Electronic structure formed by Y2O3-doping in lithium position assists improvement of charging-voltage for high-nickel cathodes

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Article https://doi.org/10.1038/s41467-024-52768-7
# Electronic structure formed by Y2O3-doping in lithium position assists improvement of charging-voltage for high-nickel cathodes

Received: 24 March 2024

Accepted: 18 September 2024

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Shijie Wang 1, Kang Liang 1, Hongshun Zhao 1, Min Wu 1, Junfeng He 1, Peng Wei 1,
Zhengping Ding 1, Jianbin Li 1, Xiaobing Huang 2 & Yurong Ren 1

High-capacity power battery can be attained through the elevation of the cutoff voltage for LiNi0.83Co0.12Mn0.05O2 high-nickel material. Nevertheless,
unstable lattice oxygen would be released during the lithium deep extraction.
To solve the above issues, the electronic structure is reconstructed by substituting Li + ions with Y 3+ ions. The dopant within the Li layer could transfer
electrons to the adjacent lattice oxygen. Subsequently, the accumulated
electrons in the oxygen site are transferred to nickel of highly valence state
under the action of the reduction coupling mechanism. The modified strategy
suppresses the generation of oxygen defects by regulating the local electronic
structure, but more importantly, it reduces the concentration of highly reactive Ni 4+ species during the charging state, thus avoiding the evolution of an
unexpected phase transition. Strengthening the coupling strength between
the lithium layers and transition metal layers finally realizes the fast-charging
performance improvement and the cycling stability enhancement under
high voltage.

High safety and sustainability are needed for lithium-ion batteries
(LIBs) to promote their practical application in the fields of power,
energy storage, and consumption. Particularly, layered LiNixCoyMn1-x
y O 2 (x ≥ 0.6) with valuable attributes such as high capacity, high vol-
tage, and environmental friendliness is a promising cathode for electric vehicles (EVs) 1 . At present, in pursuit of higher specific capacity and
lower costs, LiNi0.83Co0.12Mn0.05O2(NCM) has been produced on a
large scale and appeared on the market. High nickel ternary material
can achieve higher specific capacity by increasing the charging cut-off
voltage to meet market demand for battery life. However, the poor
structure and thermal stability of high-nickel materials, along with the
increase in Ni concentration, lead to the degradation of electrochemical properties. Specifically, the high activity of Ni 4+ could consume the electrolyte and form a thick and uneven cathode-electrolyte
interface (CEI) film, increasing the diffusion resistance of the Li + ion.
The inhomogeneous Li + ion distribution could accelerate the formation of intergranular cracks due to heterogeneous internal strain 2,3 .

Significantly, the irreversible phase transition of H2-H3 also aggravates
the intergranular microcracks under primary grain expansion and
contraction 4 . Moreover, undesired losses of lattice oxygen are also
caused by charging under the high cut-off voltage. The release of
oxygen not only raises the risk of thermal runaway but also lowers the
valence state of active nickel. This reduction in valence state may
facilitate the migration of nickel ions to the octahedral site in the
lithium layer, as both Ni 2+ and Li + ions have similar ionic radii 5,6 . TM
segregation would initiate local phase transitions and block the diffusion channels of Li + ions 7 . Overall, transition metal ions and lattice
oxygen exhibit complex coupling effects in thermal and high-chargingvoltage fields due to their strong covalence. As is well known, lattice
oxygen is the supporting framework in various layered oxide materials.
Therefore, any modification measure cannot only focus on the irreversible behavior of transition metal ions.

