Version of Record: https://www.sciencedirect.com/science/article/pii/S2211285521001361
Manuscript_b62deb20d38703ccd384d6dad37ec87d
Thermal runaway mechanism of lithium-ion battery with
LiNi0.8Mn0.1Co0.1O2 cathode materials
Yan Li,1 Xiang Liu,2 Li Wang,1,3,* Xuning Feng,1,* Dongsheng Ren,1,3 Yu Wu,1 Guiliang Xu,2
Languang Lu,1 Junxian Hou,1 Weifeng Zhang,1 Yongling Wang,1 Wenqian Xu,4 Yang Ren,4 Zaifa
Wang,5 Jianyu Huang,5 Xiangfeng Meng,6 Xuebing Han,1 Hewu Wang,1 Xiangming He,3 Zonghai
Chen,2 Khalil Amine,2,7 Minggao Ouyang1,*
1. State Key Laboratory of Automotive Safety and Energy, Tsinghua University, Beijing 100084,
China;
2. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439,
United States;
3. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China;
4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL
60439, United States;
5. Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and
Technology, Yanshan University, Qinhuangdao 066004, China;
6. Corporation Public Affairs Department, Contemporary Amperex Technology Co., Ltd., NingDe
352100, China;
7. Materials Science and Engineering, Stanford University, Stanford, CA 94305, United States;
*
Corresponding
authors:
wang-l@mail.tsinghua.edu.cn;
fxn17@mail.tsinghua.edu.cn;
ouymg@tsinghua.edu.cn
Abstract: Battery safety is critical to the application of lithium-ion batteries,
© 2021 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
especially for high energy density battery applied in electric vehicles. In this paper,
the thermal runaway mechanism of LiNi0.8Co0.1Mn0.1O2 based lithium-ion battery is
illustrated. And the reaction between cathode and flammable electrolyte is proved as
the trigger of the thermal runaway accident. In detail, with differential scanning
calorimeter tests for battery components, the material combination contributing to
thermal runaway was decoupled. Characterization with synchrotron X-ray diffraction
and transmission electron microscopy with in-situ heating proved that the vigorous
exothermic reaction is initiated by the liberated oxygen species. The pulse of highly
active oxygen species reacted quickly with the electrolyte, accompanied with
tremendous heat release, which accelerated the phase transformation of charged
cathode. Also, the mechanism is verified by a confirmatory experiment when the
highly active oxygen species were trapped by anion receptor, the phase transformation
of the charged cathode was inhibited. Clarifying the thermal runaway mechanism of
LiNi0.8Co0.1Mn0.1 based lithium-ion battery may light the way to battery chemistries of
both high energy density and high safety.
Keywords: NCM811; thermal runway; Lithium-ion battery; mechanism; battery
safety
Introduction
Lithium-ion batteries (LIBs) have been considered as the most promising power
source for electric vehicles (EVs) owing to their high energy density, extended cycle
life, and wide working condition [1–4]. However, the spate of field failures of the EVs
due to the thermal runaway of the LIBs [5-9] undermine consumer’s confidence and
imped the commercialization of the EVs [10-12]. Therefore, understanding the
mechanism of thermal runaway have become urgent for large-scale application of in
EVs, especially for LIBs of high energy density and large format.
It was reported that thermal runaway was driven by successive exothermic side
reactions between the battery components, until the heat release was out of control
[13,14]. The reactions included solid electrolyte interphace (SEI) decomposition and
regeneration, redox reaction between electrolyte and electrodes, binder reduction by
anode materials, and reactions between cathode and anode via material crosstalk
[15-19]. The contribution of each exothermic reaction to thermal runaway can be
identified with differential scanning calorimetry (DSC) or accelerating rate
calorimeter (ARC) [20-23]. However, the reactions that trigger the sharp temperature
rise during thermal runaway evolution is still controversial. Regarding the
contribution of anode and cathode, Inoue and Mukai [24] found that the formation of
LiF on the anode surface is the trigger for LiNi0.3Co0.3Mn0.3O2|artificial graphite
(NCM333|AG) battery, whereas the oxidation of electrolyte by cathode triggers the
thermal runaway in LiNi0.8Co0.15Al0.05O2|artificial graphite (NCA|AG) battery. In
contrast, Ren et al. [25] announced that the reactions between anode and electrolyte
could release tremendous heat and threw NCM333|AG battery into thermal runaway.
For NCM523|AG battery, the chemical crosstalk was proved to be the trigger of
thermal runaway. Specifically, the oxygen (O2) released from the fully charged
cathode due to phase transformation could diffuse to anode to cause redox reactions
with tremendous heat generation [13]. Overall, the oxygen-release of NCM811
cathode at early stage is considered to be the main safety concern for the application
of Ni-rich layered cathode materials, despite its obvious advantage in high energy
capacity.
NCM811 (LiNi0.8Co0.1Mn0.1O2) has been considered as promising cathode candidates
for the next-generation LIBs owing to its high energy density and potentially low
cost.[3] Severe challenges still need to be overcome to achieve successful
commercialization of NCM811 cathode, among which the most difficult is its poorer
thermal stability as compared to that of NCM materials with lower Ni content. Due to
the well-balanced Ni:Mn:Co ratio, NCM523 material was regarded as the optimal
composition for having comparably good thermal stability while maintaining a high
capacity.[10] But the safety performance should be evaluated with a full battery,
where the cathode materials are soaked in electrolyte. From commercial batteries with
NCM333 to 433, 532, 622 or 811cathode, the ethylene carbonate (EC) is looked on as
the crucial electrolyte component owing to its high dielectric constant. The boiling
point of EC is 248 oC, which is close to the phase transition/oxygen release starting
temperature of fully charged NCM523. With Ni content increase, the onset of oxygen
release shifts to lower temperature with pronounced intensity. The pulse of oxygen
species (such as O2-, O-, O22-) might react quickly with the electrolyte, generating
considerable amount of heat thus accelerate the thermal runaway.[10,26] The density
functional theory (DFT) calculations have shown that EC dissociation on Ni-rich
layered oxides is more energetically favorable than nucleophilic attack, electrophilic
attack.[27] In addition, dissociation energetics of EC on NCM811 is found to be
thermodynamically favorable. Considering of the boiling point, the other carbonate
may already evaporate at temperature lower than 200oC, then EC is also the most
available solvent that reacts with cathode, that is why NCM523 based battery showed
a watershed for battery safety. In this sense, it is understandable that the thermal
failure is more serious for NCM811 based battery.
In order to inhibit oxygen release and stable cathode-electrolyte interface, cation
doping\substitution and surface coating have been widely adopted as promising ways
to improve the thermal stability of NCM811 materials. However, these modifications
can only alleviate the oxygen-release-related issue, and it can’t be solved
fundamentally, especially at elevated temperatures. The electrolyte plays a significant
role during battery thermal runaway. If electrolyte additives have special properties,
such as oxygen species capture capability, then unwanted exothermic reactions
between oxygen and electrolyte can be minimized.
This paper intended to elucidate the thermal runaway mechanism for NCM811 battery
and reveal the role of Cathode-released oxygen on thermal runaway triggering. We
first observe the thermal features of NCM811full battery with ARC tests. In order to
locate the triggering reactions for thermal runaway, the reactants are determined by
DSC in combination with in situ heating HRXRD-MS. And the reaction between
oxygen species (O2, O2-, O-, etc.) and electrolyte is found to be the triggering reaction
of thermal runaway. This conclusion is further solid by in situ heating TEM,
confirmatory experiment and in situ heating HEXRD. This study demonstrates that
the thermally driven oxygen release pathway is strongly depended on the surrounding
electrolyte. The electrolyte could facilitate the phase transformation and the oxygen
release. This work sheds new light on the new design principles to achieve lithium-ion
batteries of both high energy density and improved safety.
Results and Discussion
Safety characterization of NCM811|AG battery with the EC/EMC electrolyte
Fig. S1b and S1c displayed the thermal features of NMC811|AG battery with 1M
LiPF6 EC/EMC electrolyte during the ARC test. The dependence of the temperature
rising rate (dT/dt) on temperature was plotted in logarithmic coordinates. The
PET/ceramic non-woven separator was used to avoid internal short circuit.
Generally, three characteristic temperatures of {T1, T2, T3} were defined to describe
the thermal behavior of the battery.[28] T1 was defined as the onset temperature of
self-heating, which was considered to be associated with the mild reactions between
anode and electrolyte. The trigger temperature of the thermal runaway was marked as
T2, which was determined when the temperature rise rate reached 1℃ s-1. After this
critical temperature, the battery temperature increase was exponential (hundreds of
degrees per second) and hard to stop even using liquid nitrogen.[13] T3 was defined
as the maximum temperature. In this study, the three characteristic temperatures were
located at 65℃ (T1), 218℃ (T2) and 750℃ (T3), respectively.
Identification of the triggering reaction for thermal runaway
The time order of the reactions during thermal runaway evolution was determined by
testing various battery materials obtained from the 4.2V charged pouch cell
mentioned above and their combinations using DSC (Fig.1). As shown in Fig. 1a, all
the possible component combinations leading to exothermic reactions including
cathode (Ca), anode (An), Ca +An, Ca +electrolyte (Ely), and Ca +Ely +An, were
tested.
Fig. 1 (a) DSC profiles of the cathode, anode, electrolyte, and the mixture were prepared
according to their ratio in pouch cell; (b) Normalized intensity of (003) peak evolution of charged
cathode during heating; (c) O2 (m/z = 32, black) and CO2 (m/z = 44, green) evolution of individual
cathode sample during the XRD test;
The cathode exhibited a broad and weak exothermic peak centered around 230℃.
This exothermic peak could be attributed to the phase transformation from layered to
spinel structure. And the exothermic peak above 300℃ was probably due to a
thermite reaction because such an exothermic peak was not observed when the
aluminum current collector was removed.[29] The anode also exhibited a broad and
mild exothermic peak around 280℃, which could be attributed to the reaction
between the lithiated graphite and the binder.[13] The Ca +An sample resulted in a
broad and obvious exothermic peak around 230℃. The exothermic peak could be
attributed to the reactions between oxygen released by fully charged NCM811 and the
lithiated graphite.[13] However, the addition of electrolyte resulted in obvious
changes in the thermal behaviors of cathode and anode. As shown in Fig. 1a, for the
Ca +Ely sample, two peaks appeared at 215℃ and 230℃. And for the Ca +Ely +An
sample, a sharp exothermic peak was also detected at 215℃. Based on the time order
of the reactions, the reaction between cathode and electrolyte was identified as the
thermal runaway trigger.
In a real battery, the delithiated cathode materials were soaked in flammable
electrolyte, the pulse of highly oxidizing oxygen species (such as O2-, O-, O22-)
released from the cathode material could react immediately with the reductive
electrolyte, and both the heat released by the redox reaction and the consumption of
the oxygen species would accelerate the phase transformation of the cathode material.
Given that the following work aims to probe the trigger of thermal runaway for
NCM811|AG battery.
Cathode-electrolyte reaction mechanism resulting in thermal runaway of
NCM811|AG battery
The state-of-the-art in situ heating with synchrotron XRD measurements and mass
spectroscopy were used to provide direct correlation between phase changes and gas
release. (Fig. S2) As shown in Fig. 1b, the intensity of (003) peak gradually decreased
over 140oC, which indicating the phase transitions were initiated. Meanwhile, the CO2
release peak was observed. However, the O2 release peak started later. It has been
reported that thermal decomposition of the binder in nitrogen flow would release CO2
in the range of 450-650oC[26,30,31], and the conductive carbon were quite stable at
temperatures below 700oC under nitrogen flow[32,33]. Therefore, the CO2 released at
such a low temperature could only be resulted from redox reaction between
conductive carbon and the oxygen species released by cathode material. This proved
the existence of the oxidizing oxygen species (such as O2-, O-, O22-) during phase
transition.
DSC and the in-situ heating XRD-MS measurements provided insight information
about the average behavior of charged NCM811 cathode. Generally, the oxidation of
the organic carbonate electrolyte by the oxygen species liberated from charged
cathode occurred at the particle interface. To fully understand the effect of higher
temperatures in materials, in situ heating TEM was used to direct investigation of the
evolution of surface topography, crystal morphology, and electronic structure.
Fig. 2 Bright-field (BF) images and selected-area electron diffraction (SAED) patterns of the fully
charged NMC811 particle at 25 oC (a, b) and at 250 oC for 3 hours (c, d); Electron energy loss
spectra (EELS) of O K-edge (e), Mn L2,3-edge (f), Co L2,3-edge (g), and Ni L2,3-edge (h) as a
function of temperatures and time. SAED patterns and EEL spectra were acquired from the areas
indicated in the BF images.
Fig.2 presented the variations of a fully charged NMC811 particle at different
temperatures. Electron energy loss spectra (EELS) were used to explore the evolution
of the electronic structure of the charged NCM811 particle. And the near-edge
structure of the O K-edge provided direct insight into the oxidation state of the
transition metals in the bulk. The O K-edge EELS composed of two distinct peaks,
including a pre-edge peak and a main peak. The pre-edge peak (at ~527-530 eV) was
attributed to a transition of electrons from O 1s to unoccupied O 2p, which hybridized
with the 3d of transition metals (TMs). The main peak (at ~538.5-540 eV) is
attributed to a transition of electrons from O 1s to the sp hybridized orbital which
formed by O 2p and TMs 4s.[34] As the temperature increased, oxygen K-edge
pre-edge peak shifted to higher energy loss can be obviously observed (the dotted box
in Fig. 2e). This indicated the reduction of the TMs around the oxygen sites at high
temperature. Together with the obvious changes in the crystallographic structure,
porosity appeared at the surface of charged cathode from 25 oC to 250 oC for 3 hours
(Fig.2a and 2c), corresponding SAED changes from single crystalline state (Fig.2b,
[-441] zone axis) to polycrystalline state (Fig.2d), which is due to the oxygen release
during the phase transitions. [34] Since the reduction of the TMs (e.g. from Ni4+ or
Ni3+ to Ni2+) occur concomitant with electron transfer from lattice oxygen, the oxygen
release from the structure is inevitable, to maintain the overall charge neutrality.
Fig. 3 (a) An illustration of the cathode and their components; The transformation process of
oxygen species into oxygen gas of charged cathode (b), in the presence of electrolyte (c) and in the
presence of TPFPB (d)[36]; (e) O2 (m/z = 32) gas evolution of the cathode, cathode mixed with
electrolyte and their mixture with TPFPB during the DSC measurement; (f) DSC traces of the
cathode, cathode mixed with electrolyte and their mixture with TPFPB.
The transformation process of oxygen species into oxygen gas was proposed in Fig. 3.
Under suitable temperature conditions, partially charged oxygen species were the
main forms of oxygen species. For the chemically absorbed oxygen species, although
their valence states are not -2 values, most of them were located at lattice positions.
When the temperature was high enough, some of the oxygen species will leave lattice
and turn into physical absorbed molecular oxygen species, which mainly locates at the
particle surface.[35] If this process happens, it could result in further evolution of
oxygen gas from the surface. However, in a real battery, where a large amount of
highly reactive electrolyte is available, the pulse of highly active oxygen species
could react immediately with the electrolyte with tremendous heat release (Fig. 3c).
Tris(pentafluorophenyl)borane (TPFPB) is a widely used anion receptor, which
composed of electron deficient borane or borane compounds as well as fluorinated
aryl or alkyl groups.[36-38] Considering the strong anion coordination effect of
TPFPB, the released oxygen species were hoped to be trapped by TPFPB instead of
attacking the electrolyte. (Fig.3d) The trapped oxygen species could be reduced to
oxygen gas, which could be detected by the STA-MS.
Fig. 3e showed the profiles of oxygen release of the dry charged NCM811 cathode.
For the dry cathode, the peak initiated at ca. 240oC, which was delayed to the phase
transformation. The process is usually associated with irreversible oxygen loss, which
could cross the separator and attack the lithiated anode and induce a severe safety
concern. However, the oxygen gas release behavior of the cathode with an electrolyte
addition was quite different and a sharp oxygen gas peak centered at ~230oC was
detected. The released oxidizing species (O2, O2-, O-, etc.) from the cathode were
reduced by the electrolyte with tremendous heat release (Fig. 3f), which accelerated
phase transformation. Big changes were observed when the electrolyte mixed with
TPFPB. As shown in Fig. 3e, the oxygen gas peak starts earlier at ~150oC. This
behavior is caused by the TPFPB serving as a reduction agent that reduces the highly
reactive oxygen species into oxygen gas. Besides, the exothermal behavior was also
changed with the TPFPB addition, the sharp exothermic peak was replaced by a small
valley peak. Overall, the released oxidizing species (O2, O2-, O-, etc.) from the
cathode might react quickly with electrolyte. In the presence of TPFPB, the highly
reactive oxidizing species might be firstly reduced to relatively lower reactive oxygen
gas. Thus, the reaction rate between the cathode and the electrolyte was decreased,
indicating that the exothermic reaction between cathode and electrolyte was initiated
by the oxygen species rather than oxygen gas.
In situ high-energy X-ray diffraction (HEXRD) measurements were used to further
understand the cathode/electrolyte reaction and the impact of TPFPB anion absorber
in preventing the abrupt heat generation. Fig. 4a shows the in-situ HEXRD patterns of
NCM811 cathode during heating from room temperature to 600 oC with heating rate
of 10 oC min-1. At room temperature, the pattern consisted of 7 major diffraction
peaks, which could be attributed to (003), (101), (012), (107), (108), (110) and (113)
of the O3-type layered structure. As the temperature increased, the reflections shifted
to a lower 2 theta values, which could be attributed to the thermal expansion of the
lattice.
Fig. 4 In-situ HEXRD characterization of dry NCM811 cathode (a), NCM811 cathode mixed with
electrolyte (1.0 M LiPF6 in EC/EMC) (b) and their mixture with TPFPB (c) during heating. The
temperatures on the right side indicated when phase transformation started or finished.
For the dry fully charged NCM811 cathode, two phase changes could be observed at
200 and 380 oC, respectively. When heating to 200 oC, the layered (108) peak had
merged with the (110) peak, meanwhile, a new peak of spinel (440) emerged at ~4.6o.
At the same time, the layered (113) peak, (107) peak and (101) peak shifted
significantly to smaller 2 theta values, and their intensities decreased. With continued
heating, three new weak spinel peaks ((220), (331), (511)) emerged and remained
visible until the temperature heated to 380oC, indicating the phase transition from
layered to disordered spinel structure with a temperature range spanning ~180 oC.
This is followed by the second phase transition from disordered spinel to rock-salt,
and the major parts of the NCM811 cathode remined in the rock-salt structure until
the end of heating (600 oC).
Adding electrolyte (1 M LiPF6 in EC/EMC) to fully charged NCM811 changed the
response of the cathode during the in-situ HEXRD experiments. As shown in Fig. 4b,
the phase transitions were ended at lower temperature with a narrow temperature
range, in comparison with dry cathode. The phase transition from layered to
disordered spinel structure started at ~200 oC and was completed at ~320 oC. This
process was similar to the dry cathode (200 oC to 380 oC), but with a narrow
temperature range. When the temperature was above 320 oC, two new rock-salt peaks
of (200) and (220) emerged, indicating the phase transition from disordered spinel to
rock-salt. When the temperature reached 550 oC, their intensities decreased, indicating
that the rock-salt structure had begun to disappear. However, for the dry cathode, no
obvious intensity change was observed until 600 oC. At the same time, new reflections
appeared around 1.8, 2.0 and 2.1o, and with increasing temperature, their intensity
increased. These new reflections indicate the formation of new intermediate phase,
which were quite different to dry cathode.
In the case of Ca +Ely+ TPFPB, the response (Fig. 4c) of the cathode during the
in-situ experiments were very similar to that shown in Fig. 4b. The phase transition
from layered to disordered spinel structure started at ~200 oC and was completed at
~350 oC. This was followed by the phase transition from disordered spinel to rock-salt,
and the major parts of the NCM811 cathode remined in the rock-salt structure until
600 oC (Fig. 4c).
Fig. 5 (a) The layered (003) peak evolution of charged dry NCM811 cathode, NCM811 cathode
mixed with electrolyte (1.0 M LiPF6 in EC/EMC) and their mixture with TPFPB during heating
from 100oC to 300oC. (b) Schematic of the cation migration and phase transformation during
heating. (c, d) Evolution of unit cell lattice parameter during heating, obtained by the Rietveld
refinement of each HEXRD pattern. (e) Lattice strain evolution during the heating process.
Fig. 5a shows the (003) peak evolution during heating (100-300oC) revealed by in situ
HEXRD, see XRD plots in Fig. 4. By Rietveld refinement of each XRD pattern, the
unit cell evolution can be obtained, see Figs. 5c-d, which can reveal the cathode
lattice structure changes during heating. As shown, the lattice a presents a linear
expanding manner below 200oC, mainly caused by the thermal expansion. However,
when the temperature exceeds 200oC, the lattice a increases exponentially, caused by
the TM ions migration with phase transformation, as well as the reduction (TM4+ →
TM3+) thus consequently a stronger repulsion between the TM cations with
surrounding oxygen atoms. For the dry cathode, the lattice c exhibits a more
complicated evolution, expanding at lower temperature (＜~220oC) and compressing
with continuous heating, which was corelate well with the a lattice and mainly related
to the phase transformation and oxygen release. However, in the presence of
electrolyte and TPFPB, the lattice c exhibits a moderate evolution. This means before
the lattice shrinkage, the dry cathode can withhold more c lattice expansion than it in
the presence of electrolyte and TPFPB, thereby the oxygen release becomes more
difficult. And the c lattice expansion is directly related to lattice strain, the dry cathode
lattice can endure a much greater lattice strain, while the strain in the presence of
electrolyte is released spontaneously by cation migration, phase transformation and
oxygen release. Therefore, the results show that electrolyte has a negative impact on
the phase structure stability of cathode, which could accelerate phase transition and
oxygen release.
According to the DSC, MS and HEXRD results, TPFPB improved safety performance
at the raw material level. However, did the TPFPB truly enhance the safety of a full
battery? To answer this question, ARC tests were conducted on NCM811 full batteries
with the TPFPB added electrolyte. As shown in Figure 6a, The T1s for NCM811 and
TPFPB added NCM811 (B-NCM811) were 63°C and 65°C, respectively (nearly the
same, as the initial heating was already 5°C/step). T2 is a critical index for evaluating
the safety of the battery, and a higher T2 means better overall thermal safety. The key
temperature, T2, was 198 oC for B-NCM811, 20 oC lower than for NCM811,
indicating that the battery was more likely to thermal runaway after TPFPB added. By
connecting the abovementioned profiles of oxygen release for the charged NCM811
cathodes without and in the presence of TPFPB (Fig. 3e), the lower T2 could be
mainly attributed to the reducibility of TPFPB, which makes oxygen gas release at
lower temperature. And the released oxygen gas could cross the separator and
consumed by the lithiated anode with tremendous heat release. The most important
improvement for B-NCM811 battery was a lower temperature of T3 (650 °C)
compared with 750 °C for NMC811 (Fig. 6a). Combined with the above discussion,
the lower of T3 can be attributed to two factors: (1) In the presence of electrolyte and
TPFPB, the highly reactive oxygen species were reduced to relatively lower reactive
oxygen gas. Thus, the reaction probability between cathode and electrolyte was
reduced. (2) The redox reaction between cathode and anode is the main heat source
during thermal runaway. As a matter of fact, the cathode oxygen release process is a
“self-destruction” process. Due to the reducibility of TPFPB, the oxygen gas could be
induced to release at a lower temperature before thermal runaway.
Fig. 6 Thermal runaway characterization of NCM811 with a conventional electrolyte (green line)
and TPFPB added electrolyte (red line). Measured by ARC. (a) Temperature versus time during
ARC test; (b) Temperature rate versus absolute temperature during ARC test; (c) Segment of Fig.
7b focusing on the temperature rate before thermal runaway.
Conclusion
In this work, the thermal runaway features of NCM811 battery are tested and the
thermal runaway mechanism is demonstrated. The cathode liberated oxygen species
(O2, O2-, O-, etc.) is considered to be blamed for the thermal runaway. The thermally
driven oxygen specieces release pathway is strongly depended on the surrounding
electrolyte. The electrolyte has a negative impact on the thermal stability of cathode,
which could facilitate the phase transformation and the oxygen release. The liberated
oxidizing species react immediately with the flammable electrolyte, the released
tremendous heat reheat the cathode and accelerate phase transformation. The reaction
between oxygen species and electrolyte is the triggering factor of thermal runaway.
This work paves the way to improve safety for battery chemistries of higher energy
density.
Acknowledgement
This research is supported by the Ministry of Science and Technology of China
under the Grant No. 2019YFE0100200, the National Natural Science Foundation of
China under the Grant No. 51706117, 52076121, 52004138. Research at the Argonne
National Laboratory was funded by the U.S. Department of Energy (DOE), Vehicle
Technologies Office. Support from Tien Duong of the U.S. DOE’s Office of Vehicle
Technologies Program is gratefully acknowledged. Use of the Advanced Photon
Source (APS), Office of Science user facilities, was supported by the U. S.
Department of Energy, Office of Science, and Office of Basic Energy Sciences, under
Contract No. DE-AC02-06CH11357.
Declaration
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.
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Dr. Yan Li received the Ph.D. degree in the College of Chemical Engineering from
Nanjing Technology University, Nanjing, China, in 2016. He is currently a Post-Doc
Researcher in Automotive Department in Tsinghua University. His main research
interests focus on the fields of battery safety.
Dr. Xiang Liu is now work as postdoctoral researcher in Argonne National
Laboratory. He obtained his PhD from the University of Hong Kong in 2016. Prior to
his current position, he worked as a postdoc in Automotive Department in Tsinghua
University. His research focus includes cathode material design and synthesis for
lithium-ion and sodium-ion batteries, as well as the in situ/operando synchrotron
X-ray based characterizations for the understanding of battery safety and degradation
mechanisms.
Dr. Li Wang is an associate professor of the vice director of the Advanced Energy
and Material Chemistry Lab in Tsinghua University. Her research is focused on the
failure analysis on lithium ion and lithium metal batteries, aiming to enhance both the
performances and safety of the batteries by exploring advanced materials and battery
design.
Xuning Feng received the B.E. Degree and the Ph.D. degrees in the Department of
Automotive Engineering from Tsinghua University, Beijing, China, in 2011 and 2017,
respectively. He is currently an associate Professor of School of Vehicle and Mobility
of Tsinghua University. His research interests include battery management system and
battery safety.
Dr. Yu Wu is now a postdoctoral researcher in Tsinghua University. He received his
B.E.(2014) and Ph.D.(2019) degree in Beijing Institute of Technology. His research
focuses on understanding the electrode-electrolyte interphase and thermal runaway
suppression mechanism of lithium-ion battery.
Dr. Dongsheng Ren is now a postdoctoral researcher in Tsinghua University. He
received his B.E.(2014) and Ph.D.(2020) degree in School of Vehicle and Mobility,
Tsinghua University. His research focuses on understanding the degradation and
thermal runaway mechanism of lithium-ion battery, as well as
electrochemical/thermal models for lithium-ion battery.
Dr. Gui-Liang Xu is currently an assistant chemist in the Electrochemical Energy
Storage group under the division of Chemical Sciences and Engineering at Argonne
National Laboratory. His researches focus on both fundamental understanding and
materials development for lithium-ion batteries and beyond. Dr. Xu earned his
Bachelor (2009) and PhD (2014) degree in the department of Chemistry of Xiamen
University. After three years postdoc research at Argonne, he was promoted to
permanent staff scientist. Dr. Xu has authors/co-authored 67 peer-reviewed research
articles and has 1 U.S. patent and several patent applications.
Dr. Languang Lu is an associate professor of School of Vehicle and Mobility
Tsinghua University. His interesting research fields include the integration,
optimization, and control of automotive new powertrains system and battery
management system. He has more than 100 academic papers, 1 book and 83 patents.
He has received 5 Technology Awards. The latest achievement “performance
optimization control and system integration design and application of lithium-ion
power battery for vehicle” won 2016 China automobile industry technology invention
first prize.
Dr. Junxian Hou is now work as postdoctoral researcher in the Battery Safety Lab of
Tsinghua University. She obtained his PhD from Beijing University of Technology in
2018. Her researches focus on much safer electrolyte development as well as thermal
runaway mechanisms of different electrolytes in lithium-ion batteries.
Dr. Weifeng Zhang is currently a postdoctoral researcher at the Battery Safety Lab of
Tsinghua University. He received his PhD from the Fuzhou University in 2019. His
research interests are rooted in materials synthesis and failure analysis on solid state
lithium-ion batteries
Dr. Yongling Wang received the Ph.D. degree in the Institute of Process Engineering
from Chinese Academy of Sciences, Beijing, China, in 2019. She is currently a
Post-Doc Researcher with Tsinghua University. Her research interests include
silicon/carbon anode material and battery safety.
Dr. Wenqian Xu is a beamline scientist at Advanced Photon Source at Argonne
National Laboratory. He operates Beamline 17-BM, an X-ray powder diffraction
instrument, and is interested in improving and applying in situ X-ray diffraction and
total elastic scattering techniques to materials research. He received Ph. D. in
Geosciences from Stony Brook University, and was a postdoctoral research associate
at Brookhaven National Laboratory prior to his current position.
Yang Ren received his M.S. degree in condensed matter physics from the Institute of
Physics, Chinese Academy of Science, China, and his Ph.D. degree in Chemical
Physics from the University of Groningen, The Netherlands. He is currently a
physicist and lead beamline scientist at the Advanced Photon Source, Argonne
National Laboratory, USA. His research interests focus on the structure-property
studies of materials by utilizing synchrotron X-ray and neutron scattering and other
techniques. His research activities include the investigation of phase transition,
correlated electron systems, engineering materials, nanoparticles and nanocomposites,
energy storage and conversion materials.
Zaifa Wang is currently a Ph.D. student in State Key Laboratory of Metastable
Materials Science and Technology at Yanshan University. He obtained his B.S. (2017)
from Shandong Jianzhu University in China. His research is focused on the design
and fabrication of novel solid-state electrolyte for high energy-density lithium–sulfur
batteries.
Jianyu Huang received his Ph. D. from Institute of Metal Research, Chinese
Academy of Sciences. He has been working in the area of electron microscopy and its
applications in nanoscience and energy technology for over 20 years. His current
research interests focus on in-situ studies of batteries and exploring new energy
storage mechanisms. He is also interested in developing new technologies to enable
multiple external fields coupling and cross length scale investigations of nano/energy
materials. Huang’s research goal is to correlate structure and composition with
electron, phonon, ion, and mass transport properties in nano/energy materials.
Dr. Meng Xiangfeng, director of corporation public affairs department (CPA) in
CATL, is engaged in technology, standards and regulation research of new energy
vehicle and traction battery for long-term. He is now the member of
SAC/TC114/SC27 (electric vehicles), SAC/TC77 (Alkaline Secondary Batteries). Dr.
Meng graduated from Beijing Institute of Technology, and before joined in CATL, he
worked for CATARC (China Automotive Technology and Research Center) for 5
years and for MIIT (Ministry of Industry and Information Technology) for 3 years.
Dr. Xuebing Han is an assistant professor of the state key laboratory of automotive
safety and energy in School of Vehicle and Mobility from Tsinghua University. His
research is focused on the lithium ion batteries, aiming to the smart battery design,
intelligent battery management and the advanced energy system.
Hewu Wang, is an associate Professor of School of Vehicle and Mobility of Tsinghua
University. Dr. WANG graduated from Xian Jiaotong University and received Ph.D in
Energy Engineering. He is the Executive Deputy Director of Clean Vehicle
Consortium of US-China Clean Energy Research Center and the Deputy Secretary
General of China Association for Electric Vehicles (ChinaEV100). He also served as
Chief Scientist of Chinese International Cooperation Program on science and
technology innovation. Dr. WANG has published more than 100 peer reviewed
original research articles in the field of lithium power battery safety and hydrogen fuel
cell vehicle technology roadmap.
Xiangming He is a Professor in Institute of Nuclear and New Energy Technology
(INET) at Tsinghua University. He is the director of New Energy and Materials
Chemistry Division in INET. In the R&D of lithium ion batteries and their key
materials over 20 years, focusing on the pivotal scientific fundamental of the
electrical performance and safety of lithium ion batteries. As the principal investigator,
his research projects are granted by National Natural Science Foundation of China,
Chinese Government and world-famous companies. He has authored/Edited 4 books.
He has published over 500 papers and has been awarded over 400 patents.
Zonghai Chen is currently a senior chemist at Argonne National Laboratory. He
received his B.S. degree (1997) from University of Science and Technology of China,
and Ph.D. degree (2004) from Dalhousie University. His research interest includes
functional electrolytes and electrode materials for advanced lithium batteries, with
particular focus on behavior of materials at extreme conditions.
Dr. Khalil Amine is an Argonne Distinguished Fellow and the leader of the Advanced
Battery Technology team at Argonne National Laboratory, where he is responsible for
directing the research and development of advanced materials and battery systems for
HEV, PHEV, EV, and satellite applications. He is an adjunct professor at Stanford
University. Among his many awards, Dr. Amine is the 2019 reception of the
prestigious Global Energy Prize. He is a six-time recipient of the R&D 100 Award,
which is considered as the Oscar of technology and innovation. He is an ECS fellow,
and associate editor of the journal of Nano-Energy.
Dr. Minggao Ouyang is Changjiang Distinguished Professor and the leader of
Advanced Powertrain System team at Tsinghua University, where he is responsible
for directing the research and development of Lithium-ion Battery Safety Design and
Management, PEM Fuel Cell Powertrain and Hydrogen Systems, Engine Control and
Hybrid Powertrains, Energy Storage and Smart Energy Systems. From 2007 to now,
Prof. Ouyang Minggao has been the chief scientist of the China National Key R&D
Program of <New Energy Vehicles>. He got many national and international awards.
He is Member of the Chinese Academy of Sciences and Editor-in-chief of the
international journal of eTransportation.