RESEARCH ARTICLE
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Stepwise Dopant Selection Process for High-Nickel Layered
Oxide Cathodes
Do-Hoon Kim, Jun-Hyuk Song, Chul-Ho Jung, Donggun Eum, Byunghoon Kim,
Seong-Hyeon Hong, and Kisuk Kang*
NCM-based lithium layered oxides (LiNi1–x–yCoxMnyO2) have become
prevalent cathode materials in state-of-the-art lithium-ion batteries. Higher
energy densities can be achieved in these materials by systematically
increasing the nickel content; however, this approach commonly results in
inferior cycle stability. The poor cycle retention of high-nickel NCM cathodes
is generally attributed to chemo-mechanical degradation (e.g., intergranular
microcracks), vulnerability to oxygen-gas evolution, and the accompanying
rocksalt phase formation via cation mixing. Herein, the feasibility of doping
strategies is examined to mitigate these issues and effective dopants for
high-nickel NCM cathodes are theoretically identified through a stepwise
pruning process based on density functional theory calculations. Specifically,
a sequential three-step screening process is conducted for 38 potential
dopants to scrutinize their effectiveness in mitigating chemo-mechanical
lattice stress, oxygen evolution, and cation mixing at charged states.
Using this process, promising dopant species are selected rationally and a
silicon-doped LiNi0.92Co0.04Mn0.04O2 cathode is synthesized, which exhibits
suppressed lattice expansion/contraction, fewer intergranular microcracks,
and reduced rocksalt formation on the surface compared with its undoped
counterpart, leading to superior electrochemical performance. Moreover,
a comprehensive map of dopants regarding their potential applicability is
presented, providing rational guidance for an effective doping strategy for
high-nickel NCM cathodes.
D.-H. Kim, J.-H. Song, C.-H. Jung, D. Eum, B. Kim, S.-H. Hong, K. Kang
Department of Materials Science and Engineering
Research Institute of Advanced Materials (RIAM)
Seoul National University
1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea
E-mail: matlgen1@snu.ac.kr
K. Kang
Center for Nanoparticle Research
Institute for Basic Science (IBS)
Seoul National University
1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea
K. Kang
School of Chemical and Bioengineering
Institute of Engineering Research
College of Engineering
Seoul National University
1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202200136.
DOI: 10.1002/aenm.202200136
Adv. Energy Mater. 2022, 12, 2200136 2200136 (1 of 9)
1. Introduction
Recently, high-nickel NCM
(LiNi1–x–yCoxMnyO2, 1 – x – y ≥ 0.8) cathode
materials have garnered considerable
research interest owing to their high spe-
cific capacities (>200 mA h g−1) and have
been extensively applied in state-of-the-
art lithium-ion batteries.[1,2] It has been
widely observed that a higher nickel con-
tent in NCM cathodes leads to an increase
in the usable specific capacity of layered
cathodes in a given voltage window and is
practically beneficial as the nickel replaces
toxic and high-cost cobalt.[3–8] Neverthe-
less, this approach of increasing the nickel
content is typically hindered by inferior
cycle performance resulting from the
chemo-mechanical failure of high-nickel
NCM particles during extended cycling.
Recent studies have revealed that the rapid
capacity fade in these materials is cor-
related to intergranular cracking in sec-
ondary particles[9–11] and the surface phase
transition[12,13] at a high state of charge.
In particular, the large variation of the
c-lattice parameter upon de/lithiation has
been reported as the main cause of inter-
granular cracking and the corresponding secondary particle
destruction.[14–16] The large c-lattice parameter change upon
repetitive cycling induces anisotropic contraction and expan-
sion among randomly oriented primary particles, consequently
leading to mechanical stress and crack propagation in sec-
ondary particles.[14,15] Not surprisingly, parasitic side reactions
continue to occur at the interface between the newly exposed
particle surface and the electrolyte, and the accumulation of the
by-products over cycling increases the cell impedance and grad-
ually leads to degradation of the cell performance.[9,15]
The low thermal stability of high-nickel NCM materials is
another drawback preventing their practical adoption. A series
of studies have indicated that the onset temperature of oxygen
evolution at charged states substantially decreases as the nickel
content increases in NCM compositions.[17,18] The low onset
temperature of oxygen evolution intensifies the risk of thermal
runaway of the battery system at charged states, making high-
nickel NCM materials unreliable with respect to safety.[19] In
addition, oxygen evolution is known to trigger the reconstruc-
tion of the surface structure of NCM particles, accompanying
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Figure 1. Schematic illustration of stepwise pruning process for selection of dopants in high-nickel NCM. The number of elements considered in each
step are displayed.