In previous studies, the stability of transition metalions and lattice
oxygen in high-nickel materials has been improved by a cooperative

1School of Materials Science and Engineering, Changzhou University, Changzhou, People’s Republic of China. 2School of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde, People’s Republic of China. [e-mail: ryrchem@cczu.edu.cn](mailto:ryrchem@cczu.edu.cn)

strategy of lattice doping and surface coating 8,9 . The common dopants
include oxides, fluoride 10, and hydrate 11 . Taking Y2O3 as an example, to
stabilize the layered structure, the substituted Y 3+ ions at the transition
metal sites provide stronger Y-O bond energy 12 . Another benefit of
doping Y 3+ ions is the increase in initial nickel valence state, thus
reducing the Li + /Ni 2+ mixing 13 . In addition to being used as a dopant,
Y2O3 can form an ultrathin coating that reduces interface impedance
and prevents electrolyte erosion 14 . Similarly, other 4d transition metal
elements show great potential. Nb substituted the transition metal
position, and effectively inhibited oxygen release under the role of
high dissociation energy in the Nb-O bond 15 . Considering the characteristics of high-valence metals, molybdenum atoms have become
common dopants in the modified strategy of high-nickel materials 16 . It
is worth noting that the Mo-substitution strategy could suppress the
generation of microcracks by eliminating the local compositional
inhomogeneity. Although these high-valence metals exploit their
advantages to the full, their rarity limits the scale of industrial production. No matter what the dopant within the transition metal layer
led to a decrease in electrochemically active components.

Recently, there has been a deep understanding of the
improvement of surface structure by synthesizing functional coatings. For example, the LiF&FeF3 coating increases the formation
energy of oxygen vacancy and slows down the release of lattice
oxygen 17 . Moreover, the doping strategy of F - or Cl - at the O site have
also been widely studied 18,19 . Specifically, F - ions can optimize the
band structure of high nickel materials. Meanwhile, the presence of
F- ions promotes the formation of cationic ordered structures caused
by the alternating occupation of lithium ions and transition metal
ions 10 . However, introducing negative ions into the structure would
decrease the valence state of nickel or increase the concentration of
oxygen vacancy, which is not conducive to structural stability. At
present, great efforts have been made to optimize the initial structure of the high nickel materials, but little attention has been paid to
the effect of dopants on the structure change in deeply charged
states.

To improve the stability of lattice oxygen and make full use of its
reversible redox, we proposed an Y 3+ -O 2- -Ni 4+ electron cloud coupling
strategy to address this issue. It was worth mentioning that Y 3+ ions can
substitute for the Li + sites. The reconstructed electronic structure can
promote the transfer of electrons to oxygen. Specifically, orbital
hybridization can be formed between Y 3d and O 2p bands, which
causes plenty of electrons to transfer from the dopant site to the
adjacent oxygen site. And then, the accumulated electrons on the
oxygen site were further transferred to the highly oxidizing Ni 4+ at high
voltage. The mechanism not only enhanced the redox reversibility of
lattice oxygen, but also reduced the concentration of high-activity
nickel. Ultimately, the improvement in the coordination environment
of nickel effectively prevented the loss of oxygen and the irreversible
behavior of transition metal ions. This work reveals the role of Y 3+ in
stabilizing surface structures and provides guidelines for the design of
cathode materials with high specific energy.

Results
Characterizations of Y2O3-modified strategy
Figure 1a shows the synthesis process of the Y2O3-modified sample,
and a schematic involving a double safeguard strategy resulting from
Y 3+ -O 2- -Ni 4+ electron cloud coupling. In Fig. 1b, all the diffraction
peaks were indexed to the R-3m space group of the layered structure.
In the magnified XRD pattern, it was noted that the diffraction peaks
of (003) crystal pane were obviously shifted after introducing Y2O3
(Fig. 1c). Considering that Y 3+ ions could enter the lattice, the XRD
pattern by Rietveld refinement of NCM and NCM@Y-2 was studied
(Fig. S1). The homologous analysis data are presented in Fig. S2. It is
found that the c axis of NCM increases gradually with increasing Y2O3
concentration, which causes an increase in cell volume (Fig. S2a, b).

