c) metal cap base; (d) top surface of the
safety valve; (e) the bottom of the safety valve; (f) collector; (g) upper part of the jelly roll.

Energy spectroscopy (EDS) and X-ray diffractometer (XRD) were
used to determine the elemental composition of the corrosion product.
Fig. 7 indicates that the precipitates mainly consisted of Fe (45.39 %), O
(25.58 %), and Al (24.46 %). XRD analysis (Fig. 8) reveals that the
primary phase composition of the corrosion product is cubic iron hy­
droxide (PDF# 22-0346) and diaspore trihydrate (aluminum hydroxide,
PDF# 20-0011). It can be inferred that the initial green precipitate
formed during corrosion is ferrous hydroxide, which subsequently
oxidized to reddish-brown iron hydroxide through electrochemical and
hydrolysis processes. In continuous corrosion, the safety valve is directly
transformed into diaspore trihydrate, which aligns with the results of the
speculative reaction equation.
3.3. Hydrogen evolution law of battery wading
As mentioned above, the release of hydrogen gas is the most
important phenomenon during the wading process of lithium ion bat­
teries, and the resulting potential explosion hazard is one of the factors
to be considered. It is learned that free ion concentration of lake water,
river water, and tap water is lower compared to higher salinity seawater.
This results in slower hydrogen evolution of a single battery in the
corresponding water quality. However, lithium-ion batteries are mainly
used in the form of battery packs in practical applications. Therefore,
this study used 2–5 batteries for series experimental research.
The data presented in Fig. 9 shows the relationship between the
wading time of a battery pack and the resulting change in hydrogen

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D. Li and Q. Zhang Journal of Energy Storage 85 (2024) 110907

Fig. 7. Energy spectrum of corrosion products.

Fig. 8. XRD diagram of corrosion products.

concentration in the confined space. The x-axis represents the wading

time, while the y-axis represents the change in hydrogen concentration
over time during the wading process. The resulting curve indicates that
the slope of each curve is largely unchanged, suggesting that the
hydrogen evolution reaction during wading is uniform and exhibits a
small rate of change. By comparing the hydrogen concentration change
curves of different solutions, it is observed that the increase of TDS value
in the wading solution led to a faster hydrogen concentration rate gen­
eration. Specifically, the hydrogen concentration produced by wading in
lake water reach the predetermined concentration of 10,000 ppm first,
with a time of only 17 min under the series connection of 5 batteries, and
only 68 min is required to reach the lower limit of hydrogen gas ex­
plosion of 40,000 ppm. As depicted in Fig. 10, the number of series cells
in a battery pack is represented on the x-axis, while the hydrogen evo­
lution rate is represented on the y-axis. The curve demonstrates that, for
a constant solution, an increase in the number of cells connected in se­
ries leads to a higher rate of hydrogen production, which is directly
proportional to the number of cells added. To explore the relationship
between the number of cells in the battery pack and the hydrogen Fig. 9. Hydrogen evolution curves: wading in (a) lake water, (b) tap water and
(c) river water.
evolution rate, a linear equation is first fitted to the hydrogen evolution
rate of different water samples with the number of series cells of the
battery pack, as showed in the following Table 2.
The analysis shows that the producing rate of hydrogen (Rv) is

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D. Li and Q. Zhang Journal of Energy Storage 85 (2024) 110907

takes place in a confined space, posing a significant threat to people and

equipment.

3.4. Thermal runaway and explosion limit

Here, thermal runaway of lithium batteries triggered by gradually

heating, simulating thermal abuse. For untreated lithium battery, the
complete thermal runaway process consists of two stages: primary
eruption and fire explosion [37]. Increasing temperature can prompt the
stepwise decomposition of the internal separator and solid electrolyte
interface (SEI). Meanwhile, the elevation in internal pressure activates
the battery’s Current Interrupt Device (CID) protection device, leading
to an abrupt cessation of current flow and an instantaneous drop in
voltage to 0 V (Supplementary Fig. S2). With temperature elevation, the
decomposition and liquefaction of the separator and SEI membrane
yield a substantial volume of gas, resulting in the internal pressure
ascent until the failure of the CID and the safety valve, accompanying a
sudden release of gases, marginally diminishing the battery’s surface
temperature. It delineates the initial phase of thermal runaway, serving
as a pivotal point for identifying potential battery thermal safety risks.
Fig. 10. Hydrogen producing rate with the number of series connections in Subsequently, temperature elevation persists, voltage exhibits fluctua­
different water samples.
tions, and internal short circuits intensify until culminating in the
complete explosion of the battery, signified by a voltage drop to 0 V. At
Table 2
this point, the surface temperature rises sharply, and a large amount of
Hydrogen evolution rate fitting equation (1.6 L). gas [38,39], flame, dust and metal beads are ejected from the pressure
relief hole, resulting in a sharp increase in ambient pressure, but the
TDS(mg/L) Fit the equation Correlation coefficient r
shape of the anode cap was not damaged (Supplementary Fig. S3 (f1)).
69 RH = 0.41n − 0.06 0.99530 Although the duration of the process is relatively short, a large amount
295 RH = 1.11n + 0.04 0.99659
of thermal energy is released to the outside. After the end of the phe­
613 RH = 2.01n − 0.25 0.99992
nomenon, the battery and confined space gradually cool, and the high
Note: RH, hydrogen generation rate, unit: ppm/s; n, the number of series con­ environmental pressure tends to stabilize.
nected batteries. As showed in Figs. 11 and 12, thermal runaway results of the battery
in different corrosion level show that the thermal runaway process of
proportional to TDS value of water sample. Therefore, the slope of the batteries in corrosion level 0 and 1 is relatively complete. As tempera­
fitting curve is extracted to continue the analysis, and the Rv and TDS ture rises, an initial explosion occurs, causing the battery an internal
values are linearly fitted. The resulting fitting equation is as follows: pressurization. When the pressure reaches the threshold value, the
RV = 0.00295 × TDS + 0.21 (3) safety valve pops open, releasing a small amount of gas, and the tem­
perature drops during the pressure release, resulting in a slight increase
The resulting correlation coefficient of the equation is 0.99828, in ambient pressure. The initial explosion phenomenon did not occur for
indicating a strong correlation between hydrogen increasing rate and batteries in corrosion level 2, 3 and 4, indicating that the initial explo­
TDS value of wading water samples. By integrating the above relation­ sion of cylindrical lithium battery is related to the integrity of the safety
ship, the estimation equation for hydrogen evolution of series battery valve body and a certain strength of the positive metal cover. When the
packs in a 1 L confined space is proposed as follows: temperature rises to about 200 ◦ C, all batteries in corrosion level of 1–3
( )
1.6 × t × n × 2.95 × 10− 3 × TDS + 0.21
C= (4)
V

where C — hydrogen concentration in confined space; t — wading time;

n — the number of cell series connections; TDS – Total dissolved solids; V
— restricted space volume.
The above analysis highlights that when a battery pack composed of
a large number of cells experience wading accident, a significant amount
of flammable hydrogen gas accumulates in the confined space inside the
battery room, concealing a huge security risk. This gas can be ignited by
a high-voltage spark, leading to a serious explosion event. Therefore,
ensuring strong sealing performance of battery components is crucial for
safe battery cell application. Moreover, moisture infiltration and water
condensation can cause long-term corrosion of battery cells, posing
additional safety risks [35]. In addition, the external positive and
negative terminals of the battery pack require particular attention in
wading research. These terminals often have high voltage characteris­
tics, and when waded in water, the resulting electrolytic reaction pro­
duces violent hydrogen. If the terminal voltage and the total dissolved
solids (TDS) value of the aqueous immersion solution are high enough, a
dangerous can form, which may break through the battery pack shell
and detonate the precipitated hydrogen [36]. The violent detonation Fig. 11. Pressure curve in thermal runaway environment.

7
D. Li and Q. Zhang
Fig. 12. Surface temperature curve of thermal runaway battery.
appear final explosive. At this time, the surface temperature of the
battery rises sharply, and the positive electrode releases a large amount
of smoke and heat, resulting in a significant increase in ambient pres­
sure. The battery in corrosion level 4 does not exhibit any phenomena
during heating due to complete failure. Following the battery explosion,
depicted in Supplementary Fig. S3 (f2), the structural integrity of the
positive electrode cap is entirely compromised, leading to the forceful
ejection of the electrode coil and core shaft. The endothermic nature of
the pressure release results in a comparatively low surface temperature
of the battery. Furthermore, batteries in corrosion level of 3 and 4
exhibit remarkably high surface temperatures, despite a relatively
modest explosion-induced impact force. The explosion of the battery in
corrosion level 3 results the safety valve falling off (Supplementary
Fig. S3 (f3)), and a minimal amount of aluminum particles, a byproduct
of safety valve melting. In corrosion level 4, the battery’s safety valve
opened with low injection intensity during the explosion, and no evi­
dence of safety valve melting was found (Supplementary Fig. S3 (f4)).
This suggests that the magnitude of pressure release during the explo­
sion is intricately linked to the structural robustness of the positive
electrode metal cap and safety valve.
The battery in corrosion level 0 takes 676 s to reach the explosion
stage. However, the battery with corrosion level of 2, 3 and 4 are
extended to 726, 744 and 792 s, respectively, as the degree of increased
corrosion delayed thermal runaway triggering. Despite the delay, the
shock pressure on the external environment and the temperature of the
battery surface did not decrease significantly. Conversely, the pressure
shock generated by thermal runaway to the outside world increases as
the strength of the positive metal cap decreases. If the positive cover of
the battery is corroded and perforated, it is possible that the initial ex­
plosion phenomenon will disappear. As a result, power management
systems that are used for the initial explosion as thermal runaway
warning control may fail [40,41]. The dichotomy method is used to
measure the gas explosion limit caused by thermal runaway of lithium-
ion batteries in wading batteries. The upper and lower explosion limits
are delineated by measuring the ratio of the explosive gas to the ex­
plosion proportional gas several times. The formula is as following.
VT
UEL (LEL) = × 100% (5)
VT + VA
where UEL is the upper explosion limit of the explosive gas, LEL is the
lower explosion limit of the explosive gas, VT is the volume of the
explosive gas, and VA is the volume of the proportioned air.
At the beginning, the lithium battery is triggered by the equal power
8
Journal of Energy Storage 85 (2024) 110907
heating method for thermal runaway. When the pressure in the ignition
device is stabilized, the required volume of explosive gas is calculated
and delivered to the ignition device through the differential pressure
heating tube. Quantitative air is also introduced into the ignition
chamber to ensure that the gases are well mixed, and then ignition is
carried out using an igniter. The pressure change in the ignition device
and the phenomenon of fireball combustion are used to determine
whether the gas ignites. The final thermal runaway upper and lower
explosion limit measurements are showed in Fig. 13. The explosion limit
of state 1 battery range from 8.25 % to 28.6 %. The upper and lower
limits of the state 2 battery range are expanded, increasing by 1.65 %
and 0.6 %, respectively. The explosion limit range of state 3 and 4 of
batteries is reduced than that of state 1 cells, and the change is corre­
spondingly related to the pressure change in the explosive device. Since
the explosion limit of an explosive gas depends on the composition of the
explosive gas [42], it can be inferred that there are differences in the
composition of the gas produced by different degrees of pressure relief.
The comparison between the state 1 battery and the battery after
wading corrosion shows that the latter has greater safety risks, especially
when the positive electrode metal cap is corroded. In this case, the
thermal runaway process still generates high heat and can lead to
greater impact pressure on the environment and a wider thermal
runaway explosion gas explosion range, increasing the likelihood of a
domino effect on the battery pack and causing more serious damage to
nearby personnel and equipment. For excessively corrosive batteries,
thermal runaway will still generate high temperatures while the impact
pressure and explosion limit range of thermal runaway gas to the
environment may be reduced. In addition, an excessively corroded
battery may lack initial explosive characteristics, which can adversely
affect early safety warnings. In addition, excessive corrosion can cause
displacement of the nickel plates connected to the battery pack, creating
the risk of battery pack failure or short circuit. Therefore, the thermal
safety consequence analysis method shows that wading corrosion is an
important risk factor in the safe application of lithium batteries. It is
necessary to adopt prevention and treatment measures such as water­
proof, anti-corrosion, and explosion-proof from multiple angles to
effectively reduce application safety risks.
4. Conclusion
To evaluate the safety of lithium ion battery after wading and
improve the safety technology of lithium battery pack, hydrogen release
kinetics, structural damage and thermal runaway characteristic of
waded lithium-ion batteries are systematically studied. Several impor­
tant results were obtained as listed below: Wading corrosion leads to a
Fig. 13. Explosion limit curve of explosive gas.
D. Li and Q. Zhang
significant amount of hydrogen gas releasing and flocculent Fe(OH)2, Fe
(OH)3, Al(OH)3 precipitate, and hydrogen producing rate is positively
correlated with concentration of free ions in the aqueous solution and
the terminal voltage of the battery pack; Wading in lake water, river
water and tap water can cause varying degrees of corrosion, such as
falling off of connection nickel plate, displacement and thinning of
anode metal cap, perforation and failure of the safety valve. In addition,
excessive wading corrosion of the anode metal cap causes the battery to
lose its initial explosion characteristic. The impact pressure and gas
explosion limit will increase after wading event, thereby aggravating the
severity of the thermal runaway consequences. This research has
important promoting effect in solving the water safety problem of
lithium-ion battery and electric vehicle design.
CRediT authorship contribution statement
Dongqi Li: Conceptualization, Data curation, Investigation, Writing
– original draft, Writing – review & editing. Qingsong Zhang:
Supervision.
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
No data was used for the research described in the article.
Acknowledgement
Supported by the Key Program of the Joint Fund for Civil Aviation
Research with National Natural Science Foundation of China (No.
U2033204) and Civil Aviation University of China Postgraduate
Research Innovation Project (2022YJS009).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.est.2024.110907.
References
[1] X.Q. Zeng, et al., Commercialization of lithium battery technologies for electric
vehicles, (in English), Adv. Energy Mater. 9 (27) (Jul 2019).
[2] J. Becker, et al., Design of a safe and reliable Li-ion battery system for applications
in airborne system, in: 52nd Aerospace Sciences Meeting, 2014, p. 0380.
[3] F. C. f. A. BatteriesFCAB, Executive Summary, National Blueprint for Lithium
Batteries, 2021–2030, US Department of Energy, 2021.
[4] T.H. Ha, K. Lee, J.T. Hwang, Large-scale multidisciplinary optimization under
uncertainty for electric vertical takeoff and landing aircraft, in: AIAA Scitech 2020
Forum, 2020, p. 0904.
[5] A. Straubinger, R. Rothfeld, M. Shamiyeh, K.-D. Büchter, J. Kaiser, K.O. Plötner, An
overview of current research and developments in urban air mobility–setting the
scene for UAM introduction, J. Air Transp. Manag. 87 (2020) 101852.
[6] D.P. Thipphavong, et al., Urban air mobility airspace integration concepts and
considerations, in: 2018 Aviation Technology, Integration, and Operations
Conference, 2018, p. 3676.
[7] C.O. Yoon, P.Y. Lee, M. Jang, K. Yoo, J. Kim, Comparison of internal parameters
varied by environmental tests between high-power series/parallel battery packs
with different shapes, (in English), J. Ind. Eng. Chem. 71 (Mar 25 2019) 260–269.
[8] J.M. Hooper, J. Marco, G.H. Chouchelamane, J.S. Chevalier, D. Williams, Multi-
axis vibration durability testing of lithium ion 18650 NCA cylindrical cells, (in
English), J. Energy Storage 15 (Feb 2018) 103–123.
[9] L. Somerville, et al., Impact of vibration on the surface film of lithium-ion cells, (in
English), Energies 10 (6) (Jun 2017).
[10] M.J. Brand, et al., Effects of vibrations and shocks on lithium-ion cells, (in English),
J. Power Sources 288 (Aug 15 2015) 62–69.
Journal of Energy Storage 85 (2024) 110907
[11] Y.Y. Fu, S. Lu, L. Shi, X.D. Cheng, H.P. Zhang, Ignition and combustion
characteristics of lithium ion batteries under low atmospheric pressure, (in
English), Energy 161 (Oct 15 2018) 38–45.
[12] Y.W. Li, L.H. Jiang, Z.H. Huang, Z.Z. Jia, P. Qin, Q.S. Wang, Pressure effect on the
thermal runaway behaviors of lithium-ion battery in confined space, (in English),
Fire Technol., Jul 24 2022.
[13] S. Ma, et al., Temperature effect and thermal impact in lithium-ion batteries: a
review, (in English), Prog. Nat. Sci. Mater. Int. 28 (6) (Dec 2018) 653–666.
[14] J.L. Liu, Z.H. Huang, J.H. Sun, Q.S. Wang, Heat generation and thermal runaway of
lithium-ion battery induced by slight overcharging cycling, (in English), J. Power
Sources 526 (Apr 1 2022).
[15] C.M. Costa, K.J. Merazzo, R. Gonçalves, C. Amos, S. Lanceros-Méndez,
Magnetically active lithium-ion batteries towards battery performance
improvement, iScience 24 (6) (2021) 102691.
[16] K. Shen, X. Xu, Y. Tang, Recent progress of magnetic field application in lithium-
based batteries, Nano Energy 92 (2022) 106703.
[17] K. Shen, et al., Magnetic field–suppressed lithium dendrite growth for stable
lithium-metal batteries, Adv. Energy Mater. 9 (20) (2019) 1900260.
[18] G.Q. Ruan, J. Hua, X. Hu, C.Q. Yu, Study on the influence of magnetic field on the
performance of lithium-ion batteries, (in English), Energy Rep. 8 (Jul 2022)
1294–1304.
[19] D. Šeruga, A. Gosar, C.A. Sweeney, J. Jaguemont, J. Van Mierlo, M. Nagode,
Continuous modelling of cyclic ageing for lithium-ion batteries, Energy 215 (2021)
119079.
[20] J. Vetter, et al., Ageing mechanisms in lithium-ion batteries, J. Power Sources 147
(1–2) (2005) 269–281.
[21] D. S. Ren et al., "A comparative investigation of aging effects on thermal runaway
behavior of lithium-ion batteries," (in English), eTransportation, vol. 2, Nov 2019.
[22] X. Feng, M. Ouyang, X. Liu, L. Lu, Y. Xia, X. He, Thermal runaway mechanism of
lithium ion battery for electric vehicles: a review, Energy Storage Mater. 10 (2018)
246–267.
[23] A. Eddahech, O. Briat, J.M. Vinassa, Determination of lithium-ion battery state-of-
health based on constant-voltage charge phase, (in English), J. Power Sources 258
(Jul 15 2014) 218–227.
[24] P. Keil, et al., Calendar aging of lithium-ion batteries, J. Electrochem. Soc. 163 (9)
(2016) A1872.
[25] S.L. Hahn, M. Storch, R. Swaminathan, B. Obry, J. Bandlow, K.P. Birke,
Quantitative validation of calendar aging models for lithium-ion batteries, J. Power
Sources 400 (2018) 402–414.
[26] J. Rentschler, M. Salhab, B.A. Jafino, Flood exposure and poverty in 188 countries,
(in English), Nat. Commun. 13 (1) (Jun 28 2022).
[27] R. Chen, W. Yu, C.F. Yang, Control strategy of an all-electric cruise ship based on
cycle life mode of lithium battery pack, (in English), Int. J. Environ. Sci. Technol.
19 (9) (Sep 2022) 8369–8384.
[28] S. Eriksen, A. Karlsen, Batteries as power sources in DP systems, in Dynamic
Positioning Conference, 2018.
[29] S. Koo, et al., Sea-water battery for maritime applications, in: Global Oceans 2020:
Singapore–US Gulf Coast, IEEE, 2020, pp. 1–4.
[30] Y.-Y. Wang, X.-Q. Zhang, M.-Y. Zhou, J.-Q. Huang, Mechanism, quantitative
characterization, and inhibition of corrosion in lithium batteries, Nano Res. Energy
2 (1) (2023) e9120046.
[31] T. Unkelhaeuser, D. Smallwood, Sandia National Laboratories Electrochemical
Storage System Abuse Test Procedure Manual, Office Of Scientific & Technical
Information Technical Reports, 1999.
[32] L. Shi, et al., Review of CT image reconstruction open source toolkits, J. Xray Sci.
Technol. 28 (4) (2020) 619–639.
[33] V. Cnudde, M.N. Boone, High-resolution X-ray computed tomography in
geosciences: a review of the current technology and applications, Earth Sci. Rev.
123 (2013) 1–17.
[34] L. De Chiffre, S. Carmignato, J.-P. Kruth, R. Schmitt, A. Weckenmann, Industrial
applications of computed tomography, CIRP Ann. 63 (2) (2014) 655–677.
[35] C. Liao, J. Wang, Study on the influence of operating environment conditions on
the performance of power lithium battery system, in: 2022 IEEE International
Conference on Electrical Engineering, Big Data and Algorithms (EEBDA), IEEE,
2022, pp. 688–692.
[36] C. Xu, M. Ouyang, L. Lu, X. Liu, S. Wang, X. Feng, Preliminary study on the
mechanism of lithium ion battery pack under water immersion, ECS Trans. 77 (11)
(2017) 209.
[37] H. Shen, Y. Zhang, Y. Wu, A comparative study on air transport safety of lithium-
ion batteries with different SOCs, Appl. Therm. Eng. 179 (2020) 115679.
[38] L. Yuan, T. Dubaniewicz, I. Zlochower, R. Thomas, N. Rayyan, Experimental study
on thermal runaway and vented gases of lithium-ion cells, Process Saf. Environ.
Prot. 144 (2020) 186–192.
[39] T. Maloney, Lithium Battery Thermal Runaway Vent Gas Analysis vol. 7, US
Department of Transportation, 2016.
[40] Y. Li, Q. Wang, X.-X. Lian, Q.-J. Zhou, X-ray computed tomography and
simultaneous multi-signal detection for evaluation of thermal runaway of lithium-
ion battery, Mater. Technol. 37 (14) (2022) 3041–3050.
[41] D. Kong, H. Lv, P. Ping, G. Wang, A review of early warning methods of thermal
runaway of lithium ion batteries, J. Energy Storage 64 (2023) 107073.
[42] Q. Zhang, J. Niu, Z. Zhao, Q. Wang, Research on the effect of thermal runaway gas
components and explosion limits of lithium-ion batteries under different charge
states, J. Energy Storage 45 (2022) 103759.