significant cation mixing[19–21] and the corresponding phase
transition from a layered to a spinel or rock-salt structure.[22–24]
These types of surface reconstruction are generally known to
increase the charge-transfer resistance, resulting in the build-
up of voltage hysteresis and premature cell failure.[22]
One common strategy to overcome these chronic issues has
been to slightly modify the composition of high-nickel NCM
materials via elemental doping while preserving the high nickel
content in the layered structure.[25–30] Numerous dopants have
been previously explored in both experimental and theoretical
case studies with the goals of mitigating microcrack forma-
tion,[25,26] suppressing oxygen-gas generation,[27–29] and/or
reducing surface phase transformation.[29,30] Although some of
these attempts have resulted in notable performance enhance-
ments,[31–34] the optimal dopant species/compositions that can
simultaneously resolve the aforementioned difficulties remain
elusive. Moreover, there have been ambiguities and/or incon-
sistent results regarding the roles of dopants even for similar
compositional NCM electrode materials.[35–38] This issue arises
partly because during the doping process, contributing factors
other than intrinsic dopant effects may arise and be dominant,
which would have a substantial effect on the overall cathode
performance. For example, the conventional doping process
often induces a change in the primary particle/grain micro-
structure[25,26,39] and sometimes leaves conductive carbon resi-
dues from using dopant precursors on the particle surface.[40,41]
The additional heating process necessary for certain dopants
may also alter the surface nature of the pristine NCM particles,
which can result in a significant change in the electrochemical
performance regardless of the presence of dopants.[42–44] Fur-
thermore, the distribution/amount of dopants in the structure/
grain boundaries critically depends on the dopant species and
the doping processes. These complexities make it challenging
to clearly understand the intrinsic effect of each dopant when
they are incorporated into the NCM layered structure; further
clarification is indispensable in establishing rational and effec-
tive doping strategies beyond the simple trial-and-error-based
dopant selections.
In this work, we investigate the effects of various dopants
through a systematic exploration of a model system of doped-
LiNiO2 based on density functional theory (DFT) calculation,
which can serve as a map of intrinsic dopant effects for high-
nickel NCM materials. In this process, a three-step sequential
filtration is applied to identify the most suitable dopants to
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mitigate microcrack generation, enhance the thermal stability,
and suppress the surface reconstruction involving cation disor-
dering. The stepwise pruning process covers 38 elements in the
periodic table, including previously proposed dopants. Inspired
by the dopant selection results, we experimentally synthesize
silicon-doped high-nickel NCM (LiNi0.92Co0.04Mn0.04O2) and
confirm that the doped-LiNi0.92Co0.04Mn0.04O2 electrode under-
goes smaller lattice changes during cycling and consequently
suffers less from microcrack formation in the secondary parti-
cles, as evidenced by in situ X-ray diffraction (XRD), scanning
electron microscopy (SEM), and scanning transmission elec-
tron microscopy (STEM) analyses. Moreover, these changes in
the material behavior are demonstrated to lead to an enhanced
electrochemical performance with prolonged capacity retention
and higher rate capability compared with that of the undoped
system. We believe that our strategy and findings enrich the
fundamental understanding of the effects of diverse dopants
and are expected to provide valuable guidance for the explora-
tion of potential dopants for stable high-nickel NCM materials.
2. Results and Discussion
In an effort to identify the potential dopant candidates and
their efficacies, we designed a three-step pruning process for
the dopant selection by considering the degradation mecha-
nism of high-nickel NCM materials, as schematically shown in
Figure 1. For 38 dopant candidates covering Group 13–15 ele-
ments and 3d to 5d metals in the periodic table, we selected
the anisotropic lattice parameter variation as the first criterion
in the pruning process, preferentially selecting candidates that
can reduce the lattice strain during de/lithiation of the layered
structure. Next, for the dopants that met the first criterion, the
effect on the oxygen-gas evolution was evaluated by estimating
the change in the formation energy of oxygen vacancies due
to the presence of the dopant. In this step, we selected ele-
ments that could increase the oxygen-vacancy formation energy
in the doped structure relative to that in the undoped system.
Finally, the effect of the dopants on the structural stabiliza-
tion was considered. Considering that the surface transition to
a spinel or rocksalt phase involves transition-metal migration
and disordering, the migration energy of nickel ions from the
transition-metal layer to the lithium layer (with or without
oxygen vacancy) was evaluated for the dopant candidates that
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passed the two prior criteria, leading to the selection of one
trial dopant for experimental verification. Although we arrived
at one final dopant that optimally satisfied all of our quantita-
tive criteria, it should be noted that during the pruning process,
several promising dopant candidates lay in the marginal region
and were excluded in the final selection. Thus, we provide the
full calculational data for all the dopants that were examined
but screened out for each pruning process in the supplemen-
tary information (Figure S1, Supporting Information) for future
reference in dopant studies.
As the nickel content in the NCM material increases, the
material properties approach those of LixNiO2 (LNO, 0 ≤ x ≤ 1),
which is the end member of the high-nickel NCM.[45,46] There-
fore, we assumed that the calculation for LNO would ade-
quately demonstrate the phenomenon that can be expressed
in high-nickel NCM materials (Figure S2, Supporting Informa-
tion). For the selection process for the lattice strain, we first
calculated the lattice-parameter variation that occurs in the
undoped LNO system, as a function of lithium content as a
reference. Figure S3 (Supporting Information) shows that the
c-lattice parameter gradually increases from 14.09 to 14.29 Å
with lithium extraction until x = 0.33. This maximum c-lattice
parameter drops to 13.56 Å with further delithiation up to
x = 0.16, resulting in c-lattice contraction of ≈5.1%.[47] In con-
trast, the maximum a-lattice parameter change was less than
0.01% (from 5.62 to 5.60 Å) for the same degree of delithia-
tion. These non-symmetrical lattice parameter changes imply
anisotropic strain generation in the secondary particles that
are typically comprised of randomly oriented primary particles.
Having this value as a reference, we investigated how the large
c-lattice contraction is affected by the 38 potential dopants
in Figure 2. We calculated high-doping concentration (8.2%)
cases considering the size of supercells in our computations to
swiftly check the intrinsic features of the dopant while under-
taking rigorous screening (Discussion S1 and Figure S4, Sup-
porting Information). The c-lattice parameter variation for the
doped system was calculated by taking the difference between
the maximum (x = 0.33) and minimum (x = 0.16) c-lattice
parameters for the LixNi0.92M0.08O2 (M = dopant) system. The
diagram shows that all the dopants are beneficial to some
extent in mitigating the abrupt c-lattice parameter contraction,
with their efficacies varying from 2.74% for Zr to 3.88% for
Os. Nevertheless, we expect that these values are rather over-
estimated given the relatively high doping concentration of our
model system (8%), considering that the typical doping level is
≈2%.[25,48,49] Thus, we applied a strict selection condition of a
c-lattice parameter change of less than 3%, even though several
previous studies have reported that even a smaller remedy of
the c-lattice parameter collapse could help in mitigating det-
rimental chemo-mechanical failure.[49,50] This process led to
12 potential dopant candidates (Al, Si, V, Mn, Cu, Zr, Mo, Ag,
Sn, W, Re, Ir), as indicated in blue in the figure, with 14 dopants
in a marginal region (yellow) and 12 dopants excluded (red).
Further investigation of c-lattice parameter changes in these
doped systems revealed the nickel-slab distance monotonically
decreased during the delithiation process, which is attributed
to the oxidation of nickel (Ni3+→ Ni4+), whereas the lithium-
slab distance increased from x = 1 to x = 0.33 and significantly
collapsed with further delithiation to x = 0.16, consistent with
the general understanding that the c-lattice parameter contrac-
tion is induced by the lithium-slab contraction at high state
of charge[15,51] (Tables S1 and S2, Supporting Information).
Table S2 (Supporting Information) clearly shows that the
selected dopants could mitigate the collapse of the lithium-slab
distance at the end of charge, thereby reducing the large aniso-
tropic c-lattice collapse of the layered structure.

Figure 2. The c-lattice parameter contraction from Li0.33Ni0.92M0.08O2 to Li0.16Ni0.92M0.08O2 for the 38 doping candidates (M: doping candidates). The
dotted line represents the baseline used to select the first filtered candidates (within 3%). All the elements were categorized into four groups: nickel
ion as a reference element (green), candidate elements (blue), marginal elements (orange), and excluded elements (red).

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Figure 3. a) Oxygen-vacancy (VO) formation energy in Li0.16Ni0.92M0.08O2
(M: first filtered dopants). The dotted line with the value of −0.12 eV indi-
cates the oxygen-vacancy formation energy in Li0.16NiO2. b) Nickel-ion
stability at tetrahedral site in the lithium layer for Li0.16Ni0.92M0.08O2 (M:
second filtered dopants). The dotted line with the value of 1.01 eV indi-
cates the nickel-ion stability at the tetrahedral site of the lithium layer
in Li0.16NiO2. c) Nickel-ion stability at the tetrahedral site of the lithium
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As a second step, we examined the change in the oxygen-
vacancy formation energies when the dopant candidates that
passed the first screening were incorporated into the structure,
helping to guide the selection of potential dopants that would
be beneficial for attaining structural stability at a high state of
charge. The oxygen-vacancy formation energies were calculated
for all the oxygen atoms in the unit cell (24 atoms) for each
doped system, and the oxygen vacancy with the lowest forma-
tion energy was selected as a representative for the system (cal-
culational details are provided in the Method section). Figure 3a
presents a schematic illustration of the oxygen-gas evolution
from the lattice oxygen (left) and the predicted vacancy forma-
tion energies (right) for each dopant species. For reference, the
oxygen-vacancy formation energy for the undoped system was
calculated to be −0.12 eV, indicating the spontaneous oxygen-
gas evolution at a highly charged state, which is consistent
with previous experimental and theorical works.[28,52,53] How-
ever, it was revealed that the lattice-oxygen stability is signifi-
cantly altered by the presence of dopants; the vacancy forma-
tion energies varied over a wide range from 0.16 eV to −1.24 eV
depending on the dopant. Al, Si, Mn, Cu, and Ir dopants were
observed to substantially increase the oxygen-vacancy forma-
tion energy compared with that of the undoped case (−0.12 eV).
In contrast, dopants such as V, Mo, Ag, and Re aggravated the
oxygen-gas evolution from the layered structure in the charged
state and were thus excluded in our screening process. There
were also some dopants that displayed a marginal difference in
the oxygen-vacancy formation such as Zr, Sn, and W compared
with the undoped reference, indicating that they might be ben-
eficial in mitigating the lattice strain, as determined in the first
screening, but do not notably contribute to the structural sta-
bility in the highly charged state. In this respect, we classified
the dopants into three categories: “candidates,” “marginal can-
didates” with oxygen-vacancy formation energies higher than or
similar to that of the undoped case, and “excluded elements”
with significantly lower oxygen-vacancy formation energies.
Recent studies have shown that the strength of the ionic bond
between two neighboring atoms is proportional to the effective
charge of each atom,[54,55] inferring that the different valence
states of dopants may influence the strength of the ionic bond
between the dopant and oxygen (Table S3 and Figure S5, Sup-
porting Information). Our results also indicate that the lattice-
oxygen stabilities are generally enhanced by dopants with high
valence states due to the stronger bonding with adjacent oxygen
ions. Accordingly, we selected five dopant candidates (Al, Si,
Mn, Cu, Ir) for further screening.
In the final step, we evaluated the tendency of nickel-ion
migration/disordering in the layered structure and its depend-
ency on the neighboring dopant species. Considering that the
irreversible phase transition from the layered to spinel or rocksalt
structures is initiated by cation mixing, the energetics of nickel-
ion migration were probed at a highly charged state.[56] Figure 3b
presents a schematic illustration of nickel-ion migration (left)
layer with neighboring oxygen vacancy (VO) in Li0.16Ni0.92M0.08O2 (M: third
filtered dopants). The dotted lines with values of −0.70 eV indicates the
nickel-ion stability at the tetrahedral site of the lithium layer with oxygen
vacancies in Li0.16NiO2. All elements were categorized into 4 groups iden-
tical to the first criterion.
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and the predicted nickel stability (right) when the nickel in the
vicinity of a dopant element migrates to a face-shared tetrahedral
site in the lithium layer. The nickel-ion stability was estimated
from the energy difference of the pristine structure and the dis-
ordered structure with the migrated nickel ion. As a reference,
the undoped system displayed an energy penalty of 1.01 eV when
the nickel-ion disorder occurred.[57] Among the five dopant can-
didates, Al, Si, and Cu were observed to help inhibit the nickel
migration, with higher energy penalties of 2.35, 2.1, and 1.92 eV,
respectively, whereas Mn and Ir were either less effective or det-
rimental. We suppose that the volume change of the tetrahedral
sites due to dopant incorporation would have caused the energy
penalty for the nickel migration to the site.
We further supposed that the phase transition on the sur-
face would be more prone to occurring simultaneously with the
formation of oxygen vacancies, as recent works have elucidated
that oxygen vacancies facilitate transition-metal migration into
the lithium layer in layered lithium oxides.[58,59] In this regard,
we additionally considered the nickel-ion stability in the con-
text of the oxygen vacancies, as illustrated in Figure 3c. It could
be confirmed that the nickel ion was substantially stabilized in
the lithium layer (−0.70 eV) in the presence of oxygen vacancies
(Figure S6, Supporting Information), implying spontaneous
nickel-ion migration into the lithium layer in the undoped ref-
erence in a highly charged state. However, when dopant ele-
ments were present nearby, the nickel-ion migration tendency
was slightly altered. The Al and Cu dopants were observed
to further promote the nickel migration to the lithium layer
(−0.97 and −0.84 eV, respectively), whereas Si doping could help
mitigate this migration (−0.50 eV) regardless of the presence of
oxygen vacancies. Before selecting the final dopant candidate,
we also re-examined their effects in different dopant sites (octa-
hedral vs tetrahedral sites) in the layered structure, however, it
did not alter the general trend of the findings (Figure S7, Sup-
porting Information).
To elucidate the intrinsic role of the final candidate, the Si
dopant, we comparatively analyzed the local electronic structure
of undoped and doped systems using Bader charge analysis,
as shown in Table S5 (Supporting Information). It is generally
accepted that the lithium-slab distance variation during del-
ithiation is affected by both the electrostatic repulsion between
oxygen planes and the screening effect of lithium ions.[54,60]
Upon delithiation, the lithium-slab distance increases with
growing electrostatic repulsion between oxygen-atom planes
because of the weakened lithium-ion screening. However,
at a high state of charge, the lithium-slab distance decreases
because of the weaker repulsion between oxygen layers with
lower electron density that is typically caused by the stronger
covalent metal–oxygen bonds at higher valence state of the
transition metal.[61–63] Bader charge analysis revealed that when
Si is doped in the structure, the loss of electron density in the
oxygen layers is notably suppressed at the highly charged state.
We observed that the average charge density of six oxygen
atoms bonded to Si dopants is relatively less affected by the del-
ithiation and remains higher than that bonded to nickel ions
in the undoped system (see Table S5, Supporting Information
for details). The relative invariance of the electron charge in the
oxygen layer for the Si-doped system can be partly attributed to
the electrochemical inactivity of Si ions, which does not change
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the bonding nature with oxygen upon delithiation unlike the
transition metal. The maintenance of the electrostatic repul-
sion between oxygen planes is expected to keep the lithium-
slab distance relatively stable even at high state of charge. We
also suppose that the high oxygen-vacancy formation energy
observed in the Si-doped system can be partially elucidated by
the modified charge distribution in the oxygen layer and the
corresponding metal–oxygen bond nature. It has been reported
that the ionic-bond strength is proportional to the effective
charge of both ions, and thus, the oxygen elimination could be
inhibited as the electron charge in the oxygen layer remains rel-
atively invariant.[54,55] This finding infers that the suppression
of the oxygen-vacancy formation in the Si-doped system can be
regarded as being the result of an enforced metal–oxygen bond
with a high effective charge of oxygen ions.
Inspired by theoretical investigations of the dopant effects,
we decided to experimentally validate the effectiveness of the
Si dopant as a model case in high-nickel NCM materials. Sil-
icon-doped LiNi0.92Co0.04Mn0.04O2 (Si-NCM9244) and undoped
LiNi0.92Co0.04Mn0.04O2 (NCM9244) were synthesized using co-
precipitation and a subsequent lithiation process, as described
in Methods. The high-resolution power diffraction (HRPD)
analysis in Figure S8 (Supporting Information) indicated
that both Si-NCM9244 and NCM9244 samples were obtained
without any noticeable impurities, showing that the diffrac-
tion patterns of both materials were well matched with those
of standard R3-m layered oxides.[27] (More details on the sample
characterization can be found in the Supporting Information
Discussion). First, we comparatively examined how the struc-
tural evolution occurs with delithiation of the two samples
using in situ X-ray diffraction and post-mortem SEM analysis,
as presented in Figure 4a,b, respectively. Figure 4a depicts the
shifts of the main (003) reflection of the layered structure for
the Si-NCM9244 and NCM9244 electrodes during the initial
charge process at a current rate of 0.2C in the voltage range of
2.5–4.4 V. The figure illustrates that the (003) reflection of the
NCM9244 electrode (left) gradually shifts to a low angle from
18.72 to 18.42°, indicating the expansion of the c-lattice para-
meter, and then abruptly shifts back to 19.48° at the end of the
charge (≈4.4 V vs Li/Li+). This shift to a higher angle implies
the drastic contraction of the c-lattice parameter at the end of
the delithiation. The tendency of the (003) reflection shift in the
Si-NCM9244 electrode (right) is analogous to that in NCM9244
from 18.72 to 18.42° during the initial delithiation process;
however, the shift to a high angle at the end of the charge is
less significant (18.42 to 19.32°). This finding clearly indicates
that the c-lattice parameter variation in the Si-NCM9244 elec-
trode was mitigated compared with that in the undoped system.
Accordingly, we performed cross-sectional SEM analysis for
both materials to verify its outcome on the formation of micro-
cracks induced after the repetitive anisotropic lattice variations.
Figure 4b shows that although the NCM9244 particles (upper
panel) had a densely packed morphology before cycling (inset),
a considerable amount of microcracks and voids were exten-
sively formed from the surface to the bulk after 50 cycles. In
contrast, fewer microcracks were formed in the Si-NCM9244
particles (bottom panel) after 50 cycles with relatively intact
primary particles, confirming the efficacy of Si doping in miti-
gating the anisotropic lattice strain.
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Figure 4. a) Charge/discharge profiles and in situ XRD patterns of NCM9244 (left) and Si-NCM9244 (right) electrodes during charging at
a current density of 0.2 C. b) Cross-sectional SEM images of secondary particles for NCM9244 and Si-NCM9244 before (inset) and after cycling
(100 cycles). c) Atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images of NCM9244 (left)
and Si-NCM9244 (right) after 50 cycles. FFTs of regions 1–3 in NCM9244 and Si-NCM9244 are described as below. d) Capacity retention of NCM9244
and Si-NCM9244 for 100 cycles at 0.3 C. e) Discharge capacities at different C-rates in NCM9244 and Si-NCM9244.

STEM analysis further revealed the suppression of transi-
tion-metal migration at the surface of the Si-NCM9244 elec-
trode compared with that of the NCM9244. The high-angle
annular dark-field (HAADF) images in Figure 4c display the
surface of NCM9244 (left) and Si-NCM9244 (right) particles at a
discharged state after 50 cycles. The fast-Fourier transformation
(FFT) results indicate that the original layered structure was
mostly retained in the bulk; however, the surface region under-
went a phase transformation with a substantial amount of
transition-metal migrations into the lithium layer. The diffrac-
tion spots from the rocksalt phases (yellow, cubic region) and
intermediate phases (green, intermediate region) containing
cubic and spinel phases were detected in both NCM9244 and
Si-NCM9244 particles. However, the thickness of the recon-
structed surface regions was markedly more extensive in the
NCM9244 than in Si-NCM9244, indicating that transition-metal
migration/oxygen evolution at the surface could be suppressed
by the Si doping in the high-nickel layered material.
Finally, we comparatively examined the electrochemical
activity and stability of the Si-NCM9244 and NCM9244 elec-
trodes, as shown in Figure 4d and Figure S10 (Supporting
Information). At a current rate of 0.1C, the Si-NCM9244
and NCM9244 electrodes delivered first cycle capacities of
223.8 and 228.5 mA g−1, respectively, in the voltage range of
2.5–4.4 V (vs Li/Li+). The slightly lower discharge capacity
of the Si-NCM9244 electrode may stem from the substitu-
tion of the electrochemically inactive Si dopant. Figure 4d
shows the capacity retention of both electrodes at a current
rate of 0.3 C. The Si-NCM9244 electrode retained a capacity
of 157.15 mA h g−1 after 100 cycles, corresponding to a
capacity retention of 75.2%, exceeding that of the NCM9244
electrode under the same conditions (138.03 mA h g−1
(≈66.9% retention)). In Figure 4e, the rate performances of
the Si-NCM9244 and NCM9244 electrodes are compared.
Notably, the Si-NCM9244 electrode could retain a higher
capacity (149.5 mA h g−1) even when the current density
increased to 2 C, in contrast to the significant capacity
drop of the NCM9244 electrode at the same current density
(114.4 mA h g−1). This improved electrochemical performance
of the doped system can be attributed to enhanced structural
stability against microcrack formation and cation disordering,
as previously discussed in the dopant screening process sec-
tion, and the corresponding suppression of side reactions in
the electrochemical cell, which confirms the validity of our
theoretical dopant screening process.
It is noteworthy that although we have selected one final
dopant candidate, Si, in our selection process, which consid-
ered three major aspects, other dopants that were marginally

Adv. Energy Mater. 2022, 12, 2200136 2200136 (6 of 9) © 2022 Wiley-VCH GmbH

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screened out should not be completely ruled out for practical
applications. Certain dopants could outperform Si in some
aspects, e.g., the Zr dopant in reducing lattice strain or the Al
dopant in suppressing oxygen gas. Considering that the three
major aspects would not have equal contributions to the degra-
dation of high-nickel NCM electrodes, more weighted selection
criteria may make the final choice of dopant different than Si.
Furthermore, beyond our three criteria, there are other aspects
such as microstructure control or coatings that have been
known to be beneficial in high-nickel NCM electrodes. These
aspects are closely related to the surface properties (e.g., surface
energy and lattice parameters at the interface), however, our
dopant selection map that revealed the intrinsic properties of
dopants on crystallographic/electronic structure will also give
the intuition on designing the better-engineered surface. More-
over, we believe that this basic information about dopant effects
can be extended to multi-dopant strategies. Taking advantage
of different single dopants with their unique characteristics,
optimal combinations of several dopant species can be incor-
porated into high-nickel NCM electrodes for practical purposes.
In this regard, the dopant map provided in Figures 2 and 3, and
Figure S1 (Supporting Information) can serve as an effective
guidebook for future endeavors.
3. Summary
Potential dopant candidates that can improve the electrochem-
ical performance of high-nickel NCM (LiNixCoyMnzO2, x ≥ 0.9)
were comprehensively investigated by applying a systematic
theoretical stepwise pruning process. From the three criteria of
mitigating anisotropic lattice collapse, reducing oxygen-gas evo-
lution, and suppressing cation mixing, a total of 38 elements
were sequentially screened, with silicon finally selected as a
model dopant for further experimental verification. Theoretical
analysis revealed that the silicon doping suppresses contraction
of the lithium-slab distance at a high state of charge, thereby
alleviating the c-lattice parameter shrinkage, and reduces
oxygen–gas evolution while inhibiting nickel-ion migration.
Experimental verification revealed that the Si-doped NCM9244
exhibited significant improvement in the electrochemical
stability and activity, which was attributed to the decrease in
secondary-particle cracking during repeated cycling and the
accompanying suppression of the side reactions. Although our
model case presented here is limited to one final dopant for
experimental verifications, we believe that our map of dopant
efficacy and theoretical stepwise pruning and validation proce-
dures can be more extensively utilized as rational guidelines
for the exploration of effective dopants for high-nickel NCM
electrodes.
4. Experimental Section
First-Principles Calculations: First-principles calculations based on
DFT with the projector augmented wave (PAW)[64,65] method were
conducted using the Vienna Ab Initio Simulation Package (VASP).[66]
The spin-polarized generalized gradient approximation (GGA) with
the Perdew–Burke–Ernzerhof (PBE) exchange-correlation model was
used as a reference for the lattice-parameter calculation.[67] Because
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of the self-interaction error and lack of van der Waals (vdW) force in
the GGA exchange functional, the vdW-density functional based on
nonlocal exchange-correlation was also adopted (optPBE, optB88, and
optB86b).[68,69] A plane-wave basis set with a kinetic energy cut-off of
500 eV and 2 × 2 × 1 k-points grid based on the Monkhorst–Pack scheme
were utilized after performing the convergence test.[70] All the structures
were fully relaxed until the residual force in the unit cell converged to
within 0.02 eV Å−1. Next, 2 × 2 × 1 supercells containing 12 formula units
of the LiNiO2 structures (space group: R3-m) were applied (Li12Ni12O24,
48 atoms). In total, 38 dopants were considered as substitutes for
one nickel ion in the supercell (Li12Ni11M1O24, M = dopant). Although
determining the favorable crystallographic site of dopants remains a
significant issue, it was assumed that the dopants replace nickel ions in
the octahedral sites in the transition-metal layer to expedite the pruning
process on the basis of extensive previous works.[28,30,71,72] The lithium-
vacancy ordering configurations with the lowest electrostatic energies
were enumerated using the Ewald summation method for each lithium
concentration.[73] Lattice expansion and contraction were depicted as the
c-lattice parameter variation as a function of the lithium concentration.
A supercell with composition Li2Ni11M1O24 was selected to reflect the
high state of charge in which oxygen gas was evolved, and the oxygen-
vacancy formation energy The oxygen-vacancy formation energy Ef(Vo)
was defined as
1
E f (Vo ) = E (Vo ) − E (pristine ) + E ( O 2 ) , (1)
2
where E(Vo) and E(pristine) are the total energies of the oxygen-
deficient and pristine structure, respectively. Because the chemical
potential of oxygen gas is dependent on the temperature and because
DFT overestimates the oxygen binding energy, the chemical potential
of oxygen was adopted, calculated to be 8.99 eV per molecule at room
temperature.[58] The nickel-ion stability was considered as the site-energy
difference between octahedral sites in the transition-metal layer and
tetrahedral sites in the lithium layer.[56,57] Because nickel-ion migration
was also sensitive to the local lithium environment, the lithium
configuration for each lithium concentration was fixed and the energy
differences for all possible sites were estimated.
Material Synthesis: LiNi0.92Co0.04Mn0.04O2 (NCM9244) was prepared
by coprecipitation and a subsequent solid-state method. The
Ni0.92Co0.04Mn0.04(OH)2 hydroxide precursor was synthesized using the
co-precipitation method with NiSO4⋅6 H2O (Daejung Chemical Co.),
CoSO4⋅7 H2O (Daejung Chemical Co.), MnSO4⋅H2O (Daejung
Chemical Co.), NaOH (Daejung Chemical Co.), and NH4OH (Daejung
Chemical Co.) as starting materials. The homogeneously mixed solution
(Ni:Co:Mn = 92:4:4 in molar ratio) was fed into a batch reactor containing
a solution of NH4OH (aq) and NaOH (aq) under an N2 atmosphere.
Next, NaOH (molar ratio of NaOH/TM = 2.0) and NH4OH as chelating
agents (molar ratio of NH4OH/TM = 1.2) were pumped separately into
the reactor. The precursor powder was obtained by filtering, washing,
vacuum drying, and precipitating at 110 °C for 12 h. The precursor was
hand-mixed with LiOH·H2O (molar ratio 1:1.03) and annealed at 740 °C
for 12 h with oxygen gas flow.
For Si-NCM9244, first, the hydroxide precursor was coated with
a silicon source using tetraethyl orthosilicate (Sigma–Aldrich) and
acetylacetone (Sigma–Aldrich). Tetraethyl orthosilicate and acetylacetone
(1:4 mole ratio) were mixed in dehydrated ethanol and stirred for 30 min.
Then, hydroxide powder (Si:NCM = 1:99 mole ratio) was subsequently
added and mixed for 30 min and dried at 100 °C overnight. Finally,
Si-NCM9244 was prepared by mixing the silicon-coated precursor with
LiOH·H2O (molar ratio of 1:1.03) followed by calcination at 740 °C for
12 h with oxygen flow.
Structural Characterization: The crystal structure was determined using
synchrotron radiation powder X-ray diffraction (HRPD) data collected
from the 9B HRPD beamline at the Pohang Accelerator Laboratory
(PAL). The FullProf program was used for the Rietveld refinement. An
X-ray diffractometer (R-AXIS IV, RIGAKU) was used to monitor the phase
transformation during the charge process for in situ XRD analysis. In
© 2022 Wiley-VCH GmbH

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detail, a modified coin cell with a 3 mm hole at its center sealed with
mylar film was used while the cells were charged up to 4.4 V versus Li/Li+
at a current density of 0.2 C. High-resolution STEM images were obtained
using a double aberration-corrected JEOL-ARM 200CF microscope with
an acceleration voltage of 200 kV. The cross-sectional TEM and SEM
specimens were prepared using a FIB (Helios Nano Lab450, FEI) and
cross-section polisher (IB-19510CP, JEOL), respectively.
Electrochemistry: The electrochemical properties of the half-cells were
measured using 2032 coin-type cells (Welcos, Korea). To prepare the
electrodes, the obtained NCM9244 powder was mixed with Super-P and
polyvinylidene fluoride (PVDF) binder (weight ratio 85:8:7) in N-methyl-
2-pyrrolidone (NMP) solvent and then cast on Al foil and dried. The cell
was assembled with lithium-metal foil as a counter electrode, a separator
film (Celgard), and an electrolyte of EC: EMC (3:7 v/v) dissolved with
LiPF6 (1.2 M) salt. The cells were cycled using an automatic battery
cycler (WBCS 3000S WonATech) in the voltage range of 2.5–4.4 V vs Li/
Li+. The current density of 1 C represents 200 mA g−1.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded by
the Ministry of Education (2020R1A6A3A13070145). This work was also
supported by the Center for Nanoparticle Research at Institute for
Basic Science (IBS) (IBS-R006-A2) and the National Supercomputing
Center with supercomputing resources including technical support
(KSC-2016-C3-0069).
Conflict of Interest
The authors declare no conflict of interest.
Author Contributions
D.-H.K., J.-H.S., and C.-H.J. contributed equally to this work. D.-H.K.,
J.-H.S., S.-H.H., and K.K. designed the project. D.-H.K., and J.-H.S.
conducted the DFT calculations. D.-H.K., J.-H.S., and B.K. analyzed the
calculation results. C.-H.J., and D.E. carried out the synthesis, structural
characterization, and electrochemical test. B.K. provided constructive
advice for the calculation designs and results. J.-H.S., D.-H.K., and K.K.
wrote the manuscript, and K.K. supervised all aspects of research.
Data Availability Statement
The data that support the findings of this study are available in the
supplementary material of this article.
Keywords
chemo-mechanical degradation, density functional theory, doping, high-
nickel NCM cathodes, layered cathode materials
Received: January 12, 2022
Revised: February 22, 2022
Published online: March 23, 2022
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