The increase in interlayer spacing has a certain effect on the
improvement of lithium diffusion 20,21 . Moreover, a ratio of c/a and
I(003)/(104) reflected the ideality of the layered structure and the
degree of cation mixing, and their values were usually higher than
4.93 and 1.2, respectively 22 . It is worth noting that all of the samples
showed higher values of c/a and I(003)/(104) except for NCM (Fig. S2c,
d). In Table S1, the degree of Li + /Ni 2+ mixing in refined result for
NCM@Y-2 sample was lower than additional Y-modified samples.
The undesirable crystal structure caused by Y2O3 excess could have a
negative impact on electrochemical performance, causing increase
in Li + /Ni 2+ mixing. According to the formula S1 and S2, the slab
thickness of transition metal (STM) and the interslab space thickness
of Li (ILi) were calculated 23 . As shown in Table S1, the value of ILi
changed obviously after the Y2O3 modification. The increased interslab space could shorten the thickness of the [MO6] octahedron
(M=Mn/Co/Ni) and decrease the length of the M-O bond, thus
improving the structural stability 24 . X-ray photoelectron spectroscopy (XPS) analyses of Y 3d, O 1s, C 1s, and Ni 2p were carried out to
detect the chemical valences of relevant elements of NCM and
NCM@Y-2. In Fig. S3, the main peak at 284.8 eV was corresponded to
the conductive carbon 25 . Two other peaks at the binding energies of
288.4 and 289.8 eV were found, corresponding to the bonds of C=O
and Li2CO326. The existence of lithium carbonate may seriously

threaten cycling stability and safety properties. Contrasting the
Li2CO3 concentrations of two samples, it was noted that the bare
sample was slightly higher than the modified sample. As for O 1s
spectra, only lattice oxygen (530.3 eV) was detected in NCM@Y-2,
while more lithium carbonate (531.8 eV) was detected in the bare
sample (Fig. S4) 27 . In addition, Fig. S5 shows the oxidation state of Ni
elements containing Ni 3+ (binding energies of 855.8 and 873 eV) and
Ni 2+ (binding energies of 854.5 and 871.9 eV) 28 . The increased concentration of Ni 2+ in the bare sample might cause undesirable Li + /Ni 2+

mixing 29 . More importantly, the bonds of 157 and 159 eV were
detected in NCM@Y-2, corresponding to Y 3d5/2 and Y 3d3/2,
respectively (Fig. S6) 30 . By contrast, no oxidation state of the Y element was detected in the bare sample, further revealing the presence
of Y in NCM@Y-2.

To further monitor the interface structure, scanning electron
microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) were carried out. As shown in Fig. S7, the morphology
of the secondary particles did not change with the addition of Y2O3.
Figure 1d shows the (003) crystal plane and a coating thickness of
~2 nm in NCM@Y-2. The TOF-SIMS result demonstrated that the element Y was distributed in the surface of secondary particle cross
section (Fig. 1e). Meanwhile, as shown in Fig. S8, pure LiYO2 could be
obtained by adding the raw materials of Y2O3 and LiOH into the system
under the same sintering environment, further demonstrating that Y 3+

ions could be enriched on the particle surface and form a LiYO2
coating. To ensure the presence of Y 3+ ions in the bulk, a line scan test
was performed from the outside to the inside of the particles in Fig. 1f.
The strength of Y and O atoms was first increased before the strength
of transition metal atoms was increased (Fig. 1g). The Y concentration
gradually decreased until the depth of 400 nm. Due to the particle size
of secondary particle were about 6～8 μm, the concentration of transition metals in the front position of line scan kept increasing. The
above results demonstrated the existence of Y 3+ both in the bulk and
on the surface of secondary particles. To confirm that Y 3+ occupies the
lithium position, aberration corrected transmission electron microscopy was used. The ordered bright spot represents a transition metal
atom in the high-angle annular dark-field (HAADF) mode (Fig. 1h) 31 . It is
worthing that a strong bright spot can be observed in the lithium layer
of the Y-modified sample. Furthermore, the increase in layer spacing
indicated that the Y atom occupies the 3a site for the lithium atom
(Fig. 1i). The above result clearly verifies the reliability of the XRD
refinement results.

