Degradation Mechanisms and Mitigation Strategies of Nickel Rich NMC Based Lithium Ion Batteries

Electrochemical Energy Reviews (2020) 3:43–80
https://doi.org/10.1007/s41918-019-00053-3
REVIEW ARTICLE
Degradation Mechanisms and Mitigation Strategies of Nickel‑Rich

NMC‑Based Lithium‑Ion Batteries
Tianyu Li1,3 · Xiao‑Zi Yuan1 · Lei Zhang1 · Datong Song1 · Kaiyuan Shi2 · Christina Bock2
Received: 25 April 2019 / Revised: 2 July 2019 / Accepted: 13 September 2019 / Published online: 21 October 2019
© The Author(s) 2019
Abstract
The demand for lithium-ion batteries (LIBs) with high mass-specific capacities, high rate capabilities and long-term cycla-
bilities is driving the research and development of LIBs with nickel-rich NMC (LiNixMnyCo1−x−yO2, x ⩾ 0.5) cathodes and
graphite (LixC6) anodes. Based on this, this review will summarize recently reported and widely recognized studies of the
degradation mechanisms of Ni-rich NMC cathodes and graphite anodes. And with a broad collection of proposed mechanisms
on both atomic and micrometer scales, this review can supplement previous degradation studies of Ni-rich NMC batteries.
In addition, this review will categorize advanced mitigation strategies for both electrodes based on different modifications
in which Ni-rich NMC cathode improvement strategies involve dopants, gradient layers, surface coatings, carbon matrixes
and advanced synthesis methods, whereas graphite anode improvement strategies involve surface coatings, charge/discharge
protocols and electrolyte volume estimations. Electrolyte components that can facilitate the stabilization of anodic solid
electrolyte interfaces are also reviewed, and trade-offs between modification techniques as well as controversies are dis-
cussed for a deeper understanding of the mitigation strategies of Ni-rich NMC/graphite LIBs. Furthermore, this review will
present various physical and electrochemical diagnostic tools that are vital in the elucidation of degradation mechanisms
during operation to supplement future degradation studies. Finally, this review will summarize current research focuses and
propose future research directions.
Keywords Lithium-ion battery · Ni-rich NMC · Degradation · Mitigation · Graphite · Diagnostic tools
1 Introduction LiNixMnyCo1−x−yO2 (NMC) layered oxides have received

increasing attention due to their enhanced specific capacity
Due to significant advantages such as high energy densi- and thermal stability [1]. As compared with L iMO2 (M = Ni,
ties, high galvanic potentials, wide temperature ranges, no Mn, or Co) cathodes, NMC-based cathodes also possess the
memory effects and long service lifespans, lithium-ion bat- combined merits of three transition metals in which nickel
teries (LIBs) have been widely employed in various appli- can offer high specific capacities, whereas Co and Mn can
cations, including in the fields of communication, aviation provide layered structures and enhanced structural integrity.
and transportation. Overall, the chemistries of LIBs are In addition, NMC-based cathodes can outperform lithium
constantly evolving, and in terms of cathode materials, iron phosphate (LFP) cathodes in many areas, particularly
in terms of operational voltage in which LFP-based LIBs
can only output voltages below 3.4 V [2] and suffer from
* Lei Zhang high rates of self-discharge. Moreover, materials such as
[email protected]
Li2MnO3 and lithium titanate do not possess great indus-
1
Energy, Mining and Environment Research Center, National trial potential as cathodes due to short lifespans and high
Research Council Canada, 4250 Wesbrook Mall, Vancouver, costs. Here, NMC-based cathode materials are much cheaper
BC V6T 1W5, Canada to produce (~ USD 23 per kg for NMC111) as suggested
2
Automotive and Surface Transportation Research Centre, by researchers using a co-precipitation method [3], and
National Research Council Canada, 75 Boulevard de the increase in NMC-based material prices from January
Mortagne, Boucherville, QC J4B 6Y4, Canada
2017 to March 2018 (~ 43% for NMC532 and NMC622,
3
Department of Chemistry, University of Victoria, 3800 and ~ 27% for NMC811) [4] indicates that more research is
Finnerty Rd, Victoria, BC V8W 3V6, Canada
13
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44 Electrochemical Energy Reviews (2020) 3:43–80
being directed to the field of NMC-based cathode materials coating as recent research progress, whereas Myung et al.
due to their commercial potential. [29] in their review only provided a brief developmental
Following the initial commercial success of history of NMC and NCA-based LIBs with a focus on the
LiNi1/3Mn1/3Co1/3O2 (NMC333 or NMC111), NMC-based categorization of gradient layers and core–shell structures
LIBs have become the mainstream with gradual improve- as remedies. A more recent and detailed review conducted
ments in NMC technology through the steady increase by Hou et al. [30] covered more mitigation topics varying
in the nickel content in each generation of cathode mate- from ion substitution and electrolyte additives to gradient
rials. And because Ni can cycle between N i 2+/ 3+ and layers; however, to the best of our knowledge, no review has
Ni3+/4+ redox couples without large variations in voltage presented a comprehensive collection of mitigation methods
during the charge/discharge process, layer-structured Ni- or has categorized them based on characteristics. Similarly,
rich NMC ( LiNixMnyCo1−x−yO2, x ⩾ 0.5) cathodes [e.g., controversies in mitigation strategies and trade-offs need to
L iNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532), L iNi 0.6 Mn 0.2 Co 0.2 O 2 be considered, such as the selection of dopants or coating
(NMC622) and the most recent L iNi 0.8 Mn 0.1 Co 0.1 O 2 materials, all of which have yet to be discussed. Based on
(NMC811)] have been developed. Here, the main advan- this, these vacancies in the literature will be covered in this
tage of Ni-rich materials is their high discharge capacity review to assist in the further investigation of Ni-rich NMC-
(200–220 mAh g−1), which represents a large increase in based LIBs.
energy density (~ 800 Wh kg−1) as compared with con- Apart from the cathode, graphite—the anode material
ventional LiCoO2 (~ 570 Wh kg−1) and LiMn2O4 spinel that has received the most attention in LIBs due to its high
(~ 440 Wh kg−1) materials [5]. In addition, increasing the Ni mass-specific capacity and economic advantages [26, 31,
content is the most effective method to enhance capacity in 32]—can function collaboratively with NMC-based cath-
the current state-of-the-art LIBs without requiring advanced odes to provide promising performances in coin cells [20,
and novel battery chemistries. As a result, researchers are 33], pouch cells [9, 34], pouch bags [11] and T-cells [35].
reviewing recent progress achieved in the development of Based on this, this review will also provide a complete pic-
Ni-rich cathode materials in an attempt to provide important ture of the aging of graphite anodes that can affect both elec-
clues for the future design of Ni-rich cathodes [6]. trodes in battery cells based on degradation mechanisms and
However, although increasing Ni percentages can allow effective mitigation strategies. Furthermore, the solid elec-
for enhanced Ni-rich NMC-based battery performances trolyte interface (SEI) is a film that forms on graphite anode
as compared with other NMC combinations in terms of surfaces during initial charging [36–39] and thickens in sub-
capacity, capacity fading becomes severely pronounced. To sequent cycles, which can protect and impede anodes and
address this, significant efforts have been made to elucidate is vital in the discussion of the aging behaviors of graphite
the mechanisms of capacity fading and associated growth anodes. Therefore, detailed mechanisms of anode SEIs are
of impedance [7, 8], as well as to find remedies [9–12]. And also reviewed to supplement previously published reviews.
in recent decades, numerous studies and reviews have been To further investigate the degradation mechanisms of
published worldwide [13–15] in which various testing proto- LIBs, multiple physical methods have been used in both
cols [16], research methodologies, models [17–19] and phys- electrochemical tests and physical characterizations [e.g.,
ical characterizations [9, 20] have been used to interpret the electrochemical impedance spectroscopy (EIS) to charac-
behavior of NMC-based cathodes with or without modifica- terize the resistance of electron transfer and surface films].
tions. Here, studies based on microscopy [21], crystallog- Conventional and modern physical characterization methods
raphy [22], mass spectroscopy [23], gas measurements [24] have also been utilized to reveal surface morphology, ele-
and calorimetry [8] have revealed that parasitic reactions [7], ment compositions, crystal lattice dimensions and reaction
cation mixing (leading to restructured surface regions) [25], processes, and are also important to the interpretation of the
active material dissolution [26] and oxygen release [23, 25] degradation of Ni-rich NMC/graphite LIBs. Based on this,
are primary factors responsible for cathode degradation at these diagnostic tools will also be presented in this review.
the atomic scale. In addition, scanning electron microscopy To fully present the evolution of electrode performances
(SEM) [13] together with computational studies [27] has in Ni-rich NMC/graphite LIBs, degradation mechanisms
revealed that intergranular cracking can weaken connec- based on various experiments and recent mitigation strate-
tions between primary particles. Despite these findings, the gies in which cell conditions were evaluated separately or
majority of recently published studies are insufficient and as a whole are presented in this review. And overall, this
only partially cover the processes through which degradation review will provide a summary of the recent advances in
occurs. For example, Liu et al. [28] reviewed surface lay- Ni-rich NMC-based batteries and can supplement pioneer-
ers and surface chemistries during Ni-rich NMC-based LIB ing reviews published previously.
operations and presented cationic doping and metal oxide
13
Electrochemical Energy Reviews (2020) 3:43–80 45
2 Degradation Mechanisms 2.1.1 Surface Degradation During Cell Operation
Ni-rich NMC-based materials are some of the most prom-

ising cathode candidates for next-generation LIBs due to Lattice Expansion/Contraction NMC oxide possesses an R3m ̄
high capacities and large voltage windows. Despite impres- structure (rhombohedral symmetry) with a Li-layer on the
sive progress in the development of advanced materials and 3a site, an NMC layer on the 3b site and an oxygen layer
fabrication processes, the development of high-capacity on the 6c site [7] and can usually be indicated in the split-
electrodes with long-term stability and prolonged cycle ting of (110) and (108) peaks and of (006) and (102) peaks.
lifespans remains an important challenge. To address this, For example, the expansion and contraction of the c-axis
the understanding of underlying degradation mechanisms (14.21 Å) of NMC811 lattices can be observed by using
presented in this review can serve as a starting point to learn in situ XRD measurements in the cell voltage windows of
and improve the performance of Ni-rich NMC-based cath- 3.0–4.0 V and 4.0–4.4 V, in which (003) peaks can decrease
odes. In addition, the information included in this review can from 18.96° (3.0 V) and subsequently rise to 19.09° (4.4 V)
provide valuable insights into the creation of new devices [7, 10, 43]. This can also be observed for the movement
with improved efficiency and productivity. And for the sake of (104), (015) and (108) peaks. Here, researchers suggest
of completeness in the understanding of degradation mecha- that the expansion of the c-axis is due to the repulsive force
nisms in LIB full cells, parasitic reactions on NMC-based generated from MO6 slabs, which are positively charged in
cathode surfaces, the aging of graphite anodes as well as SEI a highly delithiated state, whereas the loss of electrons can
formation and aging are also briefly presented in this section. shrink the radius of transition metal ions to reduce the a-axis
[44]. In addition, the (110) peak can shift to higher angles in
2.1 Ni‑Rich NMC‑Based Cathodes experiments, suggesting that the a-axis can contract during
charging due to the smaller radius of transition metal ions
The degradation of Ni-rich NMC LIBs involves differ- at elevated valences [45]. Researchers have also reported
ent types of capacity loss, including initial capacity loss that the a-axis of NMC811 lattices remains constant at
(ICL), sudden capacity loss (SCL) and gradual capacity potentials exceeding 4.3 V [10] and that a steep drop of
loss (GCL), all of which are accompanied by impedance the c-axis occurs at potentials exceeding 4.2 V in which the
growth. And in the case of GCL, which is the most fre- drop becomes steeper as the Ni content increases [7, 20, 43].
quently investigated process, a major cause is the loss of Li Here, researchers proposed that this drop is due to the fact
and transition metals on cathode surfaces. In general, the that the repulsion between O2− layers decreases with more
majority of degradation mechanisms for Ni-rich NMC-based covalent M–O bonding at higher delithiated states [46, 47]
cathodes can be indexed to the same mechanism independ- (Fig. 1a, b). Furthermore, studies have also confirmed two
ent of Ni/Mn/Co ratios because they share similar crystal pathways (Fig. 1c2, c3) involved in the delithiation of Ni-
and microspherical structures. Here, adjustments (typically rich NMC-based cathodes [40, 48], including oxygen dumb-
increases in Ni) to the relative amounts of Ni, Mn and Co bell hopping and tetrahedral site hopping, in which at the
can result in augmented performances as well as various beginning of charging, Li can exit through oxygen dumbbell
negative features. For example, enhanced mass-specific hopping until a certain degree of delithiation is reached and
capacity can be achieved but at the expense of rate capabil- continue through tetrahedral site hopping due to increased
ity and structural stability. In addition, researchers have also energy barriers as caused by Li–O bonds during delithiation.
reported higher electronic conductivity and reduced polari-
zation [40] in which the varied polarization as compared Surface Reconstruction to Fm3m Rocksalt Surface reconstruc-
with the portion of Ni is caused by the higher eg orbital of Ni tion of the particles of NMC-based cathodes can initiate
over the t2g orbital of Co [41]. Researchers have also shown if delithiation exceeds 70% as shown in NMC111 [49]. In
that the reduced Mn content can result in faster degradation addition, increasing the Ni content can lead to increased
through surface reconstruction [42] and that the increased portions of Ni3+ (usually Ni ions with higher valences) in
Ni content can result in increased cation mixing due to the the total amount of Ni. Furthermore, elemental Ni partially
bulk diffusion of N i2+ into the Li-layer and increased para- located in the transition metal layer as Ni2+ (0.69 Å) pos-
sitic reactions as the valence of surface Ni increases toward sesses a similar radius to Li+ (0.76 Å) [50], and Li+ and
highly reactive N i4+. Overall, cathode performances can be Ni2+ can exchange positions in a delithiated state through
impacted by various factors that interact with each other, and Ni2+ diffusion to the octahedral sites of Li+ (energetically
therefore, this section will discuss degradation mechanisms favorable) through a neighboring tetrahedral site (Fig. 1c)
in detail. [42, 51]. Here, the degree of N i2+ migration can be evalu-
ated by calculating the c/a ratio of the NMC lattice because
this migration reduces the c/a ratio. And based on XRD
13
measurements, ratios of I003 to I104 can decrease to less the cell, which can react with electrolytes to generate CO2
than 1.2 after significant cation mixing and can therefore and result in increased electrode interfacial resistances due
serve as an indicator of the degree of cation mixing [52]. to kinetic barriers in the Li+ insertion/desertion process [50].
Moreover, researchers reported that cation disorder can To address this, researchers reported that NMC811 cathodes
lower spacing between atomic layers in the lattice of the pretreated with ramping to 4.5 V limited the growth of the
NMC-based cathodes, hinder L i+ movement and reduce the rocksalt layer in subsequent cycles and can serve as a pillar
amount of active Ni and Li [53]. In the case of higher Ni structure to stabilize the lattice and isolate the surface of
percentage cathodes, Mn4+ can partially be replaced by Ni, NMC particles [67]. Furthermore, researchers reported that
which increases the valence of Ni and therefore lowers the the oxidation states of Mn and Co decrease in the surface
possibility of Ni atoms migrating to 3a sites [8]. However, layer/region of NMC811 and NMC442 after cycling [9, 63].
because the total amount of Ni also increases, Ni2+ migra-
tion still occurs to a larger extent. To minimize N i2+ migra- Phase Transformations Two hexagonal phases of NMC811
tion, researchers reported that mitigation methods can be can coexist on the surface of particles if freshly prepared
used to modify cathodes [54]. Furthermore, a disordered in which the evolution of one phase is irreversible and van-
spinel structure (Fd3m) due to non-ideal cation mixing [55] ishes after initial charging (with lattice constants remaining
can form if LIBs are charged to high voltages (e.g., 4.8 V) at the initial value), whereas the second phase is reversible
[21, 56–60] and consists of a L iM2O4 spinel structure and a (except for a small difference between charging and dis-
M3O4 spinel structure if Co migration into tetrahedral sites charging above 4.2 V). Here, the fading of the (110) peak at
occurs [42] (Fig. 2a). Xiong et al. [61] and Eom et al. [62] 65.12° can track the conversion of the region in which the
also reported that spinel phases can be formed on charged two hexagonal phases coexist and are converted to a single
cathodes stored at 90 °C for a week. Moreover, research- phase [7]. In addition, the broadening of the (003) peak dur-
ers found that migrated Mn and Co possess high valences ing cycling as recorded by using in situ XRD measurements
and smaller radii for movement and more vacancies in the is of great interest in which researchers [25] suggested that
Li-layer in a highly delithiated state [63]. Researchers also this phenomenon was due to the creation of a second phase
reported that long-term cycling to 4.2 V (NMC 622) [64] in the potential range of 3.8–4.0 V (H2, evolved from the
can result in phase changes to an Fm3m structure consisting monoclinic phase in contrast to the phase H1 following
of Ni2+, Mn2+ and C o2+ with lowered valence states as com- the stoichiometric composition) that possesses less Li.
pared with a spinel structure [63, 65] and ion-insulating [56, Researchers also reported that this process occurred earlier
63, 66] (a cubic rocksalt phase) (Fig. 2b). Here, the conver- with higher Ni portions (Fig. 2c) and that at higher volt-
sion from a layered structure to a cubic rocksalt phase (usu- ages, the conversion from H2 to H3 occurs with impedance
ally confirmed by HRTEM/EELS [9]) can release O 2 into growth (volume contraction) only for NMC811 (or NMCs
Fig. 1 The c-axis (a1), the a-axis (a2) and potential (a3) of an Author(s) 2015. Published by ECS). c1 Lattice of an NMC layered
NMC 811 cell as a function of specific capacity. The c-axis (b1) structure. c2 Tetrahedral site pathway and c3 oxygen dumbbell path-
and the a-axis (b2) as a function of cell potential during the second way for Li-ion diffusion in an NMC layered structure (Reprinted with
cycle and dQ/dV of the second cycle as a function of cell potential permission from Ref. [48]. Copyright © 2015 WILEY-VCH Verlag
(b3) (Reprinted with permission from Ref. [7]. Copyright © The GmbH & Co. KGaA, Weinheim)
13
with Ni portions larger than 80%) [25]. Researchers have can lead to more hydroxide (e.g., LiOH) on NMC622 [72]
also found that the phase transition from H2 to H3 can lead and that surface impurities can affect cell impedances in sub-
to (003) peaks shifting to higher degrees [68] and that Li- sequent cycles through reactions with electrolytes to form a
reordering (Li diffusing into Ni4+-rich sites) can further Li+ diffusion inhibiting layer.
convert H3 to H3-2 [69] in which the fast shrinkage of the
c-axis at potentials above 4.15 V is a clear indication of
this phase transition. Moreover, the generated microregion x
Li(Ni, Mn, Co)O2 + CO2 +
x
O
of NiO2 in the intralayer of the NMC811 lattice as a result 2 4 2
x (1)
of the phase transition from H2 to H3 can lead to the irre- → Li1−x (Ni, Mn, Co)O2 + Li CO
2 2 3
versible transformation of the NMC811 structure [45] and
this phase transition becomes severer as Ni portions further
increase to extreme numbers as indicated by rising peaks NMC Dissolution The dissolution of NMC materials can
of the differential capacity curve centered at 4.15 V [68]. also result in capacity attenuation [26, 74] because it can
Here, the fading of this peak leads to capacity fade and is decrease Li+ insertion sites and is triggered by the products
referred to as the “deleterious effect.” Furthermore, phase of electrolyte decomposition such as HF from the reaction of
changes to a second hexagonal phase for other NMC-based PF5 with H2O (Eqs. 2, 3) [31]. In addition, higher voltages
cathodes have yet to be clarified. (Fig. 2d illustrates crystal can accelerate the dissolution of NMC111 due to the release
lattice evolution during delithiation.) of more acidic components as a result of rapid electrolyte
decomposition [75]. Despite these findings, effects on Ni-
Surface Stabilizer In general, NMC-based cathodes with rich NMC have yet to be reported. The dissolution of NMC
more Mn content tend to possess better cycling stability [13, materials can also cause a concurrent issue involving the
70], whereas NMC-based cathodes with more Ni content production of resistive M
Fx as a side product on the surface
are believed to be incapable of reaching high cutoff volt- of NMC particles. Moreover, the dissolution of transition
ages due to the lack of M n4+ as a structure stabilizer [65]. metals can pose a threat to anodes through electrodeposition
Apart from N i2+, structural instability also applies to M
n3+, [32, 76], catalysis of solvent reduction [77] and formation
although with the high Ni content, Mn migration is not con- of inorganic layers in SEIs [78], all of which can impede
sidered to be significant. Here, due to low octahedral site Li+ intercalation and reduce capacity [79]. Here, Mn3+ dis-
stability energy, NMC-based cathodes possess a tendency to proportion into Mn2+ and Mn4+ was proposed to explain
form spinel-structured LiMn2O4 on surfaces [71] and Mn4+ Mn dissolution [26, 75] as previously reported in Li–Mn–O
possesses a similar tendency to migrate to the Li-layer [33, spinel structures [80, 81] and various electrolytes have been
71] and decrease capacity. Nevertheless, diffused Mn4+ on utilized to form protective surface films containing carbon
particle surfaces can stabilize structures during long-term on electrodes to isolate surfaces from electrolytes [33].
cycling [50].
LiPF6 → LiF + PF5 (2)
2.1.2 Impurities and Parasitic Reactions
LiPF6 + 2e− + 2Li+ → LiF + Lix PFy (3)
Surface Impurities To maintain a layered structure, excessive Self‑redox Reaction At highly delithiated states, the valence
Li is used for Ni-rich NMC-based cathodes. However, side of transition metals increases, and because the low-spin
reactions of Li with water vapor and CO2 in air can lead Co3+/4+:t2g band overlaps with the 2p band of O 2− (Fig. 3b),
to LiOH and L i2CO3 in which exposure to air can result electron transfer from O 2− to C
o3+/4+ can occur and reduce
in a reconstructed surface layer 3 nm thick (evidenced by oxidized transition metal ions, thus releasing O2 into bat-
STEM) that thickens if cycled [9]. A surface layer with simi- tery cells [82]. Oxygen release based on this also occurs
lar impacts can also form as cathodes come into contact at the first charging period in which O2− reduces transition
with electrolytes [65]. Here, researchers suggest that this metals oxidized to 4+ (similar effects on N i4+ also exist and
reconstructed layer can be tuned through different synthesis dominate oxygen release in Ni-rich NMC-based cathodes)
methods of the cathode powder [63] and that in the case of [14, 42].
NMC111, surface impurities can also grow on top of cath-
ode particles as resistive films over the same time period for Parasitic Reaction: Effects of Ni4+ Highly delithiated (highly
uncycled Ni-rich NMC-based LIBs [35] that contain mainly charged) states tend to generate large amounts of N i4+ that
insulating hydroxides and carbonates as revealed through can react with electrolytes. (No reaction schemes have been
Raman spectroscopy (Fig. 3a). Here, the circumstances in proposed.) This side reaction can significantly thicken cath-
which Li2CO3 (Eq. 1) or NiCO3 is favored remain unclear ode–electrolyte interfaces (CEIs) and reduce the number
[35, 72, 73]. Researchers also reported that high humidity
13
Fig. 2 a Schematic of phase transition and possible TM cation migra- graphite cells recorded at 0.1 C-rate (3rd cycle) with marked phase
tion pathways in charged NMC cathode materials during thermal transformations (Reprinted with permission from Ref. [25]. Copy-
decomposition (Reprinted with permission from Ref. [42]. Copyright right © The Author(s) 2017. Published by ECS). d Schematic of H1–
© 2014, American Chemical Society). b Degradation mechanisms of H2–H3 phase transformation from the perspective of local environ-
LiNi0.5Co0.2Mn0.3O2 after cycle tests under two upper cutoff voltage ments in different views along the c-axis (up) and the a-axis (bottom)
conditions (4.5 V and 4.8 V) (Reprinted with permission from Ref. (Reprinted with permission from Ref. [69]. Copyright © 2018, Else-
[56]. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, vier B.V. All rights reserved.)
Weinheim). c Differential capacity plot of three different NMC/
of available L i+ [14, 83], thus increasing impedance [13]. higher Ni content suffer more from parasitic reactions with
Researchers have also investigated gas evolution (CO2) from Ni4+ that are a source of emitted C O2. In addition, because
NMC532 cathodes using DEMS [84], and isothermal calo- highly reactive oxygen can be produced through O2− from
rimetry (IMC) results have shown that at highly delithiated self-redox reactions, surface reconstructions and highly del-
states above 4.2 V, the further removal of Li from NMC811 ithiated cathodes (ca. > 80%) [86], CO and C O2 can also be
cathodes can result in decreased entropy and endothermic traced back to the reaction between O2 and alkyl carbon-
heat flow [7] in which rapidly increasing heat flow indicates ate electrolytes (Eq. 4) [24, 25]. Alternatively, sweeping to
that the highly delithiated cathode is very reactive with the higher voltages can also cause the electrochemical decompo-
electrolyte and can therefore cause capacity fading. In addi- sition of electrolytes to produce CO2 (Eq. 5, Fig. 3c) [23, 24,
tion, researchers also found that remaining at a highly del- 87]. Furthermore, Gasteiger et al. [88] have experimentally
ithiated state can cause significant electrolyte oxidation as shown three other mechanisms that may contribute to CO2
well as other side reactions [9]. emission, including solvent hydrolysis (if trace amounts of
OH− exist), electrolyte impurity oxidation and HF reacting
Parasitic Reaction: CO2 generation Large N i 4+ portions with lithium carbonate as a surface impurity. Moreover, the
at higher voltages can cause increased CO2 evolution at decomposition of lithium carbonate has also proven to be a
increased upper cutoff voltages [85] in which cathodes with source of CO2 [89, 90]. Researchers have also suggested that
13
Fig. 3 a Raman spectra of fresh and stored NMC111 and NMC811 cal oxidation pathways for ethylene carbonate (EC) and their potential
electrodes before cycling, measured in air within ~ 1 h with the sam- dependence (Reprinted with permission from Ref. [25]. Copyright
ples not treated prior to measurements (Reprinted with permission © The Author(s) 2017. Published by ECS). d Schematic of the dif-
from Ref. [35]. Copyright © The Author(s) 2018. Published by ECS). ferent issues facing Ni-rich NMC materials: (1) SEI formation and
b Positions of various redox couples relative to the top of the oxy- reactivity of Ni4+; (2) Li/Ni displacement and formation of disordered
gen 2p band (Reprinted with permission from Ref. [14], https://pubs. phases; (3) microcracks in secondary particles (Reprinted with per-
acs.org/doi/10.1021/acscentsci.7b00288. Copyright © 2017, Ameri- mission from Ref. [13]. Copyright © The Author(s) 2016. Published
can Chemical Society. Further permissions related to this figure by ECS)
should be directed to ACS). c Proposed electrooxidation and chemi-
NMC-based cathodes with Ni-rich surfaces behave differ- 2.1.3 Other Issues

ently than other cathodes with different portions of Ni [7].
For example, the degradation of NMC811 cells was studied Initial Capacity Loss Initial capacity loss is strongly linked
by using different electrolyte additives including VC and to the loss of available Li and the growth of impedance
PES211 to suppress side reactions and it was revealed that in anodes due to SEI formation. Here, researchers have
NMC442/graphite cells and NMC111/graphite cells showed reported that NMC-based cathodes cannot return to their
better performances with PES211, whereas NMC811/graph- fully lithiated states after initial cycling [26] in which sepa-
ite cells aged slower with VC (with slower capacity fading rate mechanisms have been proposed, including parasitic
and impedance growth) [79]. Here, PES was also reported reactions consuming L i+ [93] and the sluggishness of L i+
to be a viable additive for the suppression of gas evolution diffusion into the few vacancies of the Li-layer [94] (cir-
[91] and impedance growth during cycling to higher volt- cumstantially proved by Gasteiger et al. [26]). In addition,
ages (above 4.3 V), and rocksalt surface layers formed with researchers have also suggested that initial capacity loss
the use of VC but not with PES211, concluding that elec- is related to the C-rate because it is kinetically influenced.
trolyte additives can significantly affect the rate of parasitic Furthermore, partial losses of available cathodic Li occur
reactions and that parasitic reactions were the main reason to compensate for losses of anodic Li+ to SEIs [26], and
for capacity fading [7, 92]. other losses of Li in the cycling period can be attributed to
parasitic reactions including the immobilization of Li in the
EC + 2O2 → 2CO2 + CO + 2H2 O (4) SEI and enlarged polarization, which become significant at
higher cutoff potentials [26, 95].
EC → CO∕CO2 + R-H+ + e− (5)
13
Cracking of Secondary Particles Reduced performances due 2.2 Graphite Anode

to the cracking of spherical secondary particles have been
extensively reported and are of significant concern [96]. Similar to the cracking of NMC secondary particles, crack-
Here, the expansion and contraction of the c-axis during ing can also occur in graphite anodes due to Li intercalation/
repeated cycling at above 4.2 V can lead to microstrains on deintercalation, which can expand and contract the distance
particles in cathodes, leading to the generation of microc- between graphite layers [102]. In addition, recent research
racks in the core of primary particles with some initially indicated that unit cell expansion (13.2% in total) during
generated cracks being able to close in subsequent cycles Li intercalation is neither continuous nor linear, but staged
[68]. These cracks can cause poor connection between par- (Fig. 4a–e) [103]. Here, Li intercalation from C 6 (Li-free
ticles and micropores and even the cracking of secondary graphite) to LiC24 (Stage 2L) showed no in-plane ordering
particles [13], all of which contribute to degradation at the of intercalated Li, whereas from 2L to LiC12 (Stage 2), the
microscale. To address this, Lim et al. [27] have used first- ordering of Li appeared and the lattice can be assigned to the
principle calculations to study these cracks generated by space group P6/mmm. Furthermore, in the transition from
gaps between primary particles and found that they were a Stage 2 to L iC6 (Stage 1), total volume change suddenly
result of anisotropic and average contractions. In addition, increases as the amount of x exceeds 0.6 in L ixC6 (where
researchers reported that these cracked particles possessed Stage 1 appears as Li presents in every interlayer). These
enlarged surface areas and therefore increased the possibil- results showed that optimal composition was between 20 and
ity of parasitic reactions [13]. Moreover, these microcracks 80% charged in which Stage 2 stably exists or extends into.
were also found to partially originate from the gas evolution Furthermore, “dead lithium,” which is Li-ions electro-
of NMC particles [13] (Fig. 3d), and recent studies on coated chemically plated onto the surface of graphite anodes, is
NMC (76 14 10) suggested that the infiltration of liquid the principal reason for capacity fading, especially at final
electrolytes into the gap between primary particles can also stages [104]. This phenomenon occurs on graphite surfaces
cause cracking [97]. Alternatively, various NMCs have also that possess limited mass transport, slow diffusion within
been found with no cracking by using SEM [7, 20]. Here, the graphite or low charge transfer speeds [105] and is
Dahn et al. [20] suggested that the shell of core–shell struc- strongly promoted by low temperatures/large polarizations
tured NMC cathodes (a Mn-rich shell and a Ni-rich core) (including high electrolyte resistances induced by high tem-
was resistant to cracking due to the absence of compressive peratures) during lithiation as well as the properties of the
stress on the core and tensile stress on the shell. Based on graphite electrode (e.g., morphology [102], loading). And
all of this, numerous mitigation methods including carbon as Li+ intercalation is replaced by Li plating, issues such
matrixes and gradient layers have been proposed to resolve as dendrite growth become more pronounced, leading to
cracking at the microscale (further details in Sect. 4.1). increased impedance and more importantly, potential safety
hazards due to internal short circuiting. To avoid this, the
The Effects of Temperature Studies have shown that cell limits of charging currents and the state of charge need to
degradation can accelerate at elevated temperatures above be established to maintain polarization in optimal ranges
30 °C and that at low C-rate cycling, cell degradation is [106]. However, large polarizations also need to be adopted
mainly affected by the time in which cells are placed under to minimize charging durations to meet industrial applica-
high temperatures and not by cycling [98]. Long-term tion demands. Here, researchers reported that the reduction
operation of LIB cells can produce large amounts of heat. of graphite thicknesses and improvements in porosity can
And although this released heat may even be useful in cold decrease charge transfer impedances [105, 107].
weather conditions, heat emissions are a major issue of Ni-
rich NMC-based LIBs due to thermal instability [33] in 2.3 SEI
which thermal runaways can occur if NMC-based cathodes
react with LiPF6 from the electrolyte and limit the com- Electrolytes used in LIBs contain two main components
mercial and practical use of these battery packs. To improve including Li salt and organic solvents. Here, the use of
thermal stability, coatings such as S
iO2 [62], TiO2 [99] and additives as film-forming agents can allow for stable SEIs
Li2ZrO3 [100] have been chosen to prevent contact between and, in general, the concentration of Li salt is maintained
cathodes and electrolytes, and an ALD-coated NMC532 at 0.8–1.3 M to optimize electrolyte viscosity and ion con-
with Al2O3 has even been reported [101] to resolve the issue ductivity. As compared with cathodes, the potential of LIB
of uneven coatings and prevent the failure of cathode separa- anodes is low and can trigger electrolyte reduction (SEI
tion from electrolytes. formation), which can cause Li loss during initial charg-
ing (Fig. 4f) [31]. However, because SEIs are electronically
insulating, further reductions of electrolytes do not occur
13
in which formed SEIs are usually 10–50 nm thick and are deposited onto graphite anodes, both of which lower stor-
conductive to Li+ ions. Researchers have extensively stud- age capacity [38]. Researchers have also proposed another
ied the constituents of passivating SEIs on graphite anodes mechanism of Li+ that suggests that even monolayer Mn2+
and have reported that lithium ethylene dicarbonate (LEDC, can impede the movement of Li+ through the graphite and
Eq. 6, Fig. 5a–d) [108] was the main component of SEIs the SEI [111]. As for PF5, it is produced from the decompo-
formed with ethylene carbonate (EC) solvent [109] apart sition of various electrolytes and can trigger the open-ring
from electronically insulating LiF and gaseous products polymerization of EC, which further increases SEI decom-
(H2 and C2H4). Propylene carbonate (PC) as a solvent has position along with the production of HF [112]. Moreover,
also been well investigated due to its thermal stability and the damage/repair process caused by gaseous P F5 consumes
wide voltage windows. Furthermore, DFT calculations have active Li-ions until Li-ions are depleted in the system [113].
shown that stable SEI films can be produced by oligom- Researchers have reported, however, that this degradation
ers of SEI film components (SFCs) [108], which are first can be mitigated through the addition of Lewis-basic addi-
created through solvent decomposition. LiF is also a prod- tives. The presence of H2O in electrolytes can also reduce
uct of almost all common Li salts such as LiPF6 (the only the production of C 2H4 (usually used as an indicator of EC
commercially available salt), L
iBF4, LiTFSi, LiTSi, etc., in reduction) and promote H2 production. Here, the existence
which researchers reported that the amount of LiF produced of SEIs can reduce the reduction of trace amounts of water
from LiBF4 was large and would result in the formation of a that usually generate H2 and CO2 [114].
grainy film instead of a smooth film. An automotive scale NMC pouch cell was also analyzed
by Dahn group using ultra-high precision cycling technolo-
2EC + 2Li+ + 2e− → Li2 EDC + C2 H4 (6) gies, and it was revealed that the performance of graphite
As aging continues during cycling, researchers believe anodes was decisive and that corresponding capacity fading
that the inorganic portions of SEIs also increase as LiF (proportional to t1/2) was related to SEI thickness and was
(can be used as an indicator of SEI maturation) is produced inversely proportional to the rate of SEI growth, suggesting
through LiPF6 reacting with lithium carbonates (Eqs. 7, 8) that the gradual lowering of SEI thickening rates can lead to
[37]. stable SEIs [115, 116]. Here, alternative relationships pro-
2RCO3 Li + LiPF6 → 2LiF + 2RF + LiPO2 F2 + 2CO2 (7) posed for SEI growth need to take stability as a factor into
consideration [117].
RCO3 Li + LiPF6 → 2LiF + RF + POF3 + CO2 (8)
After SEI formation, the resistance of anodes/SEIs toward 2.4 Summary
divalent transition metal ions such as Ni2+, Co2+, Cu2+ and
Mn2+ (relatively more impactive) is significantly enhanced, Overall, the degradation of Ni-rich NMC-based cathodes
preventing the reduction of EC solvent by these ions. How- originates from the insertion/desertion of Li+ during charge/
ever, formed SEIs remain targets to many reductive sub- discharge in which the expansion and contraction of crys-
stances in which reductive decomposition can degrade SEIs tal lattices (primary particles) gradually generates tension,
(Li2CO3 and C2H4 are produced as a result) and expose ther- leading to the cracking of secondary particles (Fig. 6). Elec-
modynamically unstable graphite anodes to reactive environ- trolyte infiltration as well as oxygen release can further dete-
ments [38]. Here, if the exposure of graphite anodes occurs, riorate this issue. On an atomic scale, Ni4+ can accumulate
a series of damage can occur on the graphite anode, includ- during charging because delithiation can elevate the valence
ing the intercalation of solvated Li+, which leads to larger state of Ni together with high-valence Mn and Co ions. And
sizes and the potential risk of the breaking of the graphite due to smaller radii, easier diffusion can lead to surface
n2+ has been reported to be able to pen-
layer. In addition, M reconstruction (from rhombohedral to rocksalt), which can
etrate SEIs and reside in the inner area between the SEI and further inhibit Li+ insertion/desertion. Moreover, increased
the anode through the exchange of positions with Li+ ions voltage levels of high-valence ions can trigger side reactions
located in the SEI [110]. Furthermore, the recurrent genera- such as the oxidization/decomposition of electrolytes and
tion of C n2+ is a destructive substance
2H4 suggests that M the further dissolution of NMC materials. Electrochemical
to both solvents and graphite anodes in which accumulated potentials of electron-depleted Co and Ni can also fall below
Mn2+ near graphite can function as a catalyst, suggest- the fermi level of O 2−, leading to the transfer of electrons
2−
ing that it is reduced at the surface of the anode but can from O to transition metal ions and the release of O 2 into
reduce EC afterward, leading to thickened SEI films and the systems, which can also cause electrolyte decomposition.
immobilization of active Li (Fig. 5e) [110]. In addition, the Throughout the operation of Ni-rich NMC-based LIBs, four
reduction of M n2+ can cause the gradual transfer of active types of unwanted substances exist on the surface of cathodic
Li to SEIs or the conversion of active Li+ into compounds
+ particles, including other phases, surface impurities (carbon-
ates and hydroxide), rocksalt structures and surface films. To
13
Fig. 4 Crystal structures of a

graphite (space group P63/mmc)
and two major Li intercalation
compounds, b LiC12 and c LiC6
(space group P6/mmm). Differ-
ent stacking of graphene layers
with d the AB sequence in
graphite and e the AA sequence
in LiC12 and LiC6 (Reprinted
with permission from Ref.
[103]. Copyright © 2018,
American Chemical Society). f
Schematic of SEI formation and
degradation on graphite anodes
(Reprinted with permission
from Ref. [31]. Copyright ©
2005, Elsevier B.V. All rights
reserved.)
sum up, aging effects on both micrometer and atomic scales As for graphite anodes, degradation primarily occurs due
can result in two common outcomes in which the first is to the plating of Li dendrites and the cracking of layered
the chemical (through chemical reactions) and mechanical graphitic structures. In addition, SEIs tend to thicken dur-
(through the breakage of crystallites) damage/loss of active ing cell operation as EC solvent is reduced electrochemi-
materials and the second is the production of detrimental cally. Furthermore, transition metals, especially Mn2+ from
substances on electrode particle surfaces, including surface dissolved NMC, can cause significant capacity loss due to
films (both SEIs and CEIs), surface impurities and surface massive damage to SEIs. A comprehensive list of identified
layers. And although many differences in the performance of degradation mechanisms for Ni-rich NMC-based cathodes,
various Ni-rich NMC-based cathodes have been discovered, graphite anodes, SEIs and CEIs is presented in Table 1.
these remain unexplained. Therefore, future studies should Here, the degradation mechanisms of SEIs are categorized
focus on the interpretation of different aging behaviors in based on anodes and the degradation mechanisms of CEIs
NMCs with or without mitigation methods.
13
3 Diagnostic Tools
3.1 Electrochemical Techniques
Throughout the development of LIBs, a variety of electro-

chemical methods have been employed to test, analyze and
diagnose LIBs. To provide a comprehensive overview, these
methods are categorized into three groups, including charge/
discharge tests, cyclic voltammetry (CV) and electrochemi-
cal impedance spectroscopy (EIS).
3.1.1 Charge/Discharge Tests
Charge/discharge tests include basic electrochemical char-

acterizations that can be used to determine the voltage at
which a certain reaction (including Li+ insertion/desertion
reactions that generate current in external circuits and side
reactions that negatively impact cell performance) occurs
and that can be used to evaluate the reversibility of cycling
performances. Data from these charge/discharge tests can
be analyzed by using many methods and can provide useful
information on cell performance, reaction and reversibility,
degradation and associated mechanisms.
Voltage versus capacity Charge/discharge curves are com-

mon and useful plots contained in almost every published
study in the field of batteries. These plots are usually dis-
played in the format of voltage versus capacity (normalized
by the mass of the active material) for a clear understanding
of total capacity within a voltage range and capacity loss
for certain cycles, including initial capacity loss (ICL), sud-
den capacity loss (SCL), gradual capacity loss (GCL) and
Fig. 5 DFT-MD snapshots of electrode/electrolyte interphases with voltage versus time. In some studies, the horizontal axis is
Li2EDC: a adhesion structure of one L i2EDC monomer on a graph-
changed to the content of Li in NMC compounds for easier
ite electrode, b dissolution structure of one L i2EDC molecule in EC
solvent, c adhesion structure of 12 Li2EDC molecule aggregates on comparison with physical characterization results in terms of
a graphite anode, d dissolution structure of 12 Li2EDC molecule lattice parameters/structures. Furthermore, the reversibility
aggregates in EC solvent (Reprinted with permission from Ref. [108]. of cycling can be interpreted through these curves in which
Copyright © The Author(s) 2015. Published by ECS). e Proposed
the presence of a reaction that can reconstruct the cathode
mechanism for the continuous decomposition of SEI and electro-
lytes as monitored by C 2H4 evolution for a preformed electrode with at a certain voltage can be clearly predicted if the curve does
a Mn2+-containing electrolyte: (1) absorption of M n2+ ions into the not repeat itself in the next cycle after reaching that point
SEI; (2) reduction of M n2+ ions in the SEI and deintercalation of Li+ [35]. Moreover, a small but important feature (a small peak)
from graphite; (3) re-oxidation of M n0 to Mn2+; (4) recurrent elec-
often found in the charge/discharge curve at the beginning of
trolyte reduction; (5) the catalytic cycle of electrolyte decomposi-
tion (Reprinted with permission from Ref. [38]. Copyright © The the initial charging can indicate the existence of impurities
Author(s) 2018. Published by ECS) (most probably nickel hydroxide and nickel carbonate) dur-
ing storage (a typical example showing the reaction of sur-
face impurities of NMC811 after long-term storage during
are categorized based on cathodes because certain degrada- cycling is illustrated in Fig. 7a) [35]. Finally, the polarization
tion mechanisms may involve both electrode materials and of battery cells can be estimated by comparing the voltage
interfaces. levels of different cycles at fixed capacities.
Differential Capacity Curve Differential capacity curves are

another kind of plots derived from charge/discharge curves [7,
13
Fig. 6 Summary of degradation

mechanisms of Ni-rich NMC-
based cathodes on the microm-
eter and atomic scale
20, 118]. These curves are also referred to as the incremental discharge curves can reveal the impact of C-rates on cell deg-
capacity and can be obtained by plotting dQ dV
versus voltage. radation. In addition, discharge capacities at each time slot
(For similar reasons mentioned above, the vertical axis is con- during discharge can be plotted versus corresponding C-rates
verted to dV
dx
in some cases, as shown in Fig. 7b.) The main use and a trendline fitting of all data points taken at the same volt-
of these curves is to cross-check features already shown in age can be drawn and extrapolate to the Q-axis, thus revealing
charge/discharge curves at certain voltages but can also pro- the relationship between maximum capacity Qmax and voltage.
vide other information. Here, the most important feature Moreover, maximum capacity fading plots based on EMF
revealed based on differential capacity curves for Ni-rich curves can be used to determine capacity loss (irreversible
NMC-based cathodes is the phase transition in which three capacity loss ∆Qir) at different C-rates. Differential voltage
peaks can be identified in both charging and discharging pro- curves can also be applied to EMF, and dQ can be regarded
dVEMF
cesses, indicating phase transition from H1 (hexagonal) to M as a nondestructive method in which peak shifting is indica-
(monoclinic), and subsequently to H2 and H3 (see Sect. 2.1.1) tive of cell degradation and can reveal anode material decay
as Li is extracted from the cathode [45]. In addition, differen- and voltage slippage effects [121].
tial capacity curves can be plotted with in situ X-ray diffrac-
tion results to correlate phases to corresponding lattice param- Capacity Fading Capacity fading curves can provide more
eters [119]. Moreover, the loss of available Li between macroscopic views of capacity loss during long-term cycling
graphite layers or in the Li-rich layers of cathodes can be and can be derived from capacity fading plots in which cell
revealed through the fading of these peaks. And by integrating capacity at different conditions is displayed. And because
peak areas and calculating the ratio of these peak areas to the electrode materials and aging conditions vary significantly in
total charge/discharge capacities for each cycle, trends in the difference battery systems, the speed of capacity fading can
pathways/steps of Li transfer can be implied (e.g., more domi- also vary significantly. Therefore, the degree of cell aging
nating, remaining the same or fading). Furthermore, the posi- needs to be normalized in which the vertical axis of capac-
tion of peak potential is indicative of cell impedance in which ity fading curves is sometimes converted to represent nor-
positive shifting during cycling implies an increasing cell malized capacity. A modified version has also been recently
impedance. Similarly, a differential voltage plot (dQ
dV
vs. Q) can presented [16] to investigate the effects of the amount of
be used to show the fluctuation of voltage during charge/dis- Li+ ions entering/exiting Li-layers in cathodes rather than
charge and is also linked to phase transitions [98]. focusing on the number of alterations. Here, an accumula-
tive discharge capacity fading plot can be drawn and used
Maximum Capacity To determine maximum capacity and to compare capacity fading in different currents, which can
associated fading, electromotive force (EMF) data [120] can provide insights into the possible relationships between the
be derived from the discharge curve of the same cell at differ- amount of Li+ transferred and structure deformations.
ent C-rates. Here, comparisons of EMF curves with charge/
13
Table 1 List of identified degradation mechanisms of Ni-rich NMC/graphite LIBs

No. Condition Degradation mechanism Electrode References
1 N/A Initial SEI formation consuming active Li Anode [108]

2 N/A Li diffusion into the NMC layer Cathode [26]
3 N/A Sluggish Li diffusion back into the cathode Cathode [94]
4 High voltage, high temperature Sudden capacity loss caused by surface film formation and thickening under Anode/cathode [31]
harsh conditions
5 High SOC Ni2+ migrating to vacant L i+ sites (cation mixing), reducing the number of Cathode [51]
Li sites and blocking Li diffusion pathways
6 N/A Structural changes from rhombohedral (layered) to spinel and later to rock- Cathode [64]
salt (NiO, nickel carbonate and minor quantities of hydroxides) as a result
of massive cation mixing
7 Long cycling Mn3+ forms a spinel structure from a layered (rhombohedral) structure Cathode [71]
because of low octahedral site stability energy (based on studies of Mn-
rich NMC cathodes)
8 High SOC Ni4+ oxidizing electrolytes and thickening CEI (self-discharge) Cathode [83]
9 Storage in air Surface impurities formed on particle surfaces due to long-term storage in Cathode [35]
air
10 N/A NMC dissolution in HF (less active sites and higher charge transfer resist- Cathode [74]
ances)
11 Extreme high temperature Thermally unstable NMC reacting with LiPF6 and causing thermal runa- Cathode [33]
ways (fire and explosion)
12 N/A Release of reactive oxygen due to surface reconstruction causing chemical Cathode [25]
oxidation of electrolytes to produce CO and C O2
13 High voltage CO2 produced from the electrochemical oxidation of electrolytes Cathode [87]
14 High voltage (above 4.6 V) Oxygen reducing metal ions due to the hybridization of electrons and orbit- Cathode [82]
als (self-redox reaction)
15 Low voltage Disproportion of Mn3+ (based on studies of Mn-rich NMC cathodes) Cathode [75]
16 N/A Carbonate layers reacting with electrolyte Cathode [35]
17 Long cycling, high DOD Secondary particles cracking along grain boundaries and enlarging surface Cathode [13]
areas for more side reactions to occur
18 N/A Loss of active Li metal to SEI as immobilized during cell operation Anode [110]
19 High voltage SEI layer decomposition facilitated by the precipitation of transition metals Anode [38]
into the SEI (huge capacity loss)
20 N/A Volume expansion and contraction of graphite during operation cracking the Anode [102]
graphitic layer
21 N/A Metal ions from the cathode inserting into the anode and blocking active Anode [111]
sites
22 N/A Mn2+ reacting at the surface of the anode to generate L i2CO3, which can Anode [38]
crack graphite surfaces
23 N/A Solvents getting into the holes of graphite Anode [31]
24 N/A Solvated Li+ cracking graphite during Li intercalation Anode [110]
25 N/A Li dendrite plating (may trigger short circuiting if growth becomes too Anode/cathode [104]
large)
26 N/A Continuous thickening of surface films during cell operation Anode/cathode [37]
Note: N/A in the condition column indicates a common degradation mechanism occurring in many conditions; Only one representative reference
is provided for each degradation mechanism because many of them have been reported extensively in many studies
Based on capacity fading plots, the number of electrons it describes the percentage of electrons charged to the
consumed by side reactions (both at the cathode and at anode that can be used to release Li+ (remaining electrons
the anode) can be measured by subtracting the discharge consumed by side reactions during charging), whereas the
capacity by the corresponding charge capacity. Here, a number of electrons that can be discharged from the cath-
charge efficiency (CE) plot focusing on the degree of side ode can be calculated by Qcharge,n+1 . And in general, the two
Q
reactions is commonly used in which the charge effi-

discharge,n
percentages should be around 100% ( CEanode is a bit less,

ciency of an anode can be calculated by Qdischarge,n , because
Q
charge,n
13
Fig. 7 a Charge/discharge curves of the 1st, the 2nd and the 3rd Li coin cell (Reprinted with permission from Ref. [33]. Copyright ©
cycles of NMC811-Li (Reprinted with permission from Ref. [35]. 2018, Elsevier B.V. All rights reserved.). d The Nyquist plot of NMC
Copyright © The Author(s) 2018. Published by ECS). b The c-lat- 811 (The inset: the equivalent circuit model used for data fitting). e
tice constant and differential capacity as a function of cell voltage for The Nyquist plot of SiO2-coated NMC 811 (Reprinted with permis-
NMC811 (LiNi0.8Mn0.1Co0.1O2) (3–4.4 V) (Reprinted with permission from Ref. [123]. Copyright © 2015, Elsevier B.V. All rights
sion from Ref. [20]. Copyright © 2016, American Chemical Soci- reserved.)
ety). c Cyclic voltammetry of the first three cycles of an NMC 811/
13
but C E cathode is a bit more); however, the existence of varied capacitance from point to point. To address this, a
kinetic barriers may cause enlarged differences. resistor in parallel with a constant phase element (CPE) can
To study impedance growth during cycling, average be used to model each process. As for the long tail attached
polarization plots combined with discharge voltage decay to the two semicircles in the EIS curve, this is related to
plots can be obtained and can reveal capacity retention mass-transfer resistance and therefore can be represented
behaviors by measuring ∆Vave increases, which can indi- by using a Warburg element. During aging, both semicircles
cate impedance growth through cell degradation as well commonly increase (Fig. 7d, e), indicating large cell polari-
i+ insertion/desertion [9].
as potential kinetic barriers of L zations and thickened CEIs; however, with remedial efforts,
the increase in both resistances (linked to both semicircles)
can usually be reduced. For example, researchers have
3.1.2 Cyclic Voltammetry reported that impedance growth of surface films and charge
transfer can be significantly reduced through a S iO2-layer
As a supplementary method, cyclic voltammetry (CV) can coating of NMC811 (Fig. 7e) [123].
be used to determine the reversibility of charge/discharge
in electrodes by measuring the difference in charge/dis- 3.2 Physical Techniques
charge peak potentials, which is related to major delithi-
ation/lithiation processes (Fig. 7c) [33]. As such, CV can 3.2.1 Crystal Lattice and Particle Morphology
assist in the investigation of transition metal oxidation and
reduction in which the plot of the initial CV can differ
from subsequent cycles due to the formation of SEIs dur- X‑ray Diffraction In situ and ex situ XRD methods are the
ing the first delithiation. In addition, upper cutoff voltages most frequently used physical characterization methods to
can also be determined by using CV [122]. determine lattice parameters and crystal structures. Here,
in situ XRD can be used to measure the evolution of lattice
3.1.3 Electrochemical Impedance Spectroscopy parameters (both a-axis and c-axis) of NMC-based cathodes
during cycling [43]. For example, the use of in situ XRD
Electrochemical impedance spectroscopy (EIS) is another can evidence the shrinking of the a-axis to a constant value
common method to investigate cell impedance evolution and and the expansion and rapid shrinking of the c-axis dur-
degradation mechanisms and involves the application of AC ing delithiation in Ni-rich NMC cathodes through the shift-
sinusoidal waves (voltage or current) to target cells. Here, ing of (003) and (006) peaks to a lower angle together with
AC sinusoidal waves are applied at an amplitude with dif- the shifting of the (101) peak to a higher angle (Fig. 8a).
ferent frequencies because semicircles in resulting Nyquist In addition, in situ XRD can allow for the comparison of
plots can overlap with each other if represented processes the lattice shrinkage percentage of the a-axis to that of the
occur in the same frequency range. In addition, half-cell EIS c-axis, leading to the conclusion that lattice shrinkage is
can be carried out with either 2-electrode symmetric cells anisotropic and that lattice parameters are linked to corre-
(e.g., Swagelok 2-electrode symmetric configuration cells) sponding phases (H1, M, H2, H3). In situ XRD can also be
or 3-electrode cells by installing a reference electrode in used to test the thermal stability of NMC cathodes and show
which the resulting EIS curve often involves a vertical short temperature-resolved (TR) results [42] similar to voltage-
tail, two depressed semicircles (only if a half cell is tested) resolved results. For example, TR-XRD results of heated
and a long tail at a certain degree to the horizontal axis from NMC-based cathodes can be used to examine thermal sta-
high to low frequencies. Here, the short tail usually appears bility in which researchers found that the structures of all
at extremely high frequencies, indicating the inductance of NMC cathodes tested experienced surface reconstruction
cables, which is rarely seen in test results. Solution resist- from rhombohedral to spinel (first the LiMn2O4 type and
ances can also be measured at the intercept of the short tail later the Mn3O4 type) and subsequently to rocksalt structure
with the real (Z) axis and therefore can be represented by a (Fig. 8b). In another study, in situ XRD plots were combined
resistor. As for the first semicircle at high frequencies (usu- with gas chromatography–mass spectroscopy (GC–MS) data
ally a small one), this is indicative of the resistance of the to reveal the relationship between the Li content and evolved
CEI, and as the CEI continuously reacts (thickening and gas from NMC-based cathodes [90].
decomposing), the impedance cannot be taken as merely
resistive. The second semicircle can be attributed to charge Ex situ XRD with Rietveld refinement is easier to conduct
transfer at the cathode. (Double-layer capacitance is gener- than in situ XRD but conveys less information because it can
ated because of voltage decay across the interface.) In typi- only illustrate the crystal structure of NMC-based cathodes.
cal EIS curves, these semicircles can appear as depressed For ex situ XRD data, more peaks can be seen if a bulk
due to surface roughness (unevenness), which can cause phase of impurities or coating materials is formed on the
13
surface of cathode materials. Here, the ratio of I003–I104 in will show two strong diffraction spots that indicate the for-
the ex situ XRD data indicates the degree of cation mixing mation of rocksalt phases with high symmetry. Phase con-
and can be used to determine the ameliorative performance version can also be tracked and compared by using HAADF-
of a mitigation method in which ratios lower than 1.2 rep- STEM results [9].
resent significant cation mixing. Moreover, the peak split- High-angle annular dark-field scanning transmission
ting of (110)/(108) and (006)/(102) represents a well-layered electron microscopy (HAADF-STEM) measurements can
hexagonal structure (Fig. 8c) [45] and the evolution of the provide array images of transition metal atoms located
full width at half maximum (FWHM) of peaks represents from the bulk to the surface of NMC particles and spectra
change in crystallinity. Surface species can also cause peak of electron energy loss spectroscopy (EELS). Here, orderly
shifting [e.g., (003) of NMC622] if stored [72], or generate arrays of atoms can clearly display layered structures of the
new peaks, and therefore, ex situ XRD can also be used to crystal lattices of NMC (Fig. 9b) [63, 124, 125]. Here, the
cross-check the existence of impurities. degree of surface reconstruction can be determined based
on changes in atom patterns and a clear boundary between
Microscopy and Electron Diffraction Scanning electron reconstructed and unreconstructed phases can be traced. In
microscopy (SEM) and transmission electron microscopy addition, region thicknesses can also be measured based on
(TEM) can be used to reveal microscopic structures of HAADF-STEM images.
NMC-based cathodes and assess structural damage [124].
In addition, diameters of primary and secondary particles 3.2.2 Chemical Analysis
can be measured from obtained images together with the
thickness of any surface coating layers [100]. Here, aggre- Elemental Analysis Elemental analysis is necessary for the
gates of primary particles, i.e., secondary particles, are usu- physical characterization of NMC-based LIBs and the com-
ally observed in electron microscopy images possessing position of NMC-based cathodes as well as the investigation
elongated or even needle-like shapes before degradation, of impurities and remedial coatings/dopants. In addition, the
whereas microcracks on secondary particles can usually be semiquantitative properties of various elemental analyses are
seen after repeated cycling, which can cause the breakage useful in the quantification of relative increases/decreases of
of particles. As a result, the spherical shape of secondary certain elements during operation or storage. Here, energy-
particles is usually distorted, and subfigures of SEM images dispersive spectroscopy (EDS) mapping analysis can illus-
obtained from samples aged under different conditions are trate elemental distributions (Li, transition metals, C, etc.)
usually displayed together for comparison. Another indis- semiquantitatively on cathode particle surfaces. For exam-
pensable microscopic method is high-resolution transmis- ple, the dissolution of these surfaces through attack with HF
sion electron microscopy (HRTEM), which can reveal can be evidenced by the increase in F element signals and
microregions of Fm3m NiO and spinel structures and allow the loss of transition metals.
for the distance between atomic layers to be clearly marked
(Fig. 9a shows a surface reconstruction region on a NMC- Alternatively, electron-probe X-ray microanalysis
based cathode and an electron diffraction pattern of selected (EPMA) accompanied with SEM can allow for the exami-
spots) [56, 70]. A drawback of HRTEM, however, is that it is nation of transition metal element concentrations within
unable to distinguish between phases with similar structures different regions of NMC particles with a spatial resolution
and lattice parameters [50]. of ~ 0.3 μm and can often be used to determine the con-
centration gradient layer of modified-NMC particles [126].
Electron diffraction is a useful tool to characterize phases Researchers have also reported that the average composition
and microregions in NMC lattice crystals and includes of Ni, Mn and Co can be measured using atomic absorption
selected area electron diffraction (SAED) and nano-beam spectroscopy (AAS) [126].
electron diffraction (NBED, in which a condenser lens and X-ray photoelectron spectroscopy (XPS) is another ele-
an upper objective lens are used to achieve nano-beams of mental analysis method that can detect the chemical and
electrons). Here, Kang et al. [56] have used electron diffrac- electronic states of transition metals and oxygen in NMC
tion to measure the space group of NMC-based cathodes cathodes as well as elemental carbon from current collec-
with the zone axis at the bulk and surface regions of a NMC tors and binders [73]. Here, the 2p orbitals of Ni, Mn and
particle. In addition, electron diffraction is usually conducted Co and the 1s orbital of O can be captured to reveal oxida-
separately on different regions of particles such as surface tion states by checking the peak positions of 2p1/2 and 2p3/2
regions, transitional regions and bulk regions. Here, the (Fig. 9c) [127]. For example, the binding energies of Ni 2p3/2
existence of secondary phases can be confirmed based on in NiO and in N i2O3 were found to be located at 854.0 and
obtained patterns in which spinel structures can lead to an 856.0 eV, respectively [50]. In addition, the shift in oxidation
additional spot (Fig. 9a2–a5), whereas Fm3m space groups states can be clearly shown by changes in peak positions,
13
Fig. 8 a In situ XRD patterns of an NMC 811 cathode over a voltage b3 NMC622 and b4 NMC811 (Reprinted with permission from Ref.
range from 3.330 to 4.298 V during the first charge (Reprinted with [42]. Copyright © 2014, American Chemical Society). c Ex situ XRD
permission from Ref. [43]. Copyright © 2015 WILEY-VCH Verlag patterns of NMC-811 and L i2MnO3-coated (10% and 30%) NMC-811
GmbH & Co. KGaA, Weinheim). b Contour plots of TR-XRD pat- (Reprinted with permission from Ref. [45]. Copyright © 2016, Amer-
terns at the selected 2θ range for charged b1 NMC433, b2 NMC532, ican Chemical Society)
and changes in the amount of Ni can be deduced from the has also been widely utilized for anodic elemental analysis
increase in peak area and intensity. Moreover, the use of (e.g., transition metals deposited on graphite anodes) under
cycle-dependent XPS can allow for the change of valence various cycling conditions [113], leading to the discovery
states to be attributed to a certain range of cycles, whereas a that the massive dissolution of Mn can occur if NMC111/
decrease in XPS peaks can indicate the loss of elements or graphite cells are charged above 4.6 V [76].
the coverage of elements with surface impurities. Further- Electron energy loss spectroscopy (EELS) is another
more, XPS can enable the identification of new substances elemental analysis method that can investigate elemental
on cathode surfaces that evolve during storage or operation energy loss and possesses three modes, including auger elec-
[35]. As for organic elements including C (1s), O (1s), F tron yield (AEY), total electron yield (TEY) and total fluo-
(1s), N (1s) and S (2p) that are contained in the components rescence yield (TFY), each of which provides information
of SEI layers, XPS can also be used to track the existence of from different depths (1–2 nm, 2–5 nm and 50 nm, respec-
these elements in different molecules versus voltage [128]. tively). Due to smaller probing depths, EELS signals reflect
To validate XPS data, X-ray absorption spectroscopy information on the top layer of cathodes [63], and the shift in
(XAS) can be used as a supplementary technique to moni- energy loss peaks from time to time or from the bulk to the
tor transition metal valence changes during charge/dis- surface can indicate shifts in oxidation states of elements,
charge and include extended X-ray absorption fine struc- in which lower energy losses translate to lower oxidation
ture (EXAFS) and X-ray absorption near edge structure states of transition metals [9]. In general, each EELS curve
(XANES) [129]. For example, stronger Ni2+ signals over consists of two peaks, including a pre-edge peak and a pri-
Ni4+ in NMC532 at 4.5 V reveal that the redox reaction of mary peak. Here, the pre-edge peak of oxygen is thought to
Ni4+ with electrolytes can occur, which reduces Ni4+ to Ni2+ be caused by the transition of electrons from the 1s to the
[130]. And due to the viability of XAS in the examination unoccupied 2p state, which can hybridize with the 3d orbit-
of transition metal concentrations and oxidation states, XAS als of transitional metals [66]. Alternatively, the primary
13
Fig. 9 HRTEM images and FFTs after 50 cycles under 3.0–4.8 V sample. b2 Corresponding X-ray spectrum from the highlighted area
conditions. a1 Lattice image of the surface region where a2–a5 cor- in (a). b3 High-resolution STEM-HAADF image showing the lattice
respond to the FFTs of regions 1–4, respectively. (11-1)C is the dif- structure from the highlighted area in (b1) (Reprinted with permis-
fraction spot of the rocksalt phase of the metal monoxide (Reprinted sion from Ref. [124]. Copyright © 2016, Elsevier B.V. All rights
with permission from Ref. [56]. Copyright © 2013 WILEY-VCH reserved.). c XPS data for lithiated FCG-Mn-F Li(Ni0.60Co0.15Mn0.25)
Verlag GmbH & Co. KGaA, Weinheim). b1 Low-magnification O2: c1 Ni 2p, c2 Co 2p and c3 Mn 2p (Reprinted with permission
STEM-HAADF image of one surface primary particle of the x = 0.10 from Ref. [127]. Copyright © 2013, American Chemical Society)
peak originates from the transition of electrons from the 1s provide relatively precise information on the amounts of Li
to the 2p state of O or to the 4sp state of transition metals. [132], transition metals [133–135] and impurities in exam-
Moreover, area-integrated EELS data can be compared to ined samples in which concentrations can be indicated by
check the homogeneity of NMC particles [63]. the intensity of characteristic waves emitted from excited
Electron paramagnetic resonance (EPR) spectroscopy atoms or ions. In addition, changes in the elemental com-
can also be applied to NMC materials such as NMC622 to position of electrodes or powder samples due to operation
investigate the effects of doping with Al and Fe on cation or modification can be reflected in ICP-AES data and the
mixing in which the change of the N i2+ line indicates the results (in ppm) are often compared with theoretical values
redistribution of Ni within the structure. Hubert Gasteiger’s or results obtained by using other elemental analysis tools
group have also demonstrated Li plating onto graphite to observe differences. Researchers have also combined ICP
anodes quantitatively and in real time by using operando with mass spectroscopy in studies. For example, ICP-MS
EPR [106] quantified the amount of Li-ions not available was used to reveal significant increases in the Ni content
for future cycling. Despite these uses, EPR cannot provide on graphite anodes related to the dissolution of Ni from
more detailed structural information, which requires other NMC 811 cathodes [136] and was also used to conduct a
physical characterization methods [131]. series of Li content measurements in sampled electrolytes,
Inductively coupled plasma–atomic emission spectros- including sample preparation procedures [137], in which the
copy (ICP-AES or ICP) is a cutting-edge technique that can
13
results were pre-calibrated with known Li concentrations 3.2.3 Thermal Stability

and proved the credibility of the ICP-MS method.
Differential scanning calorimetry (DSC) is a method that
Gas Measurement Ex situ gas measurements have been utilizes microcalorimeters to measure heat flow from cells
adopted by many researchers in the study of LIBs in which (W g−1) in which the thermal stability of NMC-based cath-
the volume of evolved gas is measured as the cell is charged odes with/without electrolyte contact is recorded to reveal
to certain voltage levels [9, 85]. Gas evolution under other heat flow from the NMC-based cathode as it is heated to a
conditions can also be measured, including the addition of certain temperature [33, 140]. For example, in two NMC-
electrolyte additives or under different compositions of Ni, based cathodes and LiNi0.7Mn0.3O2 with a concentration
Mn and Co. And if combined with mass spectroscopy, the gradient layer, one major peak can be found for each DSC
content of emitted gas can be identified (usually including H2, curve centering at a certain temperature in which a higher
C2H4, CO and CO2) and allows for volume or moles versus onset temperature of the DSC peak indicates better thermal
voltage to be plotted with various curves related to different stability (Fig. 10b) [126]. In addition, exothermic peaks can
gases [24]. Furthermore, online electrochemical mass spec- be integrated to calculate the amount of heat released, which
troscopy (OEMS) is a tool that can facilitate the detection of can translate into the degree to which corresponding reac-
gas in real time and can quantify the amount of H 2, CO2 and tions occur [99]. Here, the application of common mitigation
O2 from different mass to charge ratios [23, 90] in which gas methods usually results in smaller exothermic peak areas and
evolution (e.g., O2) is related to cathode surface reconstruc- higher onset temperatures [100]. However, small endother-
tion (if aimed at cathodic processes) through comparisons of mic peaks can also be seen for some cases, indicating the
voltage profiles (or SOC) (Fig. 10a). Similarly, anodic pro- decomposition of Li salt in the electrolyte [101]. In addition,
cesses with gas evolution can also be tracked by using OEMS. TG is often combined with DSC to record mass loss during
Researchers have also combined differential electrochemical the heating of NMC-based cathodes (Fig. 10c), including
mass spectrometry (DEMS) with differential electrochemi- processes such as the addition of carbon matrixes to remedy
cal infrared spectroscopy (DEIRS) to identify and quantify cathode degradation [141] or the release of oxygen due to
gases emitted from NMC 532/graphite cells [84] and found surface reconstruction [140], or through the loss of surface
that potential-resolved gas evolution partially originates from impurities and adsorbed species [72].
SEI formation. And if combined with thermogravimetry (TG), Accelerating rate calorimetry (ARC) is another method
the mass loss of cells can be correlated to oxygen evolution adopted by researchers to measure self-heating rates (SHRs)
from NMC-based cathodes heated to a certain temperature, versus temperature [8, 142]. For example, in the compari-
showing that the majority of weight loss can be attributed to son of the SHR of 4 types of Ni-rich NMC-based cathodes
oxygen release as they both rapidly rise to around 175 °C [85]. (Fig. 10d), the onset temperature of a rapidly increasing
SHR marks the upper limit of the temperature range for the
Impurities and Organics Raman spectroscopy can be used to safe operation of a cell [7] in which cathodes with higher
determine the existence of surface impurities that can cause SHR onset temperatures are considered to be better LIB
capacity fading such as nickel carbonate, lithium carbonate cathodes for industrial applications. Isothermal microcal-
and nickel hydroxide [35]. Because of this, Raman spectros- orimetry (IMC) has also been used to examine heat flow
copy is a useful tool in the identification of impurities pro- induced by polarization, entropy and parasitic reactions
duced during long-term storage (Fig. 3a). Similarly, Fourier versus the state of charge of NMC811 and has revealed that
transformed infrared spectroscopy (FT-IR) can be used to heat flow originating from parasitic reactions can increase
identify impurities on cathode surfaces [72] or organic coat- sharply if the relative SOC rises from 0 to 1 at certain volt-
ings [138]. For example, the O–H stretching mode from LiOH ages (Fig. 10e) [7].
possesses a characteristic band between 3650 and 3200 cm−1
in corresponding FT-IR spectra, whereas 1450 and 870 cm−1 3.2.4 Advanced Physical Characterization
are regarded as characteristic peaks of the C=O mode origi-
nating from Li2CO3 [61]. Raman spectra of NMC-based cath- Many advanced physical characterization methods have also
odes can also be voltage dependent to monitor band shifts of been used by researchers to study LIBs. For example, 3D
A1g and Eg of Ni, Mn and Co. Moreover, FT-IR and Raman transmission X-ray tomography mapping [92] can be used to
spectroscopy are widely used in the characterization of anodic determine the distribution of transition metals in NMC parti-
graphite and SEIs because they can identify substances form- cles in which 3D mappings can allow for elemental analysis
ing SEI layers such as lithium alkyl carbonates and therefore within cross-sections at different depths. Surface potential
can reveal reaction mechanisms involved in the SEI forma- mappings of NMC-based cathodes can also be conducted by
tion process and present differences in mechanisms if multiple using Kelvin probe atomic force microscopy (AFM) [143] in
electrolyte additives are used [139]. which smaller surface potentials can allow for easier electron
13
Fig. 10 a Specific charge and

CO2 and O2 evolution rate
profiles versus cathode potential
during the first and the second
charges of four NMC-based
cathodes (Reprinted with
permission from Ref. [90].
Copyright © 2017, American
Chemical Society). b DSC
traces and c TGA curves of
electrochemically delithiated
FCG Li0.25(Ni0.54Co0.16Mn0.30)
O2, Li0.25(Ni0.5Co0.2Mn0.3)O2
and Li0.27(Ni1/3Co1/3Mn1/3)O2
charged to 4.3 V (Reprinted
with permission from Ref.
[140]. Copyright © 2014
WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim). d
Self-heating rate as a function
of temperature for delithi-
ated NMC electrode samples
reacting with electrolytes in
accelerating rate calorimeter
experiments (Reprinted with
permission from Ref. [8].
Copyright © 2018, American
Chemical Society). e Isothermal
calorimetry measurements of
heat flow of extracted polariza-
tion, entropy and parasitic reac-
tions (Reprinted with permis-
sion from Ref. [7]. Copyright ©
The Author(s) 2015. Published
by ECS)
transfer from cathodes and therefore smaller polarizations. the ratios of Mn to Ni along a direction across the parti-
The use of nano-secondary-ion mass spectrometry (nano- cle. In situ neutron powder diffraction (NPD) can also be
SIMS) analysis can provide good spatial resolution (less used to obtain more accurate results of lattice parameters
than 50 nm) for elemental mapping [144]. And with higher as compared with in situ XRD [145], in which although
resolution, different phases can be identified by comparing the energy of neutrons is lower than X-rays, the penetration
13
depth is higher. In situ NPD can also be used to determine water. Furthermore, Li salts can also be used to improve
the d-spacing of anodic graphite during Li intercalation and NMC-based cell performances. For example, LiPF6 can
therefore the amounts of LiC6, LiC12 and LiC24 [44]. Despite react with excessive alkaline Li on the surfaces of cathode
these advantages, researchers have reported that hydrogen- particles to produce chemically stable Li3PO4 and LiF, and
containing species can attenuate neutrons. As for prompt significantly suppress parasitic reactions caused by exces-
gamma activation analysis (PGAA), this method can be used sive Li [152]. Surface coating is another commonly used
to quantify the amount of transition metals deposited onto strategy to separate NMC cathode surfaces from electro-
graphite anodes by placing the sample in a neutron beam and lytes [15], and atom substitution has also been reported to be
collecting signals [26]. The use of PGAA allowed research- effective in enhancing the performance of mitigated Ni-rich
ers to discover that cycling and high cutoff voltages can NMC-based LIBs. Based on these strategies, this review sec-
promote transition metal deposition onto graphite anodes. tion will present techniques applied to improve the cycling
performance of NMC cathodes in the most recent decade,
in which cited studies are divided into categories based on
4 Mitigation Strategies for Ni‑Rich the type of modification, including inner surfaces (doping/
NMC‑Based Cathodes and Graphite gradient layers) and outer surfaces (coating/matrixes) of
Anodes Ni-rich NMC-based particles. New synthesis methods of
Ni-rich NMC cathodes that enhance performance without
4.1 Ni‑Rich NMC‑Based Cathodes introducing new substances are also presented.
Ni-rich NMC-based cathodes suffer significantly more from 4.1.1 Inner Surface

capacity loss and impedance growth as compared with low
Ni content NMC-based cathodes such as NMC111. This is Doping Doping can minimize side reactions on cathode par-
because large amounts of N i4+ on cathode surface regions ticle surfaces and enhance the rate of Li diffusion and charge
can trigger side reactions and N i2+ can cause cation mixing. transfer. In addition, active material costs can be reduced if
In addition, excessive Li is usually added in the prepara- Co is substituted with other elements. To achieve doping/
tion of NMC-based cathodes and tends to accumulate on the atom substitution, researchers often use co-precipitation,
surface of particles and react with electrolytes to convert to solid-state reaction, self-combustion and co-calcination,
lithium carbonate and hydroxide. Furthermore, the continu- in which the two types of doping include cationic doping
ous charging and discharging of these cathodes can cause the and anionic doping. And in general, few dopants can affect
cracking of secondary particles. the layered structure of electrodes, but some can form new
To address these issues, researchers have proposed many phases (e.g., the presence of a L i2SnO3 phase in Sn-doped
strategies. One common method is the mixing of LMO with NMC622 [153] and the presence of L i2ZrO3 in Zr-doped
154
NMC [45, 118, 124], which can enhance capacity reten- NMC532 ).
tion (not reviewed in this review because this method does
not directly modify cathode particles) and another method Cation-doped surfaces of Ni-rich NMC particles can ben-
involves the addition of electrolyte additives. Here, organic efit from the lowered Ni content and therefore suppressed
additives can be sacrificed at high voltages (4.3–4.5 V) cation mixing [155]. Here, the selection of dopants is based
because their HOMOs are higher than the HOMOs of on the bond energy of M–O and the radius of dopant ions in
organic solvents to preferentially lose electrons and be oxi- which trade-offs between structural stability and Li+ move-
dized to prevent the oxidative decomposition of solvents ment need to be considered. For example, strongly bonded
[146]. In addition, the electropolymerization of electrolyte dopants to oxygen can improve structural stability and reduce
additives can also provide electrons to counteract the decom- the amount of oxygen released [156, 157], but in most cases
position of solvents [147]. Moreover, the use of electrolyte tend to withdraw more electron density from the M–O bond,
additives can allow for the formation of more even CEIs leading to the reduction in oxygen repulsion and the verti-
on cathode surfaces [148, 149], which can reduce contact cal contraction of the crystal lattice (Fig. 11a) [153], which
between electrode surfaces and electrolytes to prevent side negatively affects Li+ movement due to increased kinetic
reactions and lower impedance. One representative electro- barriers [158]. For easier lithiation/delithiation, increased
lyte additive is fluoroethylene carbonate (FEC) [150, 151] distances between atomic layers in the lattice structure are
in which vinyl fluoride and L i2CO3 are produced as oxida- desired and can be achieved by using dopants with larger
tion products during cell operation. Wang et al. [146] have radii. For example, dopants such as F e3+ and S
n4+ (with radii
3+
also reported that 3-IPTS as an electrolyte additive can con- larger than substituted Co ) can expand Ni-rich NMC crys-
sume trace amounts of water in electrolytes to minimize the tal lattices horizontally [145] and Ca2+ (with a radius larger
amount of HF produced from reactions between LiPF6 and than Ni2+) can expand lattices horizontally by substituting
13
Ni at 3a sites [53]. Researchers have also reported that dop- Gradient Layer Modifications of Ni-rich NMC-based cath-
ing with Al can contract cathode lattices slightly due to the ode particles have been investigated by many studies in
smaller radius of A l3+ [159]. Here, reported results of dif- which a typical modification is a concentration gradient layer
ferent cationic dopants can sometimes be contradictory in that can cover a Ni-rich NMC core [126, 173–175]. This
which enlarged lattices due to cationic dopants with larger concentration gradient layer design originates from a simple
radii can either promote (mostly reported) or hinder (block- core–shell structure in which the shell (single or multiple)
ing effect, rarely reported) Li+ diffusion in different studies. is composed of other NMC compositions (lower Ni content
Because of this, these results need to be comprehensively and higher Mn content) to stabilize the layered structure.
reviewed in the future [154, 160]. And to overcome drawbacks of voids generated between the
To achieve better cycling stability, capacity is sometimes shell and the core during long-term cycling and mismatches
sacrificed because some dopants such as Al3+ are chemi- of different lattice parameters, gradient layers were invented
cally inactive [28]. Cr doping can improve cycling stability to replace core–shell structures. Here, the composition of the
without capacity decrease [161], and Zr doping can enhance gradient layer is different from the core material, in which
cycling performance [154, 162] but will reportedly produce Ni atoms are gradually replaced by Mn atoms from the inter-
a Li2ZrO3 phase. In addition, different dopants possess dif- face to the outer edge, resulting in a surface with higher
ferent valences and stabilize crystal structures at different structural integrity (Fig. 12a). Furthermore, concentration
sites. For example, Mg2+ possesses a similar radius to Li+ gradient layers can reshape primary particles into a rod-like
and will enter the Li-layer rather than the transition metal structure, which can promote Li+ movement by minimiz-
layer on the surface region of Li-rich NMC particles [125, ing diffusion pathways [140]. This feature can be further
163], allowing for the suppression of cation mixing due magnified in needle-shaped structures for some cases and
to the repulsion of M g2+ to transition metal ions and the turned into plates if calcined [175, 176]. Modifications with
delaying of the surface transformation to a spinel structure concentration gradient layers can also prevent the separa-
(Fig. 11b, c). Alternatively, N a+ can substitute for L i+ at tion of cores and shells caused by continuous expansion and
3a sites [52, 164] to enlarge the distance between layers, contraction. Moreover, gradient layers can be extended into
and benefitting from the larger radius of N a+, cation mix- full concentration gradient (FCG) layers [175, 177, 178] and
ing can be suppressed [165] and weakened Li–O bonds can multiple gradient layers with different slopes can also be
enhance potential capacity. However, because Na+ doping obtained to maximize the Ni content at the core as compared
can enlarge primary particles, optimal amounts are limited with single-sloped gradient layers [179]. For example, Noh
to ensure a connection between primary particles. Chen et al. et al. [127] reported a NMC (60 25 15) particle with a con-
have also suggested that the standard of choosing appropri- stant Mn concentration from the center to the surface and
ate cationic dopants for NMC cathode improvements had a gradually decreasing Ni and increasing Co concentration
not been established [53], whereas others have reported and found that the composition of the surface layer did not
that ions with low valences were favored for L i+ diffusion change significantly after long-term cycling.
[166]. New methods of cation doping have also been pro-
posed in which Mn doping into NMC71515 can provide an 4.1.2 Outer Surface
outer region with Fm3m Ni2+ (reduced from Ni3+) residing
in Li slabs (pillar structure) and can be used to consolidate LixMyOz coating LixMyOz coatings can be applied to the sur-
the layered structure of cathodic crystal lattices and avoid face of primary particles to enhance performance and are
particle degradation [167]. As for anionic doping, fluorine composed of two subgroups. One group involves layered
is usually used [168] and can expand both lattice parameters NMCs with different compositions/structures as compared
by reducing transition metal ions (mainly Ni and Mn) [169] with core Ni-rich NMCs and usually possesses higher Co
and increase mean charging voltages due to increased bond or Mn content. Here, a Mn-rich NMC shell can signifi-
energy of Li–F as compared with Li–O [170]. In addition, cantly enhance the chemical and structural stability of Ni-
fluorine substitution can protect cathode materials from rich NMC cores [180, 181] in which studies have shown
HF. Furthermore, although bromine and sulfur atoms can that the coating of Mn-rich spinel oxide onto Ni-rich NMC
be used to enhance NMC cathode performances, few stud- can significantly improve chemical stability in both opera-
ies have shown their effect on Ni-rich NMC-based cathodes. tion and storage [144, 182]. The second group includes all
And currently, studies into the surface modification of Ni- other types of LixMyOz coatings (different transition met-
rich NMC-based cathodes have been insufficient and the als or structures) and also includes pioneering works with
effects of dopants such as Ti [171], Zn [160], Cl and Br disparate coating materials and methods in which Si, Zr,
[172] and their influences on Ni-rich NMC-based cathode Ti and Al are usually used. For example, Li2TiO2 with a
cycling stability need to be further explored. rocksalt structure can be coated onto NMC532 due to its
superior structural integrity and strong adhesion to the core
13
Fig. 11 a Lattice parameter trends of Co and Sn-doped NMC-622 g2+ pillared Li-rich cathode materials. b Mn migration
bare and M
cathode materials in fully lithiated (black squares) and 60% delithi- in bare Li-rich materials from the TM slab to the Li slab through
ated (red squares) states (left) along with corresponding schemat- the adjacent tetrahedral site. c Prohibition of Mn migration in
ics of Li-interlayer movement along the c-axis due to doping effects Mg2+-doped layered oxide by electrostatic repulsion between M
g2+
(right) (Reprinted with permission from Ref. [153]. Copyright © and TM ions (Reprinted with permission from Ref. [125]. Copyright
2018, Elsevier B.V. All rights reserved.) and structural evolution in © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
13
[183] and an ionically conductive L i2ZrO3 coating layer on deposition (usually used to enhance coating uniformity
NMC71515 can form large islands of the coating material, through the precise control of coating thicknesses to several
protect the core and facilitate Li movement [184]. In addi- nanometers or even thinner) of Al2O3 on NMC532 [101,
tion, Li2SiO3 is also a promising coating material because it 130] can suppress parasitic reactions and phase transitions in
is a fast ionic conductor that can provide two pathways for which one study by Dahn group suggested that performance
Li+ movement [(010) and (001) planes] [185]. Furthermore, stabilizations were due to the protection of cathode surfaces
a recent study using LPO infusion to coat NMC particles to surface-oxidized species rather than the prevention of
has gained much attention due to the creation of solid–solid electrolyte oxidation [91]. Furthermore, researchers have
interfaces in the gap between primary particles to replace also reported that the crystallization of amorphous T iO2
liquid–solid interfaces, thus reinforcing the microstructure applied on NMC811 surfaces can result in L i2TiO3, which
by shielding off liquid electrolytes and eliminating side reac- can further inhibit phase transformation from H2 to H3 [96].
tions within secondary particles (Fig. 12b) [97]. Researchers The use of metal oxide layers has also been reported to be
have also suggested that other types of cathode materials able to function as mediators of HF attacks due to the protec-
with more cycling stability can be used as coating materials tion they can provide to NMC cores from corrosion [194].
such as LFP [186]. The application of Li-free coatings can also lead to issues
in Ni-rich NMC-based cathodes. For example, Park et al.
Li‑Free Coating Li-free coatings on the outer surface of have reported that excessive Li on cathode surfaces as caused
NMC cathodes have been extensively investigated due to by the coating of metal phosphate [187] can cause gas evolu-
a unique advantage over doping in which the valence of tion due to its possible transformation into lithium carbonate
transition metal ions remains unaffected and so does the and hydroxide as well as further side reactions with elec-
theoretical capacity. Here, materials used for Li-free coating trolytes [61]. However, researchers have also reported that
include transition metal phosphates [187], metal oxides [99, the use of phosphate can lead to the formation of lithium
188, 189], fluorides [143, 190], silicon oxide [91, 100] and phosphate [195] and lithium transition metal phosphate,
organic coating layers [138, 191] in which the general con- both of which can maintain cell performance. Alternatively,
cept is to prevent cathode surfaces containing highly reactive FePO4 coatings have been shown to be resistive to cathode
Ni4+ from contacting the electrolyte and therefore to reduce dissolution in electrolytes [192] and V 2O5 coatings [189]
side reactions. Here, coating layer thicknesses are usually applied through a wet coating method by using NH4VO3
between 5 and 40 nm and similar to doping, XRD meas- were found to be capable of removing excessive Li. Moreo-
urements usually do not show new characteristic peaks and ver, the introduction of acids or metal oxides can allow for
instead, existing peak widths/positions may change slightly. excessive Li on the surface of cathodic particles to trans-
In addition, the metal ions in coating layers tend to diffuse form into LixMyOz coatings at certain temperatures [196].
into the cathode lattice and can change lattice parameters For example, researchers suggested that the use of excessive
[192]. To meet the basic demands of coating materials, high surface Li on NMC811 to form a protective layer consisting
conductivity (coatings tend to possess higher resistances and of Li+-conductive LixAlO2 and superconductive LixTi2O4
are even insulating, however) and firm adherence to NMC [197] was a cost-saving and efficient method to resolve the
cathodes are preferred [138]. And to optimize cycling sta- issue of excessive Li and improve conductivity.
bility, the weight ratios of coating precursors need to be Organic coating layers possess a unique advantage of
carefully estimated because excessive coating can block Li being stretchy, which allows for the absorption of internal
transport pathways and result in large polarization and low microstrains and the mitigation of primary particle crack-
Li-ion diffusivity. This careful estimation of coating precur- ing [191]. And recently, a novel coating method using the
sor weight ratios can also improve the uniformity and disper- transesterification of organophosphates has been reported
sity of precursor particles at the micrometer scale [141, 188]. [198] in which surface coatings were achieved through the
replacement of M–OH bonds of NMC622 with M–O–P
Among various metal oxide coatings studied, Al2O3 has bonds. Here, this novel coating differs from others because
received the most attention due to multiple beneficial fea- it can be achieved through the chemical deactivation of sur-
tures (Fig. 12c) [12]. For example, Chen et al. have found face groups. Researchers have also reported that like doped
that coating layers of A l2O3 and nano-TiO2 can suppress fluorine, fluoride coatings can also be used to prevent HF
cation mixing (Li+ and Ni2+) as indicated by the ratio of attacks [190]. For example, YF3-coated NMC111 can exhibit
I003–I104 in XRD [99, 188] and that Al2O3 layers can reduce enhanced electron transfer due to smaller surface potentials
self-redox reactions by introducing new energy levels to pre- and reduced oxidation of electrolytes due to smaller work
2−. In addition, researchers
vent the reduction of Ni ions by O functions [143]. Despite these promising results, the num-
have also found that A l2O3 surface coatings can maintain ber of studies into metal fluoride coatings on Ni-rich NMC-
stabler CEI structures [188, 193] and that the atomic layer based cathodes is limited. Alternatively, sulfated ZrO2 as a
13
Fig. 12 a SEM and EPMA results of precursor hydroxide (left) and Al2O3-coated LiNi0.6Co0.2Mn0.2O2 powder (Reprinted with permis-
final lithiated oxide Li(Ni0.64Co0.18Mn0.18)O2 (right) (Reprinted with sion from Ref. [188]. Copyright © 2014, Elsevier B.V. All rights
permission from Ref. [126]. Copyright © 2009, Springer Nature). b reserved.). d SEM image of an NMC 532 cathode obtained through
STEM-HAADF images, EDS maps and schematic of an LPO-infused filtration with 5% CNTs (Reprinted with permission from Ref. [202].
Ni-rich NMC layered cathode (Reprinted with permission from Ref. Copyright © 2014, American Chemical Society)
[97]. Copyright © 2018, Springer Nature). c TEM image of 1.0 wt%
coating material has shown particular promise [193]. This surface impurities due to the coating separating the core
is because different from regular/ultrathin ZrO2 coatings from the atmosphere [200].
[199], sulfated ZrO2 coatings can incorporate sulfate groups
into coating layers and functionalize coatings by forming Carbon Matrixes A novel method to enhance the perfor-
–SO3−– to stabilize CEIs on cathode surfaces, indicating mance of Ni-rich NMC-based cathodes is to build carbon
that these coatings to a large extent are modifiable and func- matrixes containing active material particles. Examples of
tional groups can be added to gain additional functionalities. this method include studies involving graphene nanosheets
Researchers have also reported that graphene oxide-coated for NMC811,141 carbon nanotube conductive networks for
NMC532 does not possess a carbon matrix but a thin layer NMC532 (Fig. 12d) [201, 202], and interwoven carbon fib-
covering primary particles, allowing for the reduction of ers for NMC622 [203]. Here, the matrixes chosen are usually
highly conductive carbon materials that can enhance charge
13
transfer due to 3D connections. In addition, these matrixes 4.1.4 Synergy of Multiple Mitigation Methods
can prevent side reactions and stabilize particle structures
by fully covering primary cathode particles with a conduc- Recently, many studies have focused on the synergy of two
tive matrix. Furthermore, carbon matrixes can enhance or more mitigation methods to achieve better overall Ni-rich
flexibility and strengthen adhesion between primary par- NMC-based cathode performances in which the simplest
ticles. Numerous unconventional and cutting-edge studies examples involve multiple dopants or coatings. For example,
have also emerged in recent years involving the reshaping Al and Fe can be co-doped into NMC622 [131] to combine
of aggregated NMC primary particles through the use of the polarization effects of Fe with the lower chemical poten-
carbon matrixes. For example, multi-shelled alginate hollow tial attributed to Al. As for multiple coatings, this can be
fibers were used to template NMC primary particles, which achieved with the help of organic coating layers, which can
allowed for the accommodation of Ni, Mn and Co atoms supplement the insufficiencies of single-type coatings. For
within an organic fiber matrix that possessed pinholes to example, polypyrrole is a flexible and conductive polymer
ensure Li+ exchange [204]. that is typically used in this type of modification in which
researchers have reported a dual-conductive coating layer of
4.1.3 Advanced Preparation Methods polypyrrole on NMC811 primary particle surfaces that can
convert excessive Li into Li3PO4 [191]. In another study,
Aside from materials for NMC development, preparation researchers coated a Zr-doped NMC532 with polypyrrole to
methods are also being investigated due to similar influences form a network that prevented HF attacks [157].
on the cycling/thermal stability of Ni-rich NMC materials, Apart from coatings and dopants, a newly developed
commonly allowing for the reduction of cation mixing. For trend is to combine surface modifications with gradient lay-
example, Du et al. [154] have reported that NMC532 sintered ers, which can prevent phase transitions of NMC811 and
in oxygen can exhibit lower degrees of cation disordering, NCA particles [210]. In addition, the cathodic doping of
less oxygen defects and higher discharge capacities. These Al into NMC (61 27 12) with FCG has been reported to be
researchers also reported that if N i2+ was partially replaced able to consolidate and reduce grain boundaries and improve
by Li+, the remaining Ni existed as N i3+, leading to capac- mechanical properties [211]. Moreover, researchers have
ity loss [154]. In addition, researchers have also reported combined gradient layers (the core) with Mn-rich surface
that the atomization co-precipitation method can be used to coatings on NMC532 and reported that the valences of Ni
obtain homogeneous spherical shaped primary NMC parti- and Co can be kept at lower states than regular NMC532
cles by forming an aerosol of precursors with an ultrasonic particles. Similarly, NMC811 with an exterior concentra-
nebulizer [205] and that a similar effect can be achieved by tion gradient layer was uniformly coated with Al2O3 through
using a self-combustion method, which produces massive freeze-drying and displayed better capacity retention as com-
heat flow to accelerate synthesis and therefore improve the pared with untreated samples [212]. Furthermore, LiPON as
uniformity of NMC particles [206]. Furthermore, nanoscale a conductive material used to coat anodes can also report-
surface treatments utilizing Co and Li precursors combined edly be applied to NMC811 with a surface gradient layer
with high-temperature sintering have been used to transform to maintain rate capability and improve capacity retention
NMC622 surfaces into a Co-rich area with a NiO rocksalt [213].
phase that can act as a pillar layer to prevent inter-slab col-
lapse [129]. Moreover, a hydrothermal procedure following 4.1.5 Summary
the regular co-precipitation synthesis of NMC (70 15 15)
can reportedly accelerate Li+ entering and exiting Li slabs Despite novel synthesis methods for NMC particles (which
by making use of PVP to reduce crystal growth along the usually require more demanding conditions and extra pro-
(001) plane and favor crystal growth along the (010) plane, cedures), modifications are usually applied to different parts
which is an unimpeded pathway [207]. Dahn et al. [208] of Ni-rich NMC primary particles to protect Ni-rich NMC
have also used a washing and reheating method to synthesize cores. Among these, dopants and coatings are the most
single crystal NMC622 in which superior performances as extensively studied methods. Here, dopants can affect sur-
compared with multi-crystal NMC622 can be achieved if face elemental compositions and lower the Ni content, which
a remedial electrolyte additive was added. Carbonate co- is reactive and can generate spinel phases during cycling. In
precipitation and impregnation methods can also reportedly addition, dopants can expand/contract L iNixMnyCo1−x−yO2
+
be combined to synthesize porous NMC622 microspheres lattices and influence Li movement through bulk particles.
i2+ and shorten Li diffusion
that can effectively precipitate N Furthermore, dopants possessing different valances from
pathways [209]. substituted ions can affect the valences of Ni, Mn and Co
and therefore increase/decrease their capacity as the capac-
ity is achieved by the change of valence of these elements.
13
Additional effects such as the repulsion of cation disorder 4.3 SEI

and the prevention of HF corrosion can also be achieved
through doping. As for coatings, these can impact NMC 4.3.1 Electrolyte Additive
performances by separating surfaces from electrolytes and
hindering side reactions in which optimal performances can LIBs need to be safely transported and operated. Here, the
be achieved through the accurate estimation of the amount addition of relatively small amounts of electrolyte additives
of coating applied. can improve overall cell safety without the introduction of
any detrimental products. For example, vinylene carbonate
4.2 Graphite Anode (VC) is one of the most extensively utilized electrolyte addi-
tives because it can improve compatibility between SEIs and
4.2.1 Testing Protocols graphite anodes by forming a thin film to separate electro-
lytes from graphite anodes and enhance the performance
The rate of charge, as limited by the production of plated Li, of ionic liquid-based electrolytes [128]. Researchers have
can be increased by applying the constant-current constant- also hypothesized that VC can reduce SEI thicknesses by
voltage (CCCV) protocol and the pulse charging protocol inhibiting electron transfer from graphite anodes to sol-
[105] in which Li concentration gradients are alternatingly vents. Despite many positive influences of VC as reported
enlarged and reduced during charging with the CCCV pro- by Dahn group [107], researchers have also suggested that
tocol and concentration differences between anode surface the highly resistive film formed with VC can facilitate Li
regions and bulk electrolytes are minimized in the pulse plating [217] and that the polymerization of VC can limit
charging protocol. LIB lifespans. Here, many additives have been tested to
replace VC to resolve polymerization issues in which FEC
4.2.2 Surface Coating [139], PES [218] and VEC have been used to reinforce SEIs
because they possess higher LUMOs that can prevent the
Aside from testing protocols, substantial barriers involv- reductive decomposition of VC by sacrificing themselves
ing materials being applied to graphite surfaces through (Fig. 13a, b). In addition, FEC can form an SEI that is dura-
different means can fully separate graphite anodes from ble to fast charging, thus eliminating Li plating on graphite
electrolytes, leading to significant reductions in the anodes [219]. Researchers have also reported that the use
reductive decomposition of solvents, and subsequent of FEC can suppress [139] or slow down [220] SEI for-
conversion and thickening as well as the suppression of mation (formation of lithium alkyl carbonate) to result in
exfoliation. For example, LiPON as a recently investi- a thinner SEI. The use of co-solvents can also lower the
gated material can be evenly coated onto graphite anodes viscosity and the melting point of solvents and therefore be
and can protect the anode from high-temperature storage useful in practical cases (Fig. 13c). For example, 2% PES
aging [214]. with 1% DTD and 1% TTSPi (PES211) can enhance the
cycling performance of NMC cells based on its composi-
4.2.3 Electrolyte Volume Adjustment tion [142]. Researchers have also reported that PTSI as a
less investigated additive can generate better SEIs with less
The performance of full cells is strongly dependent on the inorganic components in which due to the presence of S=O
amount of accessible active material. And because both groups, PF5 can be suppressed as delocalized N cores can
electrodes and the separator in full cells are porous, they act as weak base sites [112]. And more recently, 3-sulfolene
need to be sufficiently wetted. In addition, electrolyte vol- (3SF) as a film-forming agent was used to reduce electrolyte
umes can also be increased to maximize the amount of reduction [221]. Additives that stabilize SEI can be divided
accessible active material; however, higher electrolyte into two subgroups including SEI formers and SEI modifiers
volumes do not directly translate into higher capacities in [222] and phenyl carbonate, regarded as a “modifier” addi-
which researchers have reported that excessive electrolytes tive, can outperform VC by maintaining low impedance and
tend to decrease performance because higher fractions of gas production in NMC111/graphite pouch cells and there-
SEIs can dissolve into increased electrolyte volumes [215]. fore can be used to stabilize cells [222]. In addition, phenyl
This principle is also valid in pouch cell studies showing carbonate can remain stable until 4.2 V and possess good
the lowering of impedance and increase in cycling stabil- compatibility with 2% vinylene carbonate (VC). And since
ity [216]. electrolyte additives can be multi-functional because certain
types of additives can react with electrodes to produce gas
if cells are overcharged to unsafe voltages, which results in
pressurized internal environments that can deactivate cells
[222], the ability to reduce gas production makes phenyl
13
Fig. 13 a HOMO and LUMO energy levels of EC, FEC and VC. b blends. Cycling was conducted between 2.8 and 4.2 V at 55 °C at
Schematic showing the effects of VC- and FEC-derived SEIs on the 80 mA. Bottom: capacity versus cycle number for NMC442/graph-
fast charging capability of graphite anodes (Reprinted with permis- ite pouch cells (unclamped) containing select additives or additive
sion from Ref. [219]. Copyright © 2018, Elsevier B.V. All rights blends. Cycling was conducted between 3.0 and 4.4 V at 45 °C at
reserved.). c Up: capacity versus cycle number for NMC111/graph- 100 mA. (Reprinted with permission from Ref. [142]. Copyright ©
ite pouch cells (unclamped) containing select additives or additive The Author(s) 2015. Published by ECS)
carbonate a promising type of electrolyte additives. Further- of SEIs with capping agents such as oxalate in which the
more, PBF and PPF as electrolyte additives have also been capping agents can reductively decompose electrolytes and
reported to be able to positively enhance SEIs [36]. prevent LiF from aggregating into large particles, thus pro-
ducing LiF nanoparticles 5 nm in diameter uniformly in
SEIs [224]. Furthermore, the reduction in LiF aggregation
4.3.2 Lithium Salt and the formation of nanostructured LiF can form uni-
i+ diffusion and reduce lithium plating
form regions for L
A simple method to enhance the quality and durability (Fig. 15). Researchers have also reported that LiTFSi can
of anodes and SEIs is to raise the concentration of Li outperform conventional L iPF6 salts due to its resistance
salts to above 3 M [223], which can significantly reduce to trace amounts of water and therefore minimize the pro-
polarization that can lead to negative effects such as den- duction of harmful species [225].
drite growth and slow charging. In addition, the resulting
solvation of Li-ions possesses a disparate structure from 4.3.3 Solvent
regular Li-ions in which the planar shape of the solvated
Li-ions benefits from Li intercalation and can mitigate The polarity and the viscosity of solvents also need to be
graphite exfoliation with smaller spaces being occupied considered in the selection of appropriate solvents for Li
during operation [223]. Advanced Li salts have also been intercalation/deintercalation in which solvents with lower
widely investigated to obtain better performances with viscosity can facilitate L i+ transportation and decrease
promising results; however, few have been commercial- impedance, whereas the polarity of a solvent can deter-
ized. In addition, a new group of Li salts (Fig. 14) have mine the degree of solvation of L i+ inside [225]. Here,
been reported to significantly enhance the performance ethyl methyl carbonate and dimethyl carbonate are usually
13
toward cathode degradation. Alternatively, graphite anodes

can function collaboratively with NMC-based cathodes
to provide promising performances at cell levels. How-
ever, the aging of graphite anodes due to the formation
of dendrites as caused by the massive plating of L i+ onto
graphite surfaces remains the main reason for increased
impedance. Furthermore, side reactions involving elec-
trolyte reduction (SEI formation) on graphite anodes can
cause Li loss after initial charging, and the thickening and
decomposition of SEIs in subsequent cycles can cause
aging behaviors.
To gain a deeper understanding of degradation mecha-
nisms of Ni-rich NMC/graphite LIBs, emerging testing
protocols and characterization methods have emerged in
which currently, research on LIB degradation is focused on
the elucidation of the degree of capacity fading in certain
mechanisms so as to distinguish major factors and allow
for the design of specific remedies. And as a result of this
research, mitigation strategies, functioning individually or
synergistically, have been proposed to resolve long-term
cyclability issues, most of which have proven to be promis-
ing. Among these, dopants, gradient layers, coatings (both
Li-free and Li-contained), carbon matrixes and advanced
synthesis procedures have become mainstream methods to
enhance the performance of Ni-rich NMC-based cathodes.
In addition, coatings, advanced protocols and the use of new
Fig. 14 Comparison of a Coulombic efficiency versus cycle number
and b the total sum of reversibly cycled Li over 50 cycles obtained
electrolyte components can be applied to ameliorate anodic
from LiFePO4/Cu cells (Reprinted with permission from Ref. [224]. performances (SEIs and graphite). And with these mitiga-
Copyright © 2018, The Royal Society of Chemistry) tion strategies, the morphology, element composition and
reactivity of electrodes can be improved.
Although differences in the performance of various
considered [219]. In addition, ionic liquids as substituents Ni-rich NMC-based cathodes have been discovered, these
of conventional solvents can form thicker SEIs with high- remain unexplained and the future of degradation mecha-
capacity retentions at 90 °C [226]. nism investigations needs to rely on more advanced physi-
cal techniques such as X-ray tomography, operando neutron
diffraction and online electrochemical mass spectroscopy,
5 Summary and Prospective all of which can provide more comprehensive information
in operando and be less destructive to cells. And for the
LIBs using Ni-rich NMC-based cathodes such as NMC811 deeper understanding of mitigation strategies for Ni-rich
can produce high specific capacities (200–220 mAh g−1) NMC/graphite LIBs, trade-offs in modification techniques
and promising energy densities (~ 800 Wh kg−1) in com- and controversies need to be taken into considerations. Here,
parison with conventional LiCoO2 (~ 570 Wh kg−1) and several prospective research directions for Ni-rich NMC/
LiMn2O4 spinel (~ 440 Wh kg−1) materials. Because of graphite LIBs are proposed:
this, these materials have received extensive attention from
researchers. However, due to low portions of manganese 1. Future experiments should focus more on the quantita-
as structural stabilizers, large amounts of Ni4+ on cath- tive interpretation of different aging behaviors in NMC-
ode surface layers/regions can trigger side reactions and based cathodes with or without mitigation methods as
Ni2+ can cause cation mixing. As a result, enhanced mass- well as the understanding of correlations between dif-
specific capacity comes at the expense of rate capability ferent degradation mechanisms.
and structural stability in these Ni-rich cathode materials, 2. Efforts should be made toward profiling the performance
leading to severe capacity fading. In addition, other factors of LIBs under harsher conditions (stressors) that more
such as active material dissolution, oxygen release and the closely represent practical operational conditions.
intergranular cracking of primary particles also contribute
13
Fig. 15 a, b Proposed mechanisms of LiDFOB acting as a capping sesses active and inactive areas on its surface (Reprinted with permis-
agent for LiF nanoparticle generation; c, d models of SEIs from c sion from Ref. [224]. Copyright © 2018, The Royal Society of Chem-
LiDFOB and d LiBF4 + LiBOB electrolytes; and e, f schematics of istry)
diffusion fields at Li plated from each electrolyte. Each Li plate pos-
3. Studies should be conducted to investigate and optimize Open Access This article is distributed under the terms of the Crea-
the synergistic effects of multiple mitigation methods tive Commons Attribution 4.0 International License (http://creativeco
mmons.org/licenses/by/4.0/), which permits unrestricted use, distribu-
on Ni-rich NMC-based cathodes that can outperform tion, and reproduction in any medium, provided you give appropriate
the effects of single mitigation methods and enhance credit to the original author(s) and the source, provide a link to the
capacity retention to higher levels. Creative Commons license, and indicate if changes were made.
4. Inexpensive and nondestructive characterization tools
need to be developed to decrease research costs and pre-
vent cell destruction, especially in the inline detection References
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chim. Acta 191, 401–410 (2016). https://doi.org/10.1016/j.elect 224. Jurng, S., Brown, Z.L., Kim, J., et al.: Effect of electrolyte on
acta.2016.01.092 the nanostructure of the solid electrolyte interphase (SEI) and
210. Mohanty, D., Dahlberg, K., King, D.M., et al.: Modification of performance of lithium metal anodes. Energy Environ. Sci. 11,
Ni-rich FCG NMC and NCA cathodes by atomic layer depo- 2600–2608 (2018). https://doi.org/10.1039/c8ee00364e
sition: preventing surface phase transitions for high-voltage 225. Farhat, D., Maibach, J., Eriksson, H., et al.: Towards high-
lithium-ion batteries. Sci. Rep. 6, 26532 (2016). https://doi. voltage Li-ion batteries: reversible cycling of graphite anodes
org/10.1038/srep26532 and Li-ion batteries in adiponitrile-based electrolytes. Electro-
211. Kim, U.H., Lee, E.J., Yoon, C.S., et al.: Compositionally graded chim. Acta 281, 299–311 (2018). https://doi.org/10.1016/j.elect
cathode material with long-term cycling stability for electric acta.2018.05.133
vehicles application. Adv. Energy Mater. (2017). https://doi. 226. Rodrigues, M.T.F., Sayed, F.N., Gullapalli, H., et al.: High-tem-
org/10.1002/aenm.201700254 perature solid electrolyte interphases (SEI) in graphite electrodes.
212. Wang, J.P., Du, C.Y., Yan, C.Q., et al.: Al2O3 coated concen- J. Power Sources 381, 107–115 (2018). https: //doi.org/10.1016/j.
tration-gradient Li[Ni0.73Co0.12Mn0.15]O2 cathode material by jpowsour.2018.01.070
freeze drying for long-life lithium ion batteries. Electrochim.
13
Tianyu Li received his Bachelor Datong Song obtained his Ph.D.

of Science (B.Sc.) degree in in Computational Mechanics
Materials Science at Nanjing from Jilin University in 1994.
University. He is currently work- Currently, he is a senior research
ing toward a Ph.D. degree in officer at Energy, Mining and
chemistry at the University of Environment Research Centre,
Victoria, specializing in the National Research Council
microfluidic devices for online (NRC) of Canada. He has more
detection of alcohol electrooxi- than 20-year experience in
dation with Raman spectroscopy. mechanical engineering, fuel cell
He worked as a co-op student modeling and optimization, and
researcher at National Research energy storage modeling and
Council Canada. analysis. Prior to joining NRC,
he was a professor in the Depart-
ment of Mechanics, Jilin Univer-
sity, Jilin, China. His research
Dr. Xiao‑Zi Yuan is a Research interests cover mechanical dynamics, vibration and stress analysis,
Officer at the Energy, Mines and modeling simulation for fuel cells and batteries.
Environment (EME) Research
Centre of the National Research Kaiyuan Shi is currently an Assis-
Council Canada (NRC). Dr. tant Research Officer at Energy,
Yuan received her B.S. and Mining and Environment
M.Sc. in Corrosion and Protec- Research Centre, National
tion from Nanjing University of Research Council Canada. Prior
Technology in 1991 and 1994, to this, he worked as a Postdoc-
respectively, and her Ph.D. in toral Scholar in the Department
Material Science from Shanghai of Chemical Engineering at Cali-
Jiaotong University in 2003. fornia Institute of Technology
Beginning in 2004, she carried (Caltech) after securing his
out a 3-year postdoctoral Ph.D. degree from McMaster
research program supported by University. His research is
Natural Sciences and Engineer- mainly focused on developing
ing Research Council (NSERC). Since 2007, Dr. Yuan has been work- advanced materials for electro-
ing with NRC. Her research interests include PEM fuel cells, Li-ion chemical energy storage, includ-
batteries, Zn/Li air batteries, and other types of electrochemical devices ing supercapacitors, Li-ion
and energy storage systems. Her research areas range from cell design, capacitors, fuel cells and Li-ion batteries. Besides, he has conducted
electrode material and structure to cell testing, diagnosis and durability. substantive research on capacitive deionization, steels and cast irons,
In 2014 and 2016, Dr. Yuan was listed as a Highly Cited Researcher by surface cladding and fatigue analysis of metals.
Thomson Reuters under the Engineering Section and World’s Most
Influential Scientific Minds. Christina Bock is a Senior
Research Officer at the Energy,
Lei Zhang is currently a Senior Mining and Environment
Research Officer at Energy, Min- Research Centre, of the National
ing and Environment (EME) of Research Council Canada in
National Research Council Can- Ottawa. She is the leader of the
ada (NRC), a Fellow of the Energy Storage Materials and
Royal Society of Chemistry Formulation Team and also the
(FRSC) and a member of the program technical leader of
NSERC Industrial R&D Fellow- NRC’s Energy Storage for Grid
ships College of Reviewers. Lei Security and Modernization Pro-
received her first Master’s degree gram. She has over 25 years of
in Materials Chemistry (1993) experience in electrochemistry
from Wuhan University and her and materials research for energy
second Master’s degree in Physi- storage, energy conversion and
cal Chemistry (2000) from the environment.
Simon Fraser University, Can-
ada. Lei’s main research interests
include advanced materials and electrochemical energy technologies
in the area of PEM fuel cell electrocatalysis, supercapacitors, metal-air
batteries and Li-ion batteries. She has co-authored more than 200 pub-
lications (> 16300 citations).
13

Degradation Mechanisms and Mitigation Strategies of Nickel Rich NMC Based Lithium Ion Batteries

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Electrochemical Energy Reviews (2020) 3:43–80

Degradation Mechanisms and Mitigation Strategies of Nickel‑Rich

1 Introduction ­LiNixMnyCo1−x−yO2 (NMC) layered oxides have received

2 Degradation Mechanisms 2.1.1 Surface Degradation During Cell Operation

Ni-rich NMC-based materials are some of the most prom-

NMC-based cathodes with Ni-rich surfaces behave differ- 2.1.3 Other Issues

Cracking of Secondary Particles Reduced performances due 2.2 Graphite Anode

Fig. 4 Crystal structures of a

Throughout the development of LIBs, a variety of electro-

Charge/discharge tests include basic electrochemical char-

Voltage versus capacity Charge/discharge curves are com-

Differential Capacity Curve Differential capacity curves are

Fig. 6 Summary of degradation

Table 1 List of identified degradation mechanisms of Ni-rich NMC/graphite LIBs

1 N/A Initial SEI formation consuming active Li Anode [108]

reactions is commonly used in which the charge effi-

percentages should be around 100% (­ CEanode is a bit less,

results were pre-calibrated with known Li concentrations 3.2.3 Thermal Stability

Fig. 10 a Specific charge and

Ni-rich NMC-based cathodes suffer significantly more from 4.1.1 Inner Surface

Additional effects such as the repulsion of cation disorder 4.3 SEI

toward cathode degradation. Alternatively, graphite anodes

Tianyu Li received his Bachelor Datong Song obtained his Ph.D.

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1 Introduction LiNixMnyCo1−x−yO2 (NMC) layered oxides have received

2 Degradation Mechanisms 2.1.1 Surface Degradation During Cell Operation

NMC-based cathodes with Ni-rich surfaces behave differ- 2.1.3 Other Issues

Cracking of Secondary Particles Reduced performances due 2.2 Graphite Anode

percentages should be around 100% ( CEanode is a bit less,

results were pre-calibrated with known Li concentrations 3.2.3 Thermal Stability

Ni-rich NMC-based cathodes suffer significantly more from 4.1.1 Inner Surface

Additional effects such as the repulsion of cation disorder 4.3 SEI