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Ni‐Rich/Co‐Poor Layered Cathode for Automotive Li‐Ion Batteries: Promises

and Challenges
Article in Advanced Energy Materials · February 2020

DOI: 10.1002/aenm.201903864
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Ni-Rich/Co-Poor Layered Cathode for Automotive Li-Ion

Batteries: Promises and Challenges
Xinxin Wang, Yuan-Li Ding,* Ya-Ping Deng, and Zhongwei Chen*
owing to a huge element resource con-
To pursue a higher energy density (>300 Wh kg−1 at the cell level) and a sumption (for example: Li consumption
lower cost (<$125 kWh−1 expected at 2022) of Li-ion batteries for making is ≈15 kg for 100 kWh EVs) compared
electric vehicles (EVs) long range and cost-competitive with internal com- to portable and consumer electronics
(≈2 g Li for smartphones).[8,9] Widespread
bustion engine vehicles, developing Ni-rich/Co-poor layered cathode
adoption of EVs, however, still faces some
(LiNi1−x−yCoxMnyO2, x+y ≤ 0.2) is currently one of the most promising strate- barriers such as range anxiety, price, cap-
gies because high Ni content is beneficial to high capacity (>200 mAh g−1) ital preservation ratio, charging time, and
while low Co content is favorable to minimize battery cost. Unfortunately, safety.[8,10]
Ni-rich cathodes suffer from limited structure stability and electrode/electrolyte
interface stability in the charged state, leading to electrode degradation and
1.1. Key Parameters of Ni-Rich NCM
poor cycling performance. To address these problems, various strategies have Cathode in LIBs for EV Application
been employed such as doping, structural optimization design (e.g., core–
shell structure, concentration-gradient structure, etc.), and surface coating. In Driving range is one of the most con-
this review, five key aspects of Ni-rich/Co-poor layered cathode materials are cerned issues for consumers, and it is
explored: energy density, fast charge capability, service life including cycling expected to reach at least 300 miles in
the future.[11] In this regard, developing
life and calendar life, cost and element resources, and safety. This enables a
high-energy LIBs has become an urgent
comprehensive analysis of current research advances and challenges from research task in academic and industrial
the perspective of both academy and industry to help facilitate practical areas, which is expected to be over 300 Wh
applications for EVs in the future. kg−1 at the cell level in the near future.[12]
In general, cathode materials play a cru-
cial role in the whole cell system including
working voltage, specific capacity, power
1. Introduction density, energy density, cycle life, and safety (Figure 1).[13–15]
Currently, the state-of-the art cathode materials for EVs are
Lithium ion batteries (LIBs) have dominated the field of port- spinel LiMn2O4 (LMO, theoretical capacity: 148 mAh g−1),
able and consumer electronics owing to high energy density, olivine LiFePO4 (LFP, theoretical capacity: 169 mAh g−1),
long cycle life, no memory effect, and relatively environmental LiNi0.8Co0.15Al0.05O2 (NCA, ≈200 mAh g−1), and
benign.[1–4] In recent years, they are opening up new appli- LiNi1−x−yCoxMnyO2 (NCM, 160–200 mAh g−1 depending on Ni
cations in electric vehicles (EVs) and grid energy storage.[5-7] content).[14,16,17] Among these relatively mature cathode mate-
Especially for automotive applications, they will bring a great rials, only layered Ni-rich NCA or NCM with Ni content (>80%)
developing potential for pushing rapid development of LIBs can offer a reversible capacity of over 200 mAh g−1 with a rela-
tively high working voltage (3.8 V).[12] So Ni-rich layered cathode
would be one of the most effective candidates for achieving
X. X. Wang, Prof. Y.-L. Ding
College of Materials Science and Engineering high specific energy with over 300 Wh kg−1 at the cell level in
Hunan University the future. Besides, other performances of cathode material are
Changsha 410082, China equally important for EVs, such as power density, service life,
E-mail: ylding@hnu.edu.cn element resources and cost, and safety (Figure 1). Power density
Prof. Y.-L. Ding (in W kg−1 or W L−1) of cathode material determines the fast
State Key Laboratory of Powder Metallurgy
Central South University
charge capability of LIBs, which mainly influences the charging
Changsha 410082, China time of EVs. Cycling and calendar lifetime of cathode material
Y.-P. Deng, Prof. Z. W. Chen are major obstacles to limit the service life of LIBs, and further
Department of Chemical Engineering affect the maintenance costs and capital preservation ratio of
University of Waterloo EVs. Furthermore, elemental reserves and distributions have
200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada a direct impact on cost and supply security of cathode mate-
E-mail: zhwchen@uwaterloo.ca
rial for LIBs.[8,18] Although the cost of LIBs is reduced continu-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201903864.
ally, it still accounts for the largest proportion of the total cost
of EVs so far, thereby affecting the price and supply of EVs.
DOI: 10.1002/aenm.201903864 Moreover, the stability of cathode materials including chemical,
Adv. Energy Mater. 2020, 1903864 1903864 (1 of 28) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advenergymat.de
electrochemical, and interface stability is very important to

reduce thermal runaway of LIBs to prevent and slow down Xinxin Wang received his
fire and explosion of EVs. Based on the above concerns, cathode Master’s degree (2017) in
material for next-generation EVs should meet at least the Materials Engineering from
following five aspects: 1) high energy density; 2) high power Central South University,
density; 3) long cycling and calendar lifetime; 4) low cost where he specialized in
without element demand/supply risk; 5) high safety.[17,19] nanostructure design. He
is now pursuing his Ph.D.
in Materials Science and
1.2. The Development of NCM Cathode Engineering under the super-
vision of Prof. Yuan-Li Ding
LiCoO2 (LCO) with an α-NaFeO2 like layered structure was at the Hunan University. His
first commercialized as cathode material for LIBs since research is currently focused
1991.[20] However, the available specific capacity for LCO on the development of novel electrode structures and cell
is only 140 mAh g−1 (50% of theoretical capacity) owing to designs for long-lasting rechargeable metal-ion batteries.
unstable issue upon overcharge.[1,21] Compared to LCO, LiNiO2
(LNO) can offer a higher specific capacity up to 274 mAh g−1
Yuan-Li Ding received his
and lower cost owing to relatively abundant resource of Ni
Ph.D. in Materials Science at
element. However, LNO suffers from Li/Ni cation mixing,
Zhejiang University and then
pristine phase synthesis difficult, and limited structural and
worked as a postdoc fellow
chemical stability, thus hindering its practical application.[22,23]
at the National University
Recently, partially transition metal doping (e.g., Co, Mn, Al)
of Singapore, Max-Planck-
in LNO has become an efficient strategy to address the above
Institute for Solid State
issues. The resulting NCM cathode by introducing Co and Mn
Research, and the University
into LNO with a balanced performance and flexible combina-
of Waterloo. He is currently
tion of ingredients are favorable for higher specific capacity
a full professor at Hunan
and energy density.
University, China. His research
In the early stages, the development of NCM cathode
interest mainly focuses on the
is randomness (Figure 2). Ni-rich NCM materials, such as
Adv. Funct. Mater. for electrochemical energy storage and
LiNi0.7Co0.2Mn0.1O2 (NCM-721), LiNi0.6Co0.2Mn0.2O2 (NCM-622),
conversion in lithium ion batteries, sodium ion batteries,
and LiNi0.5Co0.2Mn0.3O2 (NCM-523), were first reported as
zinc ion batteries, and lithium sulfur batteries.
cathode materials for LIBs in 1999 by Liu et al.[24] Lately,
Yoshio et al. reported LiCoyMnxNi1−x−yO2 (0 ≤ y ≤ 0.3, x = 0.2)
cathode materials.[25] They found that the presence of Co Zhongwei Chen is Canada
Research Chair (CRC-Tier 1)
Professor in Adv. Mater.
for Clean Energy at the
University of Waterloo,
Fellow of the Canadian
Academy of Engineering,
Director of Waterloo
Center for Electrochemical
Energy, and Vice President
of International Academy
of Electrochemical Energy
Science (IAOEES). His research interests are in the devel-
opment of electrodes for fuel cells, metal–air batteries, and
lithium ion batteries.
in LiMn0.2Ni0.8O2 can suppress partial cation mixing, and

LiCoyMn0.2Ni0.8−yO2 cathode materials show a high capacity
over 155 mAh g−1. But NCM cathode does not seem to receive
so much consideration, especially Ni-rich NCM. Until 2001,
Ohzuku and Makimura reported layered NCM materials
with the same proportion of Ni, Co, and Mn, researchers
started to recognize the importance of NCM gradually.[26]
Figure 1. Key parameters of Ni-rich NCM cathode in LIBs for EV LiNi1/3Co1/3Mn1/3O2 (NCM-111) exhibited a reversible capacity
application. of 160 mAh g−1 and high safety properties compared with
Figure 2. A historical outline of the development of NCM cathode materials from low Ni content to high Ni content.
LiCoO2 and NCA.[27] It opened the door to a new era for NCM and it shows the approaching rate capability with NCM90 when
cathode materials, and low-Ni NCM cathode entered a period temperature up to 60 °C. The study may redefine the role of
of rapid development for LIBs. After that, LiNixCo1−2xMnxO2 Mn in a Ni-rich NCM cathode.
series (LiNi0.25Co0.5Mn0.25O2 and LiNi0.375Co0.25Mn0.375O2), Although Ni-rich NCM shows much more attractive merits,
LiNixCo1−2xMnxO2 (0 ≤ x ≤ 0.5), and LiNi0.4Mn0.4Co0.2O2 (NCM-424) it still suffers from some issues (e.g., chemical/electrochem-
were reported in succession.[28,29] These low-Ni NCM materials ical instability, particle degradation, interface side reaction,
show higher energy density and thermostability than LiCoO2, etc.), thus limiting its practical applications.[22,40,41] To address
but they still suffer from the capacity limitation (<200 mAh g−1). these challenges, various strategies have been used widely, for
As a result of high reversible capacity (>200 mAh g−1), low example, doping,[42,43] coating,[44,45] structural design,[46,47] and
toxicity, and low cost, Ni-rich NCM cathode materials have hybrid strategy.[48] For safety issues, program control is even
become a mainstream of research in these years, especially for introduced to reduce hazards.[49] We will discuss these contents
EVs.[6,30,31] In 2005, Liao et al. reported LiNi0.75−xCo0.25MnxO2 in detail in the following sections.
(0.1 ≤ x ≤ 0.25) cathode materials, and LiNi0.6Co0.25Mn0.15O2
showed the best electrochemical performance (initial dis-
charge capacity: 167 mAh g−1).[32] In the next year, Kim et al. 1.3. Scope of This Review
reported spherical LiNi0.8Co0.1Mn0.1O2 (NCM-811) and
LiNi0.8Co0.2O2 synthesized by coprecipitation method with a Although some reviews have well summarized existing issues,
discharge capacity of 197–202 mAh g−1.[33] NCM-811 showed material modification, and potential applications of Ni-rich lay-
better thermal stability than LiNi0.8Co0.2O2 due to the enhanced ered cathode materials,[2,4,6,12,30,31,50,51,52] most reviews mainly
structural stability with a small amount of Mn content. This focus on one aspect or two aspects (energy density, cycling life-
finding was subsequently validated by Lee et al.[34] In 2009, Li time, etc.) of the Ni-rich NCM. To push the practical applica-
et al. compared the electrochemical performance and thermal tion of Ni-rich NCM for automotive LIBs, the comprehensive
stability of LiNi0.6CoxMn0.4−xO2 (x = 0.05, 0.10, 0.15, and 0.2) and full understanding of Ni-rich NCM is highly desirable in
cathode materials.[35] They found that the discharge capacities the perspectives of both academy and industry. In this review,
of these cathode materials were improved with the increase of we give a comprehensive analysis of Ni-rich NCM materials in
Co content, but their cycling performances and thermal stabili- terms of energy density, power density, cycling and calendar
ties got worse with the decrease of Mn content simultaneously. lifetime, element resources and cost, and safety. First, crystal
Among them, LiNi0.6Co0.05Mn0.35O2 exhibited best thermal structure and chemical composition of Ni-rich NCM is systemi-
stability due to high Mn content. In 2013, Noh et al. demon- cally summarized, and the structure-energy density relationship
strated the initial discharge capacity of NCM cathode material is also discussed in detail. In the second section, we discuss fast
can improved with the increase of Ni content.[36] In 2016, Ma charging capability for Ni-rich NCM cathode since it is highly
et al. indicated that the thermal stability can be improved with desirable for automotive application. In the third section,
the increase of Mn content, but Mn doping may lead to the cycling and calendar lifetime of Ni-rich NCM are evaluated and
discharge capacity fade.[37] In the past five years, researchers discussed, respectively. In the fourth section, element reserves
and manufacturers have paid more attention to Ni-rich NCM of Ni, Co, Mn, and Li are summarized in detail for automo-
cathode.[38] From the development situation, the proportion of tive LIB application. Considering the limited element reserves,
nickel in the NCM materials is increasing continually (over the cost analyses of a series of NCM materials including NMC-
90%) with the decrease of Co and Mn. In very recently, Aishova 111, NMC-433, NCM-523, NCM-622, and NCM-811 are roughly
et al. synthesized and compared the physicochemical properties calculated and evaluated for their battery applications. Finally,
of LiNi0.9Co0.05Mn0.05O2 (NCM90), LiNi0.9Mn0.1O2 (NM90), and safety issues of Ni-rich NCM-based LIBs are overviewed and
LiNi0.9Co0.1O2 (NC90).[39] NM90 exhibits better cycling stability, discussed.
2. Energy Density of Ni-Rich NCM With the increase of Co content, Ni2+ can be substituted by
Co3+ with a ionic radius of 0.54 Å, and the unit cell size of NCM
Currently, “range anxiety” is still one of the biggest obstacles materials gets smaller. Also, the deintercalation time of Li ions
for widespread adoption of EVs, and consumers are forced from the crystal structure are shortened.[58] Thus, the presence
to endure shortening mileage. It hurts consumers’ confi- of element Co is benefit to decrease the cation mixing of NCM
dence in using EVs for long-distance travel compared with cathode materials.
internal combustion engine vehicles (ICEVs).[53] In order to
solve the problem of “range anxiety,” the range of EVs should
be increased to at least 300 miles by 2022.[54,55] Consequently, 2.2. Chemical Composition and Performance of Ni-Rich NCM
increasing energy density of LIBs becomes a key for increasing
driving range of EVs.[17] In recent years, Ni-rich NCM exhibits Figure 3b shows the relationship of the NCM performance and
more and more attraction for automotive application owing to element proportion (Ni, Co, and Mn) inside of the compositional
higher energy density and lower cost compared to counterparts. phase diagrams. In the NCM material system, the chemical
valences of Ni, Co, and Mn in NCM are +2, +3, and +4, respec-
tively. The element of Ni (Ni2+) is active and important to improve
2.1. Structure of Ni-Rich NCM specific capacity and energy density. The presence of Co (Co3+)
is beneficial for the enhancement of conductivity and rate per-
As shown in Figure 3a, NCM cathode materials exhibited formance, while the element of Mn (Mn4+) is inactive but is
α-NaFeO2-type structure with a hexagonal layered phase (space very beneficial to enhance structural stability. As such, NCM
group: R-3m).[29,56,57] Ni-rich NCM cathode materials can be has combined with the advantages of LiCoO2, LiNiO2, and
described by a general formula of LiNi1−x−yCoxMnyO2 (0 < x+y ≤ 0.5), LiMnO2 due to their synergistic reaction of Ni–Co–Mn. NCM
and be seen as LiNiO2-doped with a little bit Co and Mn, such cathode material exhibits higher specific capacity than LCO
as NCM-523, NCM-622, and NCM-811. The Li and O atoms are with a similar cut-off voltage. Among the NCM cathode mate-
placed on 3a and 6c sites of the crystal structure, respectively. rials, NCM-111 shows high reversible capacity and excellent
The transition metal atoms of Ni, Mn, and Co are distributed on cycle performance with the same proportion of Ni, Co, and Mn.
3b sites randomly. Usually, a small amount of Ni and Li atoms Furthermore, with the increasing of Ni content, the specific
exchange their position between 3a and 3b sites, due to the capacity of NCM is improved, but its safety and rate capability
approximate radius of Ni2+ cation (0.69 Å) and Li+ (0.76 Å).[57] are weakened as a result of the reduction of Mn and Co.
Figure 3. a) The crystal structure of NCM materials. Reproduced with permission.[64] Copyright 2003, Elsevier. b) Compositional phase diagrams of
layered lithium transition metal oxide. Reproduced with permission.[16,65] Copyright 2012, The Royal Society of Chemistry. Copyright 2016, Elsevier.
c) Schematic of d-electron levels of NCM materials. Reproduced with permission.[29] Copyright 2002, The Electrochemical Society. d) Schematic of the
positions of the various redox couples relative to the top of the oxygen: 2p band.
Actually, the change of chemical composition of Ni-rich capacity in NCM cathode materials at the same operating
NCM influences the outer electron arrangement of transition voltage.[16] And the elements of Mn is beneficial for enhancing
metal element. As shown in Figure 3c, the d-electron level of the chemical structure stability of NCM cathode itself.
transition metal elements (Ni, Co, and Mn) in the NCM cathode
materials splits to eg and t2g. The electronic configuration of
Mn4+ is at high spin state (t2g3eg0), but that of Ni2+ (t2g6eg2) 2.3. Energy Density Comparison of Ni-Rich NCM
and Co3+ (t2g6eg0) ions are at low spin state.[59] The electrons of
Mn3+ in the eg energy band are inclined to transfer to the elec- Conventional cathode materials in LIBs are usually transition
tronic orbit of Ni3+ in the eg energy band, forming the Mn4+ metal oxides and polyanionic compounds with the elements of
and Ni2+.[29,60] As such, the valence states of Mn, and Co in Ni- lithium (Li) and transition metals (Ni, Co, Mn, Fe, etc.), such
rich NCM cathode materials are +4 and +3, respectively. In the as layered LiMO2 (M = Ni, Co, Mn, etc.), spinel LiM2O4 (M =
electrochemical cycle, the valence state of manganese remains Mn, etc.), olivine LiMPO4 (M = Fe, Mn, Ni, Co, etc.), and their
unchanged at +4, which plays an important role in stabilizing derivatives.[4,13] Despite several novel compounds, such as sili-
the crystal structure. However, the numbers of trivalent nickel cates,[66] borates,[67] and tavorites,[68] were found that can be
ions keep increasing with the increase of the proportion of used as cathode materials, the strategy choice of improvement
Ni:Mn, and Ni-rich NCM exhibits a mixed valence state of +2 direct on the basis of conventional cathode materials has been
and +3.[61] During the charge process, the oxidation of nickel already employed by the large majority of car manufacturers in
from +2 to +4 with a two-electron transfer offers a high revers- the short term.[10,12]
ible capacity.[57,62] As shown in Figure 3d, the overlapping area To date, the specific capacity and energy density of commer-
of the t2g band of Co3+/Co4+ with the top of the 2p band of O2− cialized cathode materials (LCO, LMO, LFP, NCM, and NCA) for
is much bigger than that of the eg band of Ni3+/Ni4+ with the LIBs are shown in Figure 4. LCO shows a high theoretical spe-
top of the 2p band of O2−, so nickel with high valance states cific capacity of 278 mAh g−1, but in practice only 140 mAh g−1
exhibits a higher chemical stability than cobalt in NCM cathode can be safely released due to the structural instability over half
materials during the charge process. The eg band of Mn3+/Mn4+ delithium state.[1,21] LCO has a high volume energy density
is much higher than the top of the 2p band of O2− compared to (2642 Wh L−1 at the material level) owing to its high theoret-
Co and Ni, which presents the best chemical stability among ical compaction density (5.1 g cm−3), and it is suitable for the
them. Besides, the eg band of Ni3+/Ni4+ is higher than the t2g application of portable electronic products.[69] However, the
band in the Co3+/Co4+, and it is just touched with the top of 2p high cost of LCO can be the major drawback as cathode mate-
band of O2−. So the oxidation process of nickel ions from +3 rials for automotive Li-ion batteries, and it will hinder its devel-
to +4 is prior than that of cobalt ions after first oxidizing from opment in the near future.[12,51,70] LMO shows stable spinel
Ni2+ to Ni3+ in NCM cathode materials,[63] and the oxidation structure, nontoxicity and excellent anti-overcharge ability.[5]
process of Co3+/Co4+ in NCM cathode materials occurs only at Furthermore, the low cost is also competitive to occupy a part
high lithium deintercalation state with a high cut-off voltage.[64] of the market for EVs.[71] But it suffers from poor cycle life,
Thus, nickel in NCM cathode materials provides main capacity, high temperature, and thermal instability. Low specific capacity
and increasing the Ni content is favorable to improve specific (120 mAh g−1) and mass energy density (480 Wh kg−1 at the
Figure 4. The specific capacity and energy density (both mass and volume energy density at the material level) of commercialized cathode materials
(LCO, LMO, LFP, NCA, and NCM-811).
material level) are fatal flaws to LMO for the further develop- is equal to 6 C. A fast charging standard was also been set in
ment of automotive Li-ion batteries. In contrast to the above- China by Ministry of Industry and Information Technology
mentioned LCO and LMO, LFP shows the most stable crystal that one charge can offer 60% of the state of charge (SOC)
structure that can endure overcharged state and high current with a charging time of 30 min with a charging rate of about
density without safety issue, so it is a very promising cathode 1.2 C, or the average charging current of the battery is ≥3 A.[76]
material.[72] However, it exhibits a relatively low energy density The U.S. Advanced Battery Consortium (USABC) gave out
(528 Wh kg−1 and 1901 Wh L−1 at the material level) that could a standard of fast charging that the total battery capacity can
be not suitable for long-ranged EVs. Compared to LCO, LMO, reach to 40% with a 15 min charge (≈1.6 C).[77] The Society of
and LFP, ternary cathode materials have been considered used Automotive Engineers in the United States defined a charging
as cathode materials for automotive Li-ion batteries owing to standard (the J-1772 Standard) in three levels (Level I, Level II,
their high specific capacity (>200 mAh g−1) and high energy and Level III).[75,78] In Level I, the charging requirements is at
density (both mass and volume energy density at the material alternating current (a.c.) voltage of 120 V working in the input
level), including NCM and NCA material system. Compared to power of 1.9 kW (≈16 A), and it is suitable for charging at home
NCA cathode, NCM material system can provide more compo- for PHEVs over night with a charging rate of about 0.02 C;
sition matching to meet the needs of different application sce- The charging requirements in Level II is at voltage of 240 V
narios. Moreover, NCM material system with a coprecipitation a.c. with an input power of 19.2 kW (≈80 A), and it is suitable
method exhibits a more uniform chemical composition than for charging at workplace within 5 h with a charging rate of
NCA with a facile heat treatment.[12] Besides, the presence of about 0.2 C. Charging in Level III is required up to 550 A and
Mn in the NCM material system provides a higher thermal sta- 600 V at direct current (d.c.) with an input power of 120 kW at
bility than that of Al in the NCA material system.[36,73] So NCM fast charging station.[79] Recently, Tesla has caught more atten-
cathode materials could have a bigger market share for EVs in tion for its unique superchargers. Superchargers can offer a
the future. Furthermore, it is an inevitable trend to adopt high charging rate of over 120 kW (480 V d.c.), and it is enough to
nickel system (especially the Ni content over 80%) with a high increase the driving range to 200 miles within 30 min.[78] Nev-
specific capacity to meet the demand in high-energy LIBs for ertheless, refueling gasoline cars usually take about 5 min for
the applications of EVs (over 300 miles). a full tank. EVs have not a strong capability with ICEVs with
standards above, and there are no enough charging stations for
EVs to charge at any time and at a variety of locations by the
3. Fast Charging Capability of Ni-Rich NCM roadside so far. That is one important reason to cause “range
anxiety” for potential customers to buy EVs. To replace the
To be truly competitive with ICEVs, EVs should have a capa- ICEVs, a shorter charging time within few minutes during a
bility of being recharged quickly, like refueling gasoline cigarette break with a high charging rate of over 10 C for full
cars. Although the charging technology of lithium battery has battery charge is required for fast charging technology in the
developed rapidly, it still takes over 1 h to recharge EVs to the future, especially the successful realization of extreme fast
nominal energy of 80% currently.[74] Long charging time pro- charging (XFC).[78,80]
longs the travel time of long-distance. According to the report of
the U.S. department of energy (DOE), the charging time of EVs
should be decreased to under 15 min by 2030.[55] In general, 3.2. Challenges of Fast Charging for Ni-Rich NCM
when LIBs undergo charging, Li+ ions move from the cathode,
through electrolyte, to the anode. Key mechanisms that influ- Fast charging of single cell mainly depends on the transfer
ence this process are ion transport 1) through the solid cathode, rate of Li+ and electron between the battery components, such
2) across the electrode/electrolyte interface for both cathode as current collector, electrode materials, electrolytes, and sepa-
and anode, and 3) through the electrolyte, including Li+ solva- rator.[81] As an important part of LIBs, to reach the goal for fast
tion and desolvation. In this review, we mainly focus on the charging (over 60% of the total battery capacity at 10 C in a few
cathode side. minutes), the ionic and/or electronic conductivity of cathode
materials should be over 5 × 10−5 S cm−1 under the premise of
stable material structure.[76] However, like other cathode mate-
3.1. Fast Charging Requirements for EVs rials, the electronic conductivity and ionic conductivity of NCM
is hard to reach the standard at present. In addition to its own
What is fast charging for EVs? Generally, the charging time of weaknesses of poor electronic conductivity, the layer spacing of
slow charging for a full charge is around 3–6 h with a charging oxygen atoms and cation mixing can change with the Ni content,
rate of C/3. The charging time of quick charge is required and are also important factors to influence its rate capability.
ranging from 30 min to 1 h with a charging rate of 2 C. Only Usually, Ni3+ ions are unstable and tend to form Ni2+ due
the charging time less than 10 min with a charging rate of to the lone pair electron spin on the e orbitals.[31] So in NCM
6 C can be divided to fast charging. Nevertheless, according to cathode materials, cation mixing occurs easily between Ni2+
local conditions, fast charging standards for EVs in different (octahedral 3a site) and Li+ (octahedral 3b site) due to their
countries and regions are not identical currently. According to similar ions radius (Figure 5a).[12] Furthermore, with the
the California Air Resources Board (ARB), the fast charging increase of Ni content, cation mixing of NCM cathode mate-
standard was given out that one charge can offer a 100 miles rials is aggravated. Thus, Ni-rich NCM cathode materials
mileage with a charging time of 10 min.[75] The charging rate present higher cation mixing and activation energy barrier of
Figure 5. a) High-magnification STEM images of NCM-622 particles with cation mixing. Reproduced with permission.[85] Copyright 2015, American
Chemical Society. b) Activation barriers of Li+ ions for different transition metal elements. Reproduced with permission.[82] Copyright 2006, The
American Physical Society. c) The lattice parameter (a-axis and c-axis) of LiNixCoyMn1−x−yO2 (x = 0.6, 0.8, 0.9, and 0.95) at different applied voltages.
Reproduced with permission.[86] Copyright 2018, American Chemical Society. d) The concentration of Li+ ions in electrode at different radial locations
with different times (T = 0.01 s and T = 0.076 s) during the insertion and deinsertion processes. Reproduced with permission.[84] Copyright 2010, The
Electrochemical Society. e) The TEM image of interior primary particles with a microcrack. Reproduced with permission.[86] Copyright 2018, American
Chemical Society. f) Corresponding calculated lattice parameters of the four NCM cathode materials (a-axis, c-axis, and c/a ratio) with different Li
contents. Reproduced with permission.[22] Copyright 2019, American Chemical Society.
Li+ ions diffusion compared with low-Ni NCM cathode mate- the extraction of larger amount of Li+ ions with the same cut-
rials, resulting in lower ionic conductivity (Figure 5b).[82] Like off voltage (Figure 5c).[83] During high-rate cycles, Li+ ions
other cathode materials of LIBs, the rate capability of NCM cannot diffuse homogeneously in time, resulting in severe lat-
cathode depends on rapid extraction and insertion of Li+ ions tice volume change and microcrack evolution (Figure 5d,e).[84]
through the electrolyte and active electrode materials. So the The conductivity of electrons and ions of primary particles is
rate capability of Ni-rich NCM cathode materials is also reduced deteriorated during electrochemical cycles, which accelerates
with the increase of cation mixing. the collapse process of layered lattice structure. Contrary to
Besides, the layer spacing of oxygen atoms increases due this view, Li et al.[22] believed that the lattice collapse of NCM
to their repulsive force during the charging process, leading cathode materials was closely related to the extraction amount
to the increase of c-axis lattice parameter of NCM cathode of Li+ ions rather than the Ni content (Figure 5f). When the
materials. Meanwhile, the increase of electrostatic attrac- extraction amount of Li+ ions is around 80 mol%, c-axis lattice
tion between transition metal oxidation causes the decrease parameter with the similar shrinkage of around 5% occurs in
of a-axis lattice parameter of NCM cathode materials.[30] The NCM cathode materials with different nickel content (90, 70,
change of c-axis lattice parameter of NCM cathode materials 50, or 33 mol%); meanwhile, the a-axis lattice contracts for both
becomes bigger with the increasing of nickel content due to high-Ni NCM and low-Ni NCM cathode materials.
3.3. Strategies to Improve Fast Charging of Ni-Rich NCM active materials and electrolyte. The diffusion path of Li+ ions
is also shortened. Furthermore, 1D structure also can offer a
Until now, strategies to improve fast charging of Ni-rich NCM short electron transport path on the shell of long hollow fibers.
cathode materials are mainly focused on reducing the diffu- They found that cation mixing was effectively hindered owing
sion path of Li+ ions and electron by nanotechnology, or on to the immobilization effect of alginate with novel egg-box
improving the electrical and ionic conductivity in the bulk or at structure for transition metal elements. Higher diffusion coef-
the surface of the active material by building highly conductive ficient of multishelled NCM-523 hollow fibers than that of bulk
pathways.[76,87,88] Table 1 lists the comparison of the improve- NCM-523 was also be proved. Meanwhile, the Li+ ions diffu-
ment on the rate performance of different modified Ni-rich sion coefficient ascends with the increase of Ni content. Multi-
NCM cathode materials. shelled NCM-811 hollow fibers present a high specific capacity
The morphology and structure of the Ni-rich NCM cathode of 172.7 mAh g−1 at a rate of 10 C. When the current density
materials have a great influence on their rate performance. back to 0.1 C, full capacities were recovered, indicating an
Zou et al.[89] reported an excellent research of multishelled excellent rate performance. Liu et al.[88] prepared NCM-622 with
LiNi1−x−yCoxMnyO2 hollow fibers (HFs) (Figure 6a). Multi- hierarchical porous structure. The hierarchical porous structure
shelled hollow fibers with porous structure exhibit a large spe- can increase the active sites of Li+ ions. The diffusion path of
cific surface area, which can provide a big contact area between Li+ ions and electrons are also shortened, resulting in high Li+
Table 1. The rate performance of different modified Ni-rich NCM cathode materials.
Electrode materials Li+ diffusion conductivity Voltage Current Rate performance Refs.
[cm2 S−1] range [V] density [C] [mAh g−1]
Multishelled Ni-rich Li(NixCoyMnz)O2 HFa) 2.74 × 10−8 (NCM-523) 2.5–4.5 0.1, 0.2, 0.5, 1, 2, 5, and 10 229.6, 225.5, 216.7, 207.4, [89]
196.6, 183.4, and 172.7
Hierarchical porous NCM-622 4.63 × 10−12 2.7–4.3 0.2, 0.5, 1, 3, 5, 10, and 20 158, 148, 138, 122, 111, 97, and 82 [88]
Mo-doped NCM-523 10.67 × 10−11 3.0–4.3 8 125.5 [90]
Na-doped NCM-523 3.18 × 10−11 3.0–4.6 5, 20, and 50 130.61, 111.42, and 60.09 [91]
LiNi0.5Co0.2Mn0.3O1.99F0.01 5.364 × 10−11 2.5–4.3 10 124.49 [92]
Al-CGb)-modified NCM-523 1.01 × 10−11 3.0–4.4 1, 2, 4, and 8 166.4, 160.4, 152.9, and 142.7 [46]
Ce-doped NCM-523 1.84 × 10−13 3–4.5 5 109.75 [93]
Y2O3-coated NCM-523 8.84 × 10−12 2.8–4.6 10 and 20 160.5 and 145.9 [94]
La2O3-coated NCM-523 4.91 × 10−11 3.0–4.6 5 119.5 [95]
ZrO2-coated NCM-523 1.69 × 10−8 2.5–4.5 0.2 and 5 208.5 and 128.7 [96]
Li0.98Na0.02Ni0.5Co0.2Mn0.3O2 7.9 × 10−9 2.8–4.25 0.2, 0.5, 1, 2, and 3 170.09, 165.35, 158.30, 152.21, [97]
and 148.38
Mo-doped and -coated NCM-523 3.8 × 10−10 3.0–4.3 5 130 [98]
NaTi2(PO4)3-coated NCM-523 6.414 × 10−10 3.0–4.6 5 and 10 169.5 and 153.2 [99]
MgO-coated NCM-523 3.9 × 10−8 3.0–4.3 10 115 [100]
ZnO-coated NCM-523 4.56 × 10−9 2.5–4.5 1 and 5 198.5 and 148.2 [101]
F-doped and LiF-coated NCM-523 5.16 × 10−11 3–4.5 5 153.7 [102]
Na-doped NCM-622 4.05 × 10−9 2.8–4.3 From 0.1 to 5 180, 176, 170, 162, 153, and 113 [103]
MnPO4-coated NCM-622 2.17 × 10−8 3.0–4.3 0.5, 1, 2, 5, and 10 196.2, 182.0, 151.5, 136.4, and 114.5 [104]
NaTi2(PO4)3-coated NCM-622 1.247 × 10−9 3.0–4.5 0.2, 0.5, 1, 2, and 5 206.3, 198.6, 193.4, 187.6, and 177.0 [105]
Li2SiO3-coated NCM-622 1.68 × 10−10 2.8–4.4 0.2, 0.5, 1, 5, and 10 196, 195, 191.8, 167.6, and 157.9 [106]
LiPONc)-coated CG Li[Ni0.73Co0.12Mn0.15]O2 10−8 3.0–4.3 5 153 [107]
CG LiNi0.7Co0.15Mn0.15O2 2.61 × 10−10 and 1.19 × 10−10 3.0–4.4 20 130 [47]
Li3PO4-coated NCM-811 1.68 × 10−11 3.0–4.4 1, 2, 4, and 8 193.8, 181.9, 165.4, and 144.4 [108]
PANI-d) and PEGe)-coated NCM-811 8.92 × 10−10 2.8–4.3 10 156.7 [109]
Y-doped NCM-811 2.7997 × 10−11 2.8–4.3 1 and 10 170.5 and 118.4 [110]
Li3PO4 and PPyf)-coated NCM-811 2.4 × 10−12 2.8–4.5 10 159.7 [111]
Al2O3 (1 wt%) coated NCM-811 8.5 × 10−9 2.8–4.3 and 2.8–4.5 5 117 and 131 [112]
LaPO4-coated NCM-811 1.42 × 10−11 3.0–4.3 0.1, 1, 2, 5, and 10 196.7, 179.0, 165.6, 143.9, and 124.0 [113]
a)HF: hollow fibers; b)CG: concentration gradient; c)LiPON: lithium phosphorus oxynitride; d)PANI: polyaniline; e)PEG: poly(ethylene glycol); f )PPy: polypyrrole.
Figure 6. a) Schematic illustration, SEM images, EDS mapping, and electrochemical performance of the multishelled NCM hollow fibers for LIBs.
Reproduced with permission.[89] Copyright 2016, Wiley-VCH. b) FETEM images and electrochemical performance of pristine NCM and Li3VO4–PPy-
coated NCM cathode materials. Reproduced with permission.[118] Copyright 2018, Elsevier. c) Schematic illustration, HRTEM images, and electro-
chemical performance of NCM and rGO-NCM. Reproduced with permission.[131] Copyright 2017, American Chemical Society.
ionic and electronic conductivity. So the hierarchical porous on rate performance of Ni-rich NCM. As an example, Ran
exhibited higher Li+ diffusion coefficient (4.63 × 10−12 cm2 s−1) et al.[118] reported NCM-622 coated with the dual-conductive
than agglomerated NCM-622 and good rate performance layers with Li3VO4 and PPy. As shown in Figure 6b, NCM was
(10 C: 97 mAh g−1; 20 C: 82 mAh g−1). first coated by the Li3VO4 layer via a sol–gel method, and then
Increasing Li slab space is also an effective strategy to coated by the conductive polymer of PPy via an in situ chemical
improve the Li+ ions diffusion coefficient of the host materials, polymerization process. Two coating layers of Li3VO4 and PPy
resulting in the enhancement of the rate capacity.[103,114] Doping can combine with their advantages of fast Li+ ion and electronic
is a simple but effective strategy to material modification to conductivity, respectively. The modified sample exhibited an
change Li slab space, and it has been widely used in the field of outstanding retention rate of 93.7% at 0.5 C with a high cut-
cathode materials for LIBs. Despite dopants in the Ni-rich NCM off voltage of 4.5 V. Shim et al.[131] reported NCM-622 coated
cathode materials can improve their rate performance, but high by several reduced graphene oxide (rGO) layers. rGO-coated
content of doping elements usually causes a decrease of spe- NCM-622 reduced both the lithium ion diffusion resistances
cific capacity. So the ratio of doping elements should be con- through the surface layer and the charge transfer resistances.
trolled strictly. Li et al.[92] prepared LiNi0.5Co0.2Mn0.3O1.99F0.01 In especial, the charge transfer resistance is reduced signifi-
by a F127-assisted synthetic coprecipitation method. They cantly owing to the excellent electrical conductivity of rGO
found F127 surfactant can improve the crystallinity of shells. For the rate test, the rGO-coated NCM-622 showed a
LiNi0.5Co0.2Mn0.3O2. The F dopant is not only beneficial to fur- specific capacity of 132.6 mAh g−1 at a rate of 10 C, which is
ther stabilize the original structure, but also can enlarge the much higher than the uncoated NCM-622 cathode materials
layer spacing. Lithium ions can diffuse homogeneously in time (104.9 mAh g−1) (Figure 6c). However, thick outer shells usually
to weaken severe lattice volume change and microcrack evolu- increase the diffusion path of Li+ ions and electron, leading to
tion at a high-rate cycles. Such finding shows that F127-assisted unobvious or opposite effect for rate performance. In addition,
synthetic LiNi0.5Co0.2Mn0.3O1.99F0.01 presents a high capacity insulation materials (Al2O3, ZnO, ZrO2, AlF3, AlPO4, SiO2, etc.)
retention of 79.04% after 500 cycles at 10 C, indicating a good with a poor electronic and Li+ ion conductivity can also block
rate capability of modified materials. the transmission path of electron and ions, which is not benefi-
Coating materials with a good ionic or electronic con- cial to the rate performance of active materials.[12,132]
ductivity, such as carbon,[115] lithium ionic conductors Building fast channels of Li+ ions and electron by nanotech-
(Li3PO4,[108,116] LiMn1.9Al0.1O4,[117] Li3VO4,[118,119] Li2SiO3,[106] nology is effective to provide excellent rate capacity for Ni-rich
Li2TiO3,[120] LiFePO4,[121] LiAlO2,[122] Li2ZrO3,[123–125] etc.) and NCM cathode. Specifically, design hollow or porous cathode
conductive polymer (poly(ethylene glycol),[126] polyacrylate,[127] materials are beneficial to increase the surface area with the
poly(3,4-ethylenedioxythiophene),[126] polyaniline,[109,128] poly- electrolyte, and the diffusion path of Li+ ions can be shortened
propylene,[129] polypyrrole (PPy),[130] etc.), can also improve Li+ effectively.[88] Furthermore, increasing Li slab space by doping
ions or electron diffusion coefficient, providing a positive effect can also improve the Li+ ions diffusion coefficient of the host
materials on the crystal scale.[103,114] In addition to the above

two methods, combining with high conductivity substrate or
coating with good electrical and ionic conductivity materials
can provide short and fast transmission path for electronic and
Li+ ions.[89,118,119] The interface resistance of composite mate-
rials and contact resistance with current collector can also be
reduced to a certain extent. These strategies can improve the
power density of the battery, but the tapped density of mate-
rials will be reduced to some extent, leading to a relatively low
energy density of the cell.[133] Thus, it is important to give a rea-
sonable choice to balance the power density and energy density
of LIBs in a specific application scenario.
4. Service Life of Ni-Rich NCM for LIBs

The service life of LIBs includes cycle life and calendar life.
The former is determined by capacity retention after repeated
charge/discharge cycles while the latter is determined by
capacity retention after LIBs laid aside for a certain period at
a certain state of charge. Thus, battery cycle and calendar life- Figure 7. a) Cross-sectional images of fully discharged Li[NixCoyMn1−x−y]
time should be both considered and evaluated for automotive O2 (x = 0.9) electrodes before and after 15 days of storage. Reproduced
applications. In general, service life of LIBs for EVs is required with permission.[41] Copyright 2018, Wiley-VCH. b) Comparison of cross-
sections of the NCA82 and TSFCG85 electrodes aged in electrolyte for dif-
to ensure smooth and quiet operation over 10 years.[10,12] Con-
ferent times. Reproduced with permission.[138] Copyright 2017, American
sidering the existing drawbacks (chemical and electrochemical Chemical Society.
instability, material degradation upcycling, and calendar aging)
of Ni-rich NCM cathode, we will give a comprehensive analysis
for cycle and calendar lifetime of Ni-rich NCM for LIBs in this charging state with the increasing of Ni content. Highly active
section. Ni4+ in cathode materials can react with the electrolyte, leading
to capacity fading and voltage polarization.[137] This reaction
occurs during all the service life of LIBs. During the accelerated
4.1. Calendar Lifetime of Ni-Rich NCM calendar aging, rock-salt structure appears on the surface of pri-
mary particles, and microcracks develop across the secondary
Usually, EVs remain stationary for long period in the fully particle (Figure 7a).[41,86] Fresh surfaces of cathode materials
charged state for most car owners. Consequently, calendar with highly active Ni4+ can exposure to the electrolyte, causing
aging will have an important effect on the lifetime of elec- vicious spiral with the extension of aging time.
tronic automobiles, similar to cycling aging. The common Many researchers have mentioned ways (e.g., coating, con-
phenomena of calendar aging are unusual capacity fading centration gradients) that can improve calendar life of Ni-rich
and loss during cycling tests after long-term standing. There NCM cathode, but few reports can provide specialized experi-
are three main influencing factors for calendar aging: state of mental design, such as accelerated aging. Yoon et al.[138] pro-
charge (SOC), standing time, and ambient temperature.[134] posed that accelerated aging test of cathode should store in the
Often, the recession is getting worse with the increase of SOC, electrolyte at a high temperature due to the higher temperature
standing time and ambient temperature, owing to the aggra- in vehicles than the ambient temperature exposed directly to
vation of internal chemical reactions and structure. For NCM sunlight. The Li[Ni0.85Co0.05Mn0.10]O2 (TSFCG85) with concen-
cathode, the main mechanisms of performance degradation are tration gradients cathode remained more mechanically intact
described differently. Some experimental results indicate that even after being aged for a few days in the electrolyte compared
the major degradation mechanisms of low-Ni NCM cathode to the commercial Li[Ni0.82Co0.14Al0.04]O2 (NCA82) cathode
is the gradual inactivation of active lithium rather than struc- (Figure 7b). This is attributed to the chemical stability of rel-
tural degradation due to its high structural stability.[135] Lithium atively stable outer part with low Ni content from the unique
ions in electrolyte can react with cathode and anode material structure.
to form a cathode electrolyte interphase (CEI) and solid elec-
trolyte interphase (SEI) layer on the surface, respectively. As a
result of the formation of concentration difference of Li+, some 4.2. Cycling Lifetime of Ni-Rich NCM
active Li-ions extract from cathode materials to electrolyte. The
thickness of CEI and SEI layers are increasing as the reaction Excess lithium is often used in the production process of
proceeds, leading to irreversible capacity loss and inner resist- highly ordered Ni-rich NCM cathode material with layered
ance (IR) increasement.[136] However, Ni-rich NCM cathode structure, so residual lithium (converted into Li2O) remaining
exhibits poor structural stability although with high energy den- on the surface of active materials can react with H2O and CO2
sity. Moreover, more Ni4+ exist in Ni-rich NCM cathode at full in the ambient air during assembly and long-term storage
can accelerate microcrack evolution further. Crack evolution

can cause morphological collapse and shedding of active mate-
rials on the electrode surface, leading to large capacity loss.
4.3. Strategies to Improve Cycling Lifetime of Ni-Rich NCM
In order to improve the cycle performance of Ni-rich NCM

cathode materials for automotive Li-ion batteries, researchers
have made many efforts. Table 2 lists the comparison of the
improvement on the cycle performance of different modified
Ni-rich NCM cathode materials.
4.3.1. Doping Strategy
Doping is generally recognized as an effective strategy to

adjust the properties of materials.[178] And many elements
have been reported doped into the Ni-rich NCM cathode
materials to improve their cycle performance, such as B,[42]
F,[165,179,180] Na[91,97] Mg,[114,161,181] Al,[43,181,182] Si,[181,183] S,[184]
Ca,[185] Ti,[164,181] V,[181] Cr,[161] Mn,[186] Mo,[90,98] Sn,[187] Nb,[148,170]
Ga,[181] Y,[110] Zr,[40,163,181] Ce,[93] Al–Mg,[162,188] Al–Fe,[156] and
Figure 8. a) Surface evolutions of nickel-rich cathode materials storage Mg–Al–B.[147] There are several mechanisms for improving
in ambient air. Reproduced with permission.[139] Copyright 2014, The the cycle performance: 1) Inactive elements can substitute the
Electrochemical Society. b) Active mass dissolution of Ni-rich layered unstable elements (Ni and Li) in the Ni-rich NCM system to
oxide cathodes after 1500 cycles (the fragments of secondary ions).
hold the original structure;[185,189] 2) fixing the primary particles
Reproduced with permission.[144] Copyright 2018, Wiley-VCH. c) HRTEM
images and SAED patterns after 50 cycles of the surface region on the of cathode materials to relieve the evolution of cracks.[42]
NCM-523 with different phases. Reproduced with permission.[146] Copy- Schipper et al.[190] presented NCM-622 cathode material
right 2013, Wiley-VCH. doped with Zr4+ and studied the role of element doping on a
transformation in Ni-rich NCM system combined with first-
process,[12] forming lithium compounds of LiOH and Li2CO3 principles theory approach. From the computational studies,
(Figure 8a).[139,140] In this process, the formation of unwanted they found that nickel ions irreversible migration can lead
lithium compounds are often accompanied by an increase of to the phase transformation from layered to spinel structure
hydroxyl ions. It is unfavorable to the slurry preparation pro- (Figure 9a). Furthermore, the element of zirconium (+4) not
cess when pH value increase to more than 11, and it also can only causes the destabilization of Ni tetrahedral sites, but
cause further accumulation of unwanted lithium compounds also can relieve the Jahn Teller effect of Ni3+ ions. As such,
on the surface of active materials.[2,31] Furthermore, these com- the phase transformation from layered to spinel structure can
pounds are insulating and can impede channels for the diffu- be suppressed effectively in the modified sample. And the
sion of lithium ions, leading to large irreversible capacity.[141] cycle life of modified cathode materials showed a big increase
Besides, electrolytes in LIBs are usually liquid with the of 20%.
mixtures of carbonate esters based blends and LiPF6 salt. The Eilers-Rethwisch et al.[189] reported a research of NCM-622
moisture in the cell can react with fluoride in the electrolyte to cathode materials doped with Al, Fe, and Sn by a coprecipita-
form HF (LiPF6 ⇌ LiF↓ + PF5, H2O→POF3 + 2HF).[142] HF can tion method. These materials all show a hexagonal α-NaFeO2
etch the surface of Ni-rich NCM cathode materials, causing the phase. As shown in Figure 9b, they found that the repulsion of
dissolution of transition metals (Mn > Co > Ni) and capacity the transition metal layer in the NCM cathode materials after
loss (Figure 8b).[143,144] Ni4+ with high activity can accelerate the doped with the element of tin was smaller than undoped one,
decomposition of electrolyte during repeated charge/discharge and the volume expansion of their cell sizes was also relieved.
cycles, resulting in large electrolyte depletion, Ni2+ dissolution Also, the capacity fading of undoped sample started first, and
and a thick SEI layer.[137,145] then the capacity fading of Al-, Fe-, and Sn-doped ones began
Due to high cation mixing in Ni-rich NCM cathode mate- successively.
rials, the migration of Ni2+ ions can destroy active sites of Park et al.[42] reported B-doped LiNi0.90Co0.05Mn0.05O2
lithium and cause a phase transition from layer structure to cathode material by adding B2O3 in the precursors. B-doped
spinel and/or rock-salt structure (Figure 8c), leading to capacity LiNi0.90Co0.05Mn0.05O2 produced a highly textured micro-
fade during the long electrochemical cycles.[146] The volume structure. The microstructure fixed the primary particles, and
change of the grains can be caused by phase transition leading retarded crack evolution. So the internal strains come from
to microcrack evolution.[30,85] Electrolyte can penetrate to the the anisotropic volume changes were relieved (Figure 9c). Fur-
interior particles along the grains microcrack, promoting thermore, LiNi0.90Co0.05Mn0.05O2 cathode material doped with
unwanted side reactions and gas production. Gas production 1 mol% of boron element presented an excellent capacity of
Table 2. Comparison of the improvement on the cycle performance of different modified Ni-rich NCM cathode materials.
Electrode materials Voltage Current Cycles Specific capacity Capacity Refs.

range [V] density [C] [mAh g−1] retention [%]
Mo-doped NCM-523 3.0–4.3 1 500 154.4 89.7 [98]
Mg–Al–B codoped NCM-523 3.0–4.3 0.5 200 146.9 84.9 [147]
Li1−xNaxNi0.5Mn0.3Co0.2O2 2.8–4.25 0.2 50 170.09 97.8 [97]
Li(Ni0.5Co0.2Mn0.3)0.99Nb0.01O2 3.0–4.3 1 100 – 93.77 [148]
MgO-coated NCM-523 3.0–4.3 1 180 130 82 [100]
TiO2-coated NCM-523 3.0–4.4 0.5 100 149.2 88.0 [149]
AlF3-coated NCM-523 2.8–4.5 4 100 149.7 98 [150]
MoO3-coated NCM-523 2.7–4.4 0.2 100 148.3 90.9 [151]
ZrO2-coated NCM-523 2.5–4.5 5 60 155.1 88.1 [96]
LiTiO2-coated NCM-523 3.0–4.4 1 100 145 89 [152]
Li2ZrO3 (1 wt%) coated NCM-523 3.0–4.6 1 100 163.6 87.1 [124]
Al2O3-coated NCM-523 3.0–4.5 0.5 100 ≈140 85 [153]
LiFePO4-coated NCM-523 3.0–4.6 1/3 150 168.5 92.8 [121]
Artificial SEIa)-coated LiNi0.6Co0.1Mn0.3O2 2.5–4.6 0.5 100 214 95.1 [154]
CH4-coated LiNi0.6Co0.1Mn0.3O2 2.5–4.5 0.1 100 210.5 91.83 [155]
LiNi0.6Mn0.2Co0.15Al0.025Fe0.025O2 2.5–4.4 C/5 100 189 75.4 [156]
MDA (2.5 wt%)b) coated NCM-622 3.0–4.5 1 100 196.5 92.7 [157]
Li3PO4-coated NCM-622 2.8–4.7 1 100 192.7 79.7 [116]
Nanoscale Fm-3m phase coated NCM-622 3.0–4.45 1 150 156 80 [85]
Mn3(PO4)2-coated NCM-622 3.0–4.45 0.5 50 149 93.3 [158]
rGOc)-coated NCM-622 3.0–4.6 0.5 100 179.9 – [131]
SiO2-coated NCM-622 3.0–4.3 1 50 146 92 [159]
Nanoscaled pillaring layer coated LiNi0.62Co0.14Mn0.24O2 3.0–4.5 0.5 100 166 85 [160]
Li2ZrO3-coated LiNi0.7Co0.15Mn0.15O2 2.5–4.4 1/3 1500 175 73.3 [125]
LiNi0.78Co0.1Mn0.1Cr0.01Mg0.01O2 2.7–4.3 5 50 122.5 84.8 [161]
LiNi0.8Co0.1Mn0.98Al0.01Mg0.01O2 3.0–4.3 0.5 70 191 92 [162]
LiNi0.8Co0.1Mn0.09Al0.01O2 2.7–4.3 10 1000 78 70.0 [43]
Li(Ni0.8Co0.1Mn0.1)0.985Zr0.015O2 2.8–4.5 0.1 100 210 93.2 [163]
Ti-doped NCM-811 2.8–4.5 1 200 158.6 87.4 [164]
LiNi0.8Co0.1Mn0.1O2−zFz (0 ≤ z ≤ 0.06) 2.8–4.3 2 100 170.1 94.3 [165]
AlF3-coated NCM-811 3.0–4.2 1 600 and 1000 – 95 and 93 [166]
Li3PO4- and PPyd)-coated NCM-811 2.8–4.5 0.1 50 159.7 95.1 [167]
Al2O3-coated NCM-811 2.8–4.5 5; 1 60 131 99 [112]
Artificial CEIe) layer coated NCM-811 3.0–4.3 1 50 174 97.4 [168]
Li2ZrO3-coated NCM-811 2.8–4.3 10; 1 200 144.3 94.5 [123]
B-doped Li[Ni0.90Co0.05Mn0.05]O2 2.7–4.3 0.5 100 230 91 [42]
Al-doped ZnO-coated NCM-523 3.0–4.5 10 100 148.9 90.5 [169]
Partial Nb5+-doped and Li3NbO4-coated NCM-622 3.0–4.5 1 100 160.9 91 [170]
Nanoscale LiYO2 coating and inner gradient Y3+-doped NCM-811 2.8–4.5 1 100 189.4 98.4 [110]
Zr-modified NCM811 2.8–4.3 1 100 171 92 [48]
Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 3.0–4.3 1 500 120 98 [171]
CG Li[Ni0.64Co0.18Mn0.18]O2 3.0–4.4 1 50 209 96 [172]
FCGg) LiNi0.6Co0.15Mn0.25O2 3.0–4.4 5 1000 – 80 [173]
Al-doped FCG Li[Ni0.61Co0.12Mn0.27]O2 3.0–4.2 1 3000 – 84.5 [174]
LiPONh)-coated CG Li[Ni0.73Co0.12Mn0.15]O2 3.0–4.3 1 1000 183 87.3 [107]
Table 2. Continued.
Electrode materials Voltage Current Cycles Specific capacity Capacity Refs.
range [V] density [C] [mAh g−1] retention [%]
TSFCGi) Li[Ni0.65Co 0.13Mn0.22]O2 3.0–4.2 1 1500 200 88 [175]
CG Li[Ni0.83Co0.07Mn0.10]O2 2.8–4.3 0.2 50 190 96.9 [176]
Li4Ti5O12/CG-LiNi0.7Co0.15Mn0.15O2 3.0–4.2 10 2000 – 95 [47]
FCG LiNi0.75Co0.10Mn0.15O2 3.0–4.2 1 1000 215 90 [177]
a)
SEI: solid electrolyte interface; b)MDA: MOF-derived alumina; c)rGO: reduced graphene oxide; d)PPy: polypyrrole; e)CEI: cathode electrolyte interphases; f)CG: concentra-
tion-gradient; g)FCG: full concentration-gradient; h)LiPON: lithium phosphorus oxynitride; i)TSFCG: two-sloped full concentration gradient.
237 mAh g−1, which was much higher than undoped one. And found that Al2O3-coated NCM-523 prepared by higher annealing
the modified cathode materials showed an enhanced cycle life temperature presented a better cyclability than that prepared by
with a capacity retention over 90% after 100 cycles. lower annealing temperature, owing to the enhanced Li trans-
portation and bulk chemistry protection of more homogeneous
and denser Al2O3 coating layer after higher annealing tempera-
4.3.2. Surface Coating Strategy ture. Zhao et al.[202] reported NCM-523 cathode materials coated
by Al2O3 and AlPO4 agents. In this design (Figure 10d), double
Coating layer on the surface of cathode materials are usually coating layers can be beneficial for suppressing the connection
applied to act as a role of physical or chemical protection to sup- between active materials and HF in the electrolyte. Isolation
press the contact of active materials with external substances, such layer also can prevent O2 and H2O in air coming into the shell.
as electrolyte, HF, H2O, and CO2.[12,191] In view of coating mate- These advantages led to good cycle capacity of the modified
rials with the protection effect, representative examples are oxides materials. The capacity maintenance in the rate test of double
(Al2O3, TiO2, ZrO2, CeO2, ZnO, MgO, etc.),[95,143,159,192,193,194] coating layers is much better than that of bare and single
sulfides,[45] fluoride,[166,195] artificial CEI layers,[168,196] artificial SEI coating cathode materials after storing for 60 days in air, indi-
layer,[154] and phosphates.[99,104,105,108,113,116,158,197] cating strong protective effect of double coating layers.
Inactive material for full coverage model can be used as a
physical protection barrier to insulate the cathode materials
from ineffective reaction. Choi et al.[198] reported the Na2SO4- 4.3.3. Structural Engineering
coated LiNi0.88Co0.10Mn0.02O2 and NCM-523 cathode materials
by sodium dodecyl sulfate (SDS). The full covered Na2SO4 Improving the performance of materials by designing special
layer prevented the direct contact of active materials with the nanostructures has emerged as an important strategy in energy
electrolyte, so these materials exhibited an enhanced cycle per- functional materials and devices.[203] For Ni-rich NCM cathode,
formance used as cathode materials in LIBs (Figure 10a). For a special core–shell structure of concentration gradient emerged
the large battery test, Na2SO4-coated LiNi0.88Co0.10Mn0.02O2 and been adopted to improve cycle performance in recent years.
showed a better capacity retention (96.1%) than washed sam- In 2005, Sun et al.[171] first proposed the core–shell structure
ples (95.7%). of Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2. Different from the
Flexible layer of coating materials can adapt to large volume conventional core–shell structure, the active materials are usu-
expansion and contraction of host cathode materials, so the ally used as the coating shell. These outer coating materials
crushing and shedding on the cathode surface can be appro- not only can protect the bulk cathode material in the core posi-
priately mitigated. Min et al.[199] proposed a simple method to tion, but also can provide partial capacity. The novel core–shell
form a spinel interphase on the surface of primary particles structure was also deemed to be the first generation concentra-
of LiNi0.91Co0.06Mn0.03O2. The spinel phase can provide excel- tion gradient strategy (Figure 11a). Nevertheless, a small space
lent mechanical properties and a small volume change during was found between the core and shell after cyclic charging and
lithium intercalation and deintercalation process, so the coating discharging process due to the different degrees of shrinkage
layer can help to prevent excessive volume change of the pri- of the core and shell. Hou et al.[204] reported a core–shell struc-
mary particle. By tracking the same particle during charge–dis- ture of [Li[(Ni0.8Co0.1Mn0.1)2/7]core[(Ni1/3Co1/3Mn1/3)3/14]inner-shell
charge process, they found that cracks of LiNi0.91Co0.06Mn0.03O2 [(Ni0.4Co0.2Mn0.4)1/2]outer-shellO2 prepared by a coprecipitation
coated by spinel interphase were greatly reduced (Figure 10b). route. In this design, NCM-811 provides a high capacity, and
These evolving cathode materials exhibited a superior capacity the two outer shells of NCM-111 and NCM-424 can provide
retention over 90% after 50 cycles. structural and thermal stability. The two shelled structural
Amphoteric metal oxide, such as Al2O3,[112,194,200] ZnO,[169] cathode material prepared at 800 °C showed better capacity
and ZrO2,[125,193] can react with HF in the electrolytes and act a retention of 85.95% than that of uncoated sample (77.20%) at
role of scavenger, so the dissolution process of transition metal 150th cycle. After that, they reported the shell concentration
(Ni, Co, and Mn) from electrode surface to electrolytes can be gradient model, which was considered to be the second genera-
relieved. Han et al.[201] studied the role of Al2O3 with lower tion concentration gradient cathode materials (Figure 11b).[172]
coating content and thinner coating on the surface of NCM-523 In this model, the outer shell shows a concentration gradient
prepared by different annealing temperature (Figure 10c). They of transition metal elements.[176,205] The Ni content is reduced
Figure 9. a) The electrochemistry performance of Zr-doped NCM-622 materials and the energy profiles for Ni migration. Reproduced with permis-
sion.[190] Copyright 2016, The Royal Society of Chemistry. b) Lattice parameter trends, DSC curves, and cycle performance of NCM-622 cathode mate-
rials with different dopants (Al, Fe, and Sn) and the illustration of Li-interlayer movement (c-axis). Reproduced with permission.[189] Copyright 2018,
Elsevier. c) Schematic illustration of the effect and cycle performance of B-doping LiNi0.90Co0.05Mn0.05O2. Reproduced with permission.[42] Copyright
2018, Wiley-VCH.
with the increasing of the relative contents of Co and Mn on high energy density. Then, two-sloped full concentration gra-
the shell wall from inside to outside.[47] Compared with the dient Ni-rich cathode materials were reported.[175,207] Compared
early model, more capacity can release from the shell wall of with one-sloped model, the cycle life and energy density of two-
cathode material. However, the shell walls of this model are sloped model are improved with the further increasing of Ni
usually thin, so the stabilizing effect is limited. In 2012, Sun content and Mn content in the core and outer shell, respectively.
et al. proposed a new model of full concentration gradient, The single optimization strategy usually has multiple func-
which was classified as the third generation concentration gra- tions, but no one strategy can solve all the existing problems
dient model (Figure 11c).[177] Different from last generation, the of Ni-rich NCM cathode materials. So hybrid strategy was
concentration of transition metal elements changes through proposed to solve multiple problems to optimize the cycle
the entire particle.[206] The Ni content is reduced from center performance of Ni-rich NCM cathode materials, although
to the surface, and the relative contents of Co and Mn increase more complex to realize. Schipper et al.[40] reported improved
gradually.[173] This structure can provide a consistent protection NCM-811 cathode materials with a hybrid strategy of surface
from outside to inside and maintain a longer cycle life with a coating and bulk doping of ZrO2 and Zr4+ ions by wet chemical
Figure 10. a) The electrochemistry performance of Na2SO4-coated LiNi0.88Co0.10Mn0.02O2 and NCM-523 cathode materials. Reproduced with per-
mission.[198] Copyright 2016, Wiley-VCH. b) SEM images of NCM surface coated by spinel interphase after cycles. Reproduced with permission.[199]
Copyright 2018, American Chemical Society. c) STEM images and cycle performance of pristine NCM523 and as-coated NCM523. Reproduced with
permission.[201] Copyright 2017, American Chemical Society. d) Working mechanism, SEM image, and electrochemical performance of the NCM-523
with double coated layers (Al2O3 and AlPO4). Reproduced with permission.[202] Copyright 2017, Elsevier.
approach. As shown in Figure 12a, the dopants of Zr4+ ions as ZrO2 coating agent/Zr4+ ions dopant,[48] Al2O3 coating agent/
can increase the layer spacing of lithium layers, leading to Al3+ ions dopant,[208] Al3+ ions concentration gradient dopant/
high deintercalation/intercalation rates of Li+ ions. The spe- Al2O3 coating agent,[46] Al3+ ions doped ZnO coating agent,[169]
cific capacity of the modified NCM-811 was retained about 82% Li2SiO3 coating agent/Si4+ ions dopant,[183] Mo6+ ions dopant/
from 0.1 to 2 C, which is much higher than bare NCM-811. ZrF4 coating agent,[209] Mo6+ ions dopant/Li–Mo–O compounds
The coating agents of ZrO2 can suppress the impedance growth coating agent,[98] F− ions dopant/LiF coating agent,[102] S2−
of NCM-811 effectively, and the modified material shows a ions dopant/LiNiPO4 coating agent,[184] Nb5+ ions dopant/
stable voltage hysteresis. The high cycle stability of the modi- Li3NbO4 agent,[170] and inner gradient Y3+ ions dopant/LiYO2
fied NCM-811 was attributed to a synergetic effect of ZrO2 coating agent.[110] Wang et al.[107] reported concentration gra-
coating and Zr4+ ions doping. Similar coating/doping hybrid dient LiNi0.73Co0.12Mn0.15O2 cathode material coated with a Li+
strategy for Ni-rich cathode materials was also studied, such ion conductive layer of lithium phosphorus oxynitride (LiPON).
Figure 11. Schematic illustration, SEM images, and EDS mappings of the a) first, b) second, and c) third generation concentration gradient Ni-rich
NCM cathode materials. a) Reproduced with permission.[171] Copyright 2005, American Chemical Society. b) Reproduced with permission.[172] Copyright
2009, Macmillan. c) Reproduced with permission.[177] Copyright 2012, Macmillan.
This hybrid model combined with concentration gradient and reported LiNi0.61Co0.12Mn0.27O2 cathode materials combined
coating strategy (Figure 12b). The thickness of LiPON layer is with concentration gradient and doping strategy (Figure 12c).
about 4 nm. The nanocrystalline LiPON coating and concentra- The particle of Al-doped LiNi0.61Co0.12Mn0.27O2 exhibited a con-
tion gradient strategy can provide a stable protection to inter centration gradient of Ni and Mn from center to surface with a
core of LiNi0.73Co0.12Mn0.15O2. The modified material showed constant Co content. The dopant of Al strengthened the grain
an excellent cyclic stability with a slight capacity retention of boundaries and relieved the microcracks, leading to a long cycle
87.3% at 25 °C after 1000 cycles. The rate capacity of LiPON- life. The experimental results indicated that the outstanding
coated cathode materials (153 mAh g−1) is also higher than capacity retention of 84% was obtained after 3000 cycles. It is
that of pristine cathode materials (148 mAh g−1). Kim et al.[174] long enough to give a service life nearly 10 years for EVs.
Figure 12. a) The interface models (side view and interface) and electrochemical performance of modified NCM-811 cathode materials.
Reproduced with permission.[40] Copyright 2017, Wiley-VCH. b) EDX results of the pristine LiNi0.73Co0.12Mn0.15O2 and SEM image of LiPON-coated
LiNi0.73Co0.12Mn0.15O2. Reproduced with permission.[107] Copyright 2016, Elsevier. c) The structure and cycle performance of Al-doped concentration
gradient LiNi0.61Co0.12Mn0.27O2. Reproduced with permission.[174] Copyright 2016, Wiley-VCH.
5. Element Resource and Cost Analysis of NCM including lithium, nickel, cobalt, and manganese. Lithium
resource has been identified totally over 62 million tons all
Ever-increasing market penetration of EVs is speeding up large over the world. Until 2018, about 14 million tons of lithium
amount of consumption of element resources for Li-ion bat- resources can be extracted economically, and the total reserve
tery materials since the total installed capacities (50–100 kWh) is substantial growing with the increasing of investment in
of EVs are far higher than those of consumer and electronics exploration and extraction technology.[210] The distribution
products (4–5 Wh: 3.7 V@1300 mAh for smartphones). As for of lithium reserves are uneven, and concentrated in Chile
anode, graphite is abundant and cheap, which can well meet (46.88%), China (20%), Australia (16.88%), and Argentina
the requirement of LIBs in the future. On the contrary, cathode (12.5%). Thus, the supply of lithium may be affected by geo-
materials could suffer from demand and supply risks in the political conditions. In the long run, supply will adjust to the
future owing to limited element resources and mining tech- demand due to the recycling and promising mining tech-
nology. Meanwhile, the shortage of required element resources nology.[211] Manganese reserves are the most abundant element
for LIBs will inevitably lead to battery cost rising, which is con- among these required element reserves (about 760 million tons
tradictory with reducing EV cost for increasing market penetra- on land), mainly in South Africa (29.41%), Ukraine (20.59%),
tion in the future. Therefore, it is highly necessary to identify Brazil (17.64%), Australia (13.82%), China (7.06%), India (5%),
whether the element resource available can fulfill the demand Gabon (2.94%), and Ghana (1.91%).[210] Even if the distribution
of LIBs for automotive application. In this section, we give a of resources is slightly imbalanced, the huge reserves make
comprehensive analysis for element resource and cost of NCM it confident enough to meet the problem of supply shortage.
cathode materials for automotive applications. Nickel resources are widely distributed in laterites and sulfide
deposits on land (more than 130 million tons), and about
89 million tons of nickel reserve can be extracted economically.[210]
5.1. Required Element Resource Overview for NCM Compared to manganese, the nickel reserve is smaller, but the
wide distribution of nickel reserve on the earth reduces supply
As shown in Figure 13, four main metal elements are con- dependency from single country. For cobalt, more than 25 and
sumed in the fabrication process of NCM cathode materials, 120 million tons of resources have been identified on the land and
Figure 13. Global reserves and distribution of element Li, Co, Ni, and Mn. Reproduced with permission.[210] Copyright 2019, U.S. Geological Survey.
floor of the oceans, respectively. Unfortunately, only 6.9 million (million tons) of various elements (Li, Ni, Co, Mn) has been
tons of cobalt resources can be extracted currently, which is roughly calculated with single NCM cathode material based on
only comparable with about 1% of manganese reserve.[210] Fur- the installed capacity (kWh) of total quantity of EVs on the road in
thermore, cobalt shows an unbalance distribution on land, and 2018 (5.1 million) and 2030 (new policies scenario: 125 million;
Democratic Republic of Congo (DRC) possesses nearly 50% of EV30@30 scenario: 228 million).[11] The installed capacity
total cobalt reserve.[9,212] So cobalt element seems to be more (kWh) of batteries in EVs varies dramatically. The electric pas-
critical for the Co containing cathode materials in LIBs. senger cars (excluding electric two/three-wheelers) with a set
of LIBs ranging from 20 to 100 kWh are chosen as a model to
predict the consumption of element reserves here as a result of
5.2. Demand and Supply of Raw Materials for NCM their largest market shares of EVs. As shown in Figure 14, the
demand for lithium is similar for NCM cathode materials in unit
Information on the proportion of cathode materials is not fully kWh, but manganese and cobalt have a substantially reduction
consistent from various providers of current and prediction data, with the increase of nickel content from NCM-111 to NCM-
but there is broad consensus that NCM material is becoming 811. According to our estimates (Figure 15), the total accumu-
to the main cathode for automobile LIBs. According to Global lation demand (million tons) of cathode materials for EVs will
EV Outlook 2019,[11] the annual material demand in 2018 for Li, cause a huge consumption of raw material from 2018 to 2030
Co, Mn, and Ni in LIBs for EVs are about 0.011, 0.015, 0.011, as a result of the huge growth of EVs market. The largest accu-
and 0.034 million tons, accounting for 12.94% (0.085 million mulation consumption of manganese and lithium (million tons)
tons), 10.71% (0.14 million tons), 0.06%
(18 million tons), and 1.48% (2.3 million tons)
of the annual output, respectively.[210] Com-
pared with the annual material demand for
automotive batteries, it is no doubt that the
rapid growth of EVs markets will bring great
pressure between the supply and demand of
lithium and cobalt in the near future, and
continues investment on mining technology
and scale by governments and enterprises to
expand production may be one of the most
effective ways to avoid supply shortages in
short term.[213,214]
To identify whether the required element
reserves for NCM cathode can fulfill the Figure 14. Element requirements (Li, Co, Ni, and Mn) for different NCM-based cathode mate-
increasing needs for EV applications in the rials (kg kWh−1) (anode materials: graphite). Reproduced with permission.[212,215] Copyright 2018,
next ten years, total accumulation demand OECD/IEA. Copyright 2017, Elsevier.
Figure 15. Total accumulation amount of global element requirements (million tons) for battery cathodes in 2018 and 2030: a) cobalt; b) nickel;
c) manganese; d) lithium. Total element requirements were calculated according to the element requirements in unit (shown in Figure 14), the energy
density range in LIBs for electric passenger cars (20–100 kWh), and EV stocks (2018: 5.1 million; the new policies scenario in 2030: 125 million;
EV30@30 scenario in 2030: 228 million).
with single NCM-111 will be about 8.44 and 3.42 million tons significant barriers to influence the widespread application
until 2030 in the EV30@30 scenario (Figure 15a,b), accounting and customer acceptance currently. According to strategic
for about 1.11% and 24.43% of manganese and lithium reserves, energy analysis of clean energy manufacturing analysis center
respectively. The NCM cathode for automotive LIBs is transi- (CEMAC) in 2015,[18] materials provides about 74% of total cost
tioning toward higher nickel content to provide higher energy in the manufacturing process, and the cost of cathode materials
density. As shown in Figure 15c, the total element consumption cover about 32% of the total material cost (Figure 16a). Further-
of nickel will increase from NCM-111 to NCM-811, and reach the more, raw material costs take on added importance with the
top of 3.42 million tons (22.9%) with single NCM-811 cathode decrease of production costs, especially when the total cell cost
materials until 2030 (EV30@30 scenario). The total reserves of approaches to 100 USD kWh−1.[212] So the burden of reducing
Li, Mn and Ni are enough to meet the element requirements battery costs further is inevitable to fall on the shoulder of
for EVs on the road in the next ten years. However, as shown in cathode materials.
Figure 15d, the maximum cobalt requirements for EVs on the As shown in Figure 16b, the price of Li has risen sharply in
road will exceed the total cobalt reserve (6.9 million tons) with recent years due to the large-scale application of LIBs in life
single NCM cathode material (cobalt content: >30%) until 2030 and industry. Furthermore, the price of Co is much higher than
with the EV30@30 scenario. Despite in the new policies, the total other elements, and the trend is turning to follow the Li in the
cobalt consumption is still possible to exceed 70% of the total past decades due to the effects of development trend of LIBs. In
cobalt reserve until 2030. The supply shortage of cobalt reserves the long run, the price of Co will have a big increase due to the
for automotive LIBs with the application of Ni-rich cathode mate- huge demand for cathode materials in LIBs. On the contrary,
rials will be much relieved, especially NCM-811. In the long run, Mn exhibits the lowest price among the required elements, and
the research and development (R&D) of technology recycling the trend fluctuates slightly. The price of Ni fluctuated greatly,
and Co-free cathode of LIBs is the fundamental way to solve the but the fluctuating range has reduced gradually. The minor
problem of resources shortage of cobalt for EVs.[214,216] influence on the price of Mn and Ni can be attributed to the
huge reserves and adequate supply in recent years. As shown
in Figure 16c, the cost of NCM cathode materials rely heavily
5.3. Cost Analysis of NCM on the prices of Ni and Co, but the influence of element prices
is not fully consistent on the cost of cathode materials. Obvi-
Despite electric vehicles are promoted by policies and subsi- ously, the cost of raw materials in NCM-111 (22.37 USD kg−1)
dies, but higher total cost, compared to ICEVs, is one of the is the highest of all listed cathode materials, and most of the
Figure 16. a) Detailed material cost in battery chemistry. Reproduced with permission.[18] Copyright 2015, The U. S. National Renewable Energy
Laboratory. b) The price of Ni, Co, and Mn (USD ton−1) from 1990 to 2019. c) The cost of raw materials in cathode materials (USD). The results were
calculated by average prices of Li (16 500 USD ton−1), Ni (13 844 USD ton−1), Co (33 980 USD ton−1), and Mn (2060 USD ton−1). Reproduced with
permission.[217] Copyright 2020, London Metal Exchange (LME) and Metalary. (The price is floating with the date.)
cost is from cobalt (60.79%). With the increasing of Ni con- The intrinsic structure characteristics of Ni-rich NCM including
tent, the cost of raw material reduces by over 30% from NCM- structural instability and electrode/interface instability are first
111 to NCM-811 (Co content reduced by 23%). Unfortunately, summarized and discussed. Then, the strategies to improve the
Co still accounts for about 20% of the total cost in NCM-811 safety of Ni-rich cathode materials are been presented and dis-
owing to its high price. The rising price of cobalt will result in cussed in detail.
the further increase of the cost gap of NCM cathode materials
in the near future. Furthermore, the cost of cobalt will make
a major impact on the technological strategies and raw mate- 6.1. Structural Stability of Ni-Rich NCM
rials cost, and further affects the selling prices of EVs. There-
fore, it is highly desirable to develop Ni-rich/Co-poor NCM Excess lithium is often used in the production process of highly
cathode materials with higher energy densities and lower cost ordered Ni-rich NCM cathode material with layered struc-
for pushing widespread adoption of EVs in the future. ture, so residual lithium (converted into Li2O) remaining on
the surface of active materials can react with H2O and CO2 in
the ambient air during assembly and long-term storage pro-
6. The Safety of Ni-Rich NCM for LIBs cess, forming lithium compounds of LiOH and Li2CO3.[139,140]
Unwanted lithium compounds such as Li2CO3 can react with
As discussed previously, Ni-rich cathode materials for LIBs the electrolyte, resulting in the gas evolution (CO2 and CO)
show attractive merits (high energy density, low cost, etc.) during the electrochemical cycle (Figure 17a).[218,219] Gas emis-
for speeding up their market penetration in the areas of EVs. sion can increase the internal pressure of the cells, leading to
Unfortunately, battery safety is also increasingly concerned leakage, distortion, and detonation.
owing to some drawbacks of Ni-rich NCM. With the contin- Moreover, NCM cathode shows the tendency of oxygen
uous increase of Ni content in NCM cathode, the consequently evolution, and the oxygen partial pressure increases approxi-
structural and interfacial instability, and low thermostability of mately in a line with the potential (vs Li) in ternary cathode
Ni-rich NCM would cause material degradation, serious side system. When the voltage is over 3 V, the oxygen partial pres-
reaction, electrolyte decomposition, cell swelling, and finally sure is already larger than the atmospheric pressure.[220] Fur-
trigger the whole cell thermal runaway, thus limiting the thermore, Mn and Co are very important for maintaining the
widespread application of Ni-rich NMC.[52] In this section, we layered oxide structure of NMC cathode materials inherently,
mainly focus on safety issues of LIBs caused by Ni-rich cathode so Ni-rich NCM exhibits low structural stability and high sur-
at the abused conditions including overcharged state, thermal face activity due to the content reduction of Mn and Co. Often,
stability, thermal runaway, oxygen release, and so on, which is attempting to increase the cutoff voltage is regarded as an
different with Part 4 (mainly focuses on cycling stability at the effective strategy to get higher energy density, but the charging
normal working state and calendar lifetime at the rest state). process of LIBs is often accompanied by an exothermic
inevitably during the charge process when

the cutoff voltage is over 4.7 V. Moreover,
Ni-rich NCM cathode materials with mas-
sive Ni4+ ions exhibit high chemical activity
at fully charged state, so they can react with
electrolyte violently during repeated charge/
discharge cycles, leading to the decomposi-
tion of liquid electrolyte with a dispropor-
tionation reaction and strong exothermic
reaction.
Besides, mechanical abuse (puncture,
collision, extrusion, etc.), internal short
circuit, operating with a large current, and
thermal abuse can also lead to intense
chemical reactions and strong exothermic
reaction. As shown in Figure 17b, low
thermal conductivity and stability of electro-
lyte and active materials may cause safety
problems such as heat accumulation of
the cells. First, the SEI begins to decom-
pose when the internal temperature of
the cell rises to about 90 °C.[221] After that,
lithium ions embedded in anode materials
react with electrolyte and binder, causing
the temperature up to 150 C. The PE sepa-
rator begins to melt and the base electrolyte
reacts violently at this temperature, forming
PF5.[222] PF5 can catalyze the decomposi-
tion of electrolyte, leading to the increase of
temperature further. However, the thermal
stability of NCM cathode materials turns
worse with the increase of Ni content owing
to the faint stabilizing effect of low Mn con-
tent, although the capacity has increased
(Figure 17c).[36] So when the temperature
up to 180–300 °C, Ni-rich NCM cathode
materials decompose and react with elec-
trolyte violently, resulting in gas emission
strong exothermic and elevated temperature
Figure 17. a) Illustration of the decomposition process of unwanted lithium compounds on further (Figure 17d).[223] Then, the separator
the surface of NCM-622. Reproduced with permission.[219] Copyright 2017, American Chemical
collapses and massive internal short cir-
Society. b) Temperature ranges of large format prismatic LIBs for thermal runaway test. Repro-
duced with permission. [222] Copyright 2014, Elsevier. c) The relationship between discharge cuit occurs in the cell, leading to electrolyte
capacity, and thermal stability and capacity retention of the main NCM cathodes. Reproduced burning. The components and materials in
with permission.[36] Copyright 2013, Elsevier. d) Mass spectroscopy profiles for the oxygen the cell decompose one after another with
collected during the phase transitions for NCM cathode materials. Reproduced with permis- the rising of temperature abnormally, and
sion.[223] Copyright 2014, American Chemical Society. the chain reactions result in thermal run-
away, such as fuming, fire and explosion.
phenomena owing to the existence of internal resistance. The So retarding and interrupting thermal runaway are very valu-
elevated temperatures make lower chemical and structural sta- able for passengers to leave sufficient time to escape from a
bility, resulting in the risk raised by decomposition and gas damaged EV.
emission.
6.3. Strategies to Improve Safety of Ni-Rich NCM-Based LIBs

6.2. Interface Stability of Ni-Rich NCM
Improving the structural/interface stability or reducing contact
Overcharging can cause permanent damage to body cells, area with electrolyte is beneficial to reduce side and exothermic
leading to severe safety accidents. Because the operation voltage reactions. Furthermore, the thermal runaway can be effectively
of conventional nonaqueous electrolytes are usually range from prevented if the temperature rise can be controlled in the ini-
1.0 to 4.7 V (vs Li/Li+),[2] the decomposition of electrolyte occurs tial stage due to the broken chain reactions by improving the
Table 3. The thermal stability of different modified Ni-rich NCM cathode materials.
Electrode materials Cut-off Decomposition Generated Refs.

voltage [V] temperature [°C] heat [J g−1]
Na-doped NCM-523 4.5 225.44 (Peak1), 105.68 (Peak1), [97]
293.69 (Peak2) 244.70 (Peak2)
Li2ZrO3 (1 wt%) coated NCM-523 4.6 294.7 484 [124]
Al2O3-coated NCM-523 4.8 367 3600 [224]
Normal layered NCM-523, 4.3 290.2, 972.6, [83]
the specific structured layered NCM-523 302.1 609.9
La2O3-coated NCM-523 4.6 293.3 – [95]
Anatase TiO2 (1.0 wt%) coated NCM-622 4.5 287.7 – [225]
SiO2-coated NCM-622 4.3 288 1217 [159]
MnPO4-coated NCM-622 4.3 285.6 264.6 [104]
Mn3(PO4)2-coated NCM-622 4.3 292 1170 [158]
Al2O3/PEDOT-co-PEGa)-coated NCM-622 4.3 284.0 (Peak1), 391.0 (Peak1), [226]
288.5 (Peak2) 345.1 (Peak2)
Mn surface doped NCM-811 4.3 224 – [186]
LiNi0.8Co0.1Mn0.1O1.94F0.06 4.3 245 1304 [179]
AlF3-coated NCM-811 4.3 248.3 3079 [166]
LiYO2-coated/inner gradient Y3+-doped NCM-811 4.3, 240.35, –, [110]
4.5 229.64 –
Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 4.3 250 2261 [171]
Full concentration-gradient NCM-622 4.4 282.7 692 [137]
Concentration-gradient LiNi0.67Co0.15Mn0.18O2, 4.3 263, 1530, [205]
outer-layer LiNi0.58Co0.15Mn0.28O2, 271, 858,
core LiNi0.8Co0.15Mn0.05O2 217 2632
Constant-concentration LiNi0.62Co0.14Mn0.24O2, 4.3 286, –, [227]
concentration-gradient Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2, 295, –,
Al2O3-coated concentration-gradient Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2 301 –
Concentration-gradient LiNi0.7Co0.15Mn0.15O2 4.4 245.6 812.7 [47]
Concentration-gradient LiNi0.83Co0.07Mn0.10O2 4.3 227 662 [176]
Core-shelled Li[(Ni0.8Co0.1Mn0.1)2/7]core[(Ni1/3Co1/3Mn1/3)3/14]inner-shell[(Ni0.4 4.3 250 (Peak1), 660 [228]
Co0.2Mn0.4)1/2]outer-shellO2 290 (Peak2)
Al substituted full concentration gradient LiNi0.600Co0.121Mn0.272Al0.007O2 4.3 289.2 889 [174]
Two-sloped full concentration gradient LiNi0.65Co0.13Mn0.22O2 4.3 274 – [175]
a)PEDOT-co-PEG: poly(3,4-ethylenedioxythiophene)-co-poly(ethylene glycol).
thermal stability of Ni-rich NCM cathode. Here, we listed the is also reduced due to the isolating mechanism of the coating
improvement on the thermal stability of different modified layer of Mn3(PO4)2. So the generated heat of pristine NCM-
Ni-rich NCM cathode materials in Table 3. 622 was also decreased after coated by Mn3(PO4)2 from 1882
Coating is one of the most effective strategies to improve the to 1170 J g−1. After that, Chen et al.[104] reported the thermal
interface stability due to its exceptionally good protection and stability of MnPO4-coated NCM-622. The onset decomposition
isolation effect to passivate chemical reaction. Phosphates is a temperature of NCM-622 shifts to higher temperature from 274
promising coating material for Ni-rich NCM cathode materials to 285.6 °C after coated MnPO4. This result verified the pre-
that can improve the thermal stability and overcharging per- vious research that strong PO4 covalent bonds and isolating
formance due to their strong PO4 covalent bonds and isolating functions of outer MnPO4 coating layer could improve the
functions. Cho et al.[158] prepared NCM-622 cathode materials thermal stability and suppress the direct contact between the
coated with the uniform nanocrystalline Mn3(PO4)2 by a simple electrolyte and cathode materials effectively.
heat treatment in air (Figure 18a). Mn3(PO4)2-coated NCM-622 Oxides are also effective coating materials to improve their
exhibited higher decomposition temperature (292 °C) than the interface stability of Ni-rich NCM cathode materials. Cho
pristine NCM-622 (275 °C). The result indicated the thermal et al.[159] reported the thermal properties of NCM622 coated
stability of NCM622 was improved after coated by Mn3(PO4)2, by SiO2 (Figure 18b). Nanosized SiO2-coated NCM-622 exhib-
which was attributed to strong PO4 covalent bonds. Further- ited higher decomposition temperature (288 °C) than the pris-
more, the contact area between the electrolyte and NCM-622 tine NCM-622 (275 °C), and the generated heat of pristine
Figure 18. TEM images, DSC curves, and cycle performance of a) Mn3(PO4)2-coated NCM-622 and b) SiO2-coated NCM-622 cathode materials. Reproduced
with permission.[158,159] Copyright 2015 and 2016, Elsevier. c) HRTEM images and DSC curves of pristine and Al2O3-coated NCM-523 cathode materials.
Reproduced with permission.[224] Copyright 2016, Elsevier. d) TEM images and DSC curves of LiNi0.8Co0.1Mn0.1O1.94F0.06 cathode materials. Reproduced with
permission.[179] Copyright 2007, The Electrochemical Society. e) TG, DTG, and DSC curves of Li[Ni0.8Co0.1Mn0.1−x−yAlxMgy]O2 (x, y = 0.0–0.02). Reproduced
with permission.[162] Copyright 2009, Elsevier. f) TEM, HRTEM images, and DSC curves of the concentration-gradient Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2,
constant-concentration LiNi0.62Co0.14Mn0.24O2, and Al2O3-coated concentration-gradient Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2. Reproduced with permission.[227]
Copyright 2015, Elsevier. g) SEM images, EDS pattern, TEM images, and electrochemical performance of Li[Ni0.84Co0.06Mn0.09Al0.01]O2. Reproduced with
permission.[229] Copyright 2016, American Chemical Society.
NCM-622 was also decreased after coated by Mn3(PO4)2 from thermal stability. Woo et al.[179] reported the thermal proper-
1882 to 1217 J g−1, indicating the improved thermal stability of ties of NCM-811 doped by the element of F with a spherical
NCM622 after coated by SiO2. These results are attributed to the morphology (Figure 18d). The decomposition tempera-
high meting point of SiO2 (1719 °C). Shi et al.[224] investigated ture of LiNi0.8Co0.1Mn0.1O2−zFz was increased, and their
the thermal properties of NCM-523 coated with ultrathin Al2O3 generated heats are also reduced as the concentration of F
by atomic layer deposition (Figure 18c). After the first charging increased. These results indicate that the thermal stability of
process, the exothermic peak of decomposition temperature LiNi0.8Co0.1Mn0.1O2−zFz was improved significantly, which was
(379 °C) and generated heat (2700 J g−1) are no difference for attributed to the surface protection effect and high structural
the pristine and Al2O3-coated cathode materials. However, the stability with the substitution of fluorine. After that, they inves-
decomposition temperature of pristine and Al2O3-coated NCM- tigated the thermal properties of NCM-811 cathode materials
523 is decreased to 355 and 367 °C after 20 cycles, respectively. doped by different content of Al and Mg (Figure 18e).[162] The
The reduction of decomposition temperature both of the pris- exothermic heat generation of Li0.3Ni0.8Co0.1Mn0.1−x−yAlxMgyO2
tine and Al2O3-coated NCM-523 is mainly because the decrease decreased with the increase of Al and Mg, resulting in high
of structural stability. Al2O3-coated NCM-523 showed higher structural stability and thermal stability.
decomposition temperature compared with pristine NCM-523, Ni-rich cathode materials with a concentration gradients
indicating the better thermal stability of Al2O3-coated NCM-523. usually have a shell of Mn-rich cathode materials that can
Element substitution can effectively stabilize the chemical improve their interface and structural stabilities with the
and structural stability of Ni-rich NCM cathode materials by mostly preserved capacity. Liao and Manthiram[227] compared
suppressing phase transitions, resulting in enhancement of the thermal stability of the concentration-gradient layered
Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2 (CG), constant-concentration for improving intrinsic structural stability in the short term.
LiNi0.62Co0.14Mn0.24O2 (CC), and Al2O3-coated concentration- Meanwhile, developing highly stable electrolyte or electrolyte
gradient layered Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2 (CG-Al2O3) additives and solid electrolyte would be also effective solutions
(Figure 18f). The CG cathode material (295 °C) represents to enhance the stability of electrolyte and electrode/electrolyte
higher decomposition temperature than CC cathode material interface for Ni-rich NCM. From a practical point of view, it
(286 °C), indicating its better thermal stability. This is mainly would be highly desirable to develop fast charging capability
because the high decomposition temperature of Mn-rich outer for making EVs refueling like ICEVs. Strategies to improve
shell on the surface of CG cathode material. Among them, the rate performance of Ni-rich NCM cathode materials are mainly
CG-Al2O3 cathode material shows the highest peak tempera- focused on reducing the diffusion path of Li+ ions and electron
ture (301 °C) due to the stabilizing effect on the base of CG by nanotechnology, or on improving the electrical and ionic
cathode material. Li[Ni0.84Co0.06Mn0.09Al0.01]O2 with two-step conductivity in the bulk or at the surface of the active material.
concentration gradients of Ni and Mn content was prepared Ever-increasing development of EVs will certainly speed up
by Lim et al (Figure 18g).[229] On the one hand, this two-step a large amount of consumption of element resources for elec-
concentration-gradients structure offers a maximized Ni and trode materials (e.g., Li, Ni, Mn, Co, Al, Cu, graphite, etc.). As
Mn content in the center and surface layer to get a high dis- for NCM cathode material, the consumption amounts of the
charge capacity and thermal stability, respectively. On the other required four elements (Li, Ni, Mn, and Co) are roughly cal-
hand, the Al substitution can improve the cycle performance culated to identify whether there exists a demand and supply
of the NCM cathodes.[162] The two-step concentration gradients risk in the future. Element Li (reserves: 14 million tons), Ni
Li[Ni0.84Co0.06Mn0.09Al0.01]O2 shows a higher thermal stability (reserves: 89 million tons), and Mn (reserves: 760 million tons)
(220 °C) and much better cycle performance than that of the possess relatively abundant reserves and there is almost no
commercial Li[Ni0.85Co0.11Al0.04]O2 (NCA). demand and supply risk for EVs by 2030. However, the total
demand of cobalt for EVs will have a risk of exceeding the total
cobalt reserve (6.9 million tons) by 2030. As such, developing
7. Summary and Outlooks Co-less cathode materials (e.g., Ni-rich NCM) is an effective
solution in the near future. In the long run, exploiting Co-free
To push widespread market penetration of LIB-powered EVs, cathode materials and LIB recycling will be a dominant trend.
driving range is expected to at least 300 miles in the future Furthermore, new battery chemistries with earth-abundant
and thus requires the search of electrode materials with higher resources (e.g., Na-ion batteries, Zn-ion batteries, etc.) would be
energy density, both cathode and anode, which unquestionably a substitution of LIBs in the low-power application fields.
depends on the material breakthroughs. Especial for cathode
material, it is a key because specific capacity, working voltage,
and energy density of the whole cell are dominated by cathode Acknowledgements
side. In recent years, Ni-rich NCM brings a great promise owing
to its high specific capacity (>200 mAh g−1 at the material level) The authors would like to acknowledge the financial support from high
level introduction of talent research startup fund of Hunan University
and a high energy density of over 300 Wh kg−1 at the cell level,
(531118010133) and from Project supported by the State Key Laboratory
which is much higher than those of conventional cathode mate- of Powder Metallurgy, Central South University, Changsha, China. The
rials (LCO, LMO, LFP, NCM-111, etc.). Besides the concern authors also acknowledge the support provided by the Natural Sciences
of energy density, some other factors (fast charge capability, and Engineering Research Council of Canada (NSERC), University of
cycling life and calendar life, element resource and cost, and Waterloo, and Waterloo Institute for Nanotechnology.
safety) also have a great effect on facilitating the practical appli-
cation of Ni-rich NCM for automotive batteries. In this Review
article, we give a comprehensive analysis and discussion for Ni- Conflict of Interest
rich/Co-poor NCM materials in terms of energy density, power
density, service lifetime, battery cost and elemental resources, The authors declare no conflict of interest.
and safety.
Although Ni-rich NCM shows attractive merits for EV
application, it still suffers from unwanted drawbacks such as Keywords
intrinsic structural instability, interfacial instability, and electro- battery cost, electric vehicles, energy density, lithium ion batteries,
lyte side reaction upon charge process. Moreover, phase trans- Ni-rich/Co-poor cathodes
formation from layered phase to spinel and/or rock-salt phases,
and oxygen evolution from host lattice of the highly delithiated Received: November 25, 2019
high-Ni NCM cathode are main reasons to cause short service Revised: January 7, 2020
life and safety hazard. Structural design (core–shell structure, Published online:
concentration gradient, etc.), intrinsic structure modifica-
tion, and surface coating have been employed to address the
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Ni‐Rich/Co‐Poor Layered Cathode for Automotive Li‐Ion Batteries: Promises

Article in Advanced Energy Materials · February 2020

Xinxin Wang Yuan-Li Ding

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Ya-Ping Deng Zhongwei Chen

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Ni-Rich/Co-Poor Layered Cathode for Automotive Li-Ion

electrochemical, and interface stability is very important to

in LiMn0.2Ni0.8O2 can suppress partial cation mixing, and

materials on the crystal scale.[103,114] In addition to the above

4. Service Life of Ni-Rich NCM for LIBs

can accelerate microcrack evolution further. Crack evolution

4.3. Strategies to Improve Cycling Lifetime of Ni-Rich NCM

In order to improve the cycle performance of Ni-rich NCM

4.3.1. Doping Strategy

Doping is generally recognized as an effective strategy to

Electrode materials Voltage Current Cycles Specific capacity Capacity Refs.

inevitably during the charge process when

6.3. Strategies to Improve Safety of Ni-Rich NCM-Based LIBs

Electrode materials Cut-off Decomposition Generated Refs.

a)PEDOT-co-PEG: poly(3,4-ethylenedioxythiophene)-co-poly(ethylene glycol).

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