Fig. 1 | Physical characterizations of Y2O3-modified strategy. a Synthesis schematic and modification mechanism. b, c XRD pattern and selected range image of
NCM and NCM@Y-2. d The high-resolution TEM of NCM@Y-2. e TOF-SIMS image of

Interlayer coupling mechanism
To reveal the effect of interlayer coupling mechanism for transition
metal layer and Li layer, X-ray absorption near-edge structure (XANES)
in NCM and NCM@Y-2 during the first cycle were collected. As shown
in Fig. 2a, b, the Ni-edge position of both samples shifted to higher
energy under a full-charging state, which means that the valence state
of Ni was elevated 32 . Then, the Ni-edge position returned to low energy
with the reduction of Ni during the discharge state due to the local
electron exchange effect, indicating that Ni 2+/3+ was involved in a redox
reaction. Significantly, the energy difference of 1.41 eV for the
NCM@Y-2 sample mean that the valence state of nickel was relatively
small under the charging state. It was mainly because the plenty of
electrons in high-charge-density YO6 octahedron further transferred
to the high activity of Ni 4+ . Therefore, the coupling of Y 3+ -O 2- -Ni 4+

electron cloud improved the coordination environment of nickel.
Additionally, the Ni edge positions of the discharge state and the
pristine state were well-overlapped in NCM@Y-2, demonstrating the
surface oxygen was stable 33 . Soft X-ray adsorption spectroscopy
(sXAS) of O K-edge was employed to study the electronic structure
changes of oxygen. Figure 2c, d show O K-edge spectra detected by
TEY (total electron yield) mode. After being charged to 4.5 V, an abrupt

cross section for NCM@Y-2. f, g TEM line scanning result for NCM@Y-2. STEMHADDF image of (h) NCM and (i) NCM@Y-2 and their corresponding
intensity plots.

peak appeared at the photon energy of ~530.8 eV, which represents the
redox reaction of O 2- ions being activated 34 . In sharp contrast, the
relating peak in Y-modified sample became stronger than that of the
NCM, indicating more anions were oxidized to participate in charge
transfer under overcharge conditions (Fig. 2d). Even if discharged to
2.75 V, the Y-modified sample still retained certain a reversibility of
anions.

The Fourier transformed extended X-ray absorption fine structure
(EXAFS) has better sensitivity to the local coordination information of
Ni-edge. From Fig. 2 e, f, the first peak observed in the range of 1~2 Å
was related to the oxygen around the transition metal (Ni-O), while the
second peak in the range of 2~3 Å was related to the bonds between the
transition metal (Ni-TM) 17,35 . The Ni-O bond length of the two samples
in the final state of charging was obviously shortened, and the Ni-O
bond length was recovered in the subsequent discharging reaction.
However, comparing the amplitude and strength of Ni-O and Ni-TM
bonds in the initial state and discharging state, the coincidence degree
of the bare sample was obviously lower than that of the Y-modified
sample. In general, the change was attributed to the movement of
Ni 3+ O6 octahedra due to the existence of Jahn-Teller active Ni 3+ ions 36,37 .
The results show that the Y-modification strategy can effectively

Fig. 2 | Interlayer coupling mechanism. Ex situ XANES spectra of Ni K-edge for (a)
NCM and (b) NCM@Y-2 during the first cycle. Ex situ sXAS spectra of O K-edge for
(c) NCM and (d) NCM@Y-2. Ex situ Ni K-edge EXAFS of (e) NCM and (f) NCM@Y-2

restrain transition metal migration caused by Jahn-Teller distortion
and improve the cation order in transition metal layer. Similarly, for
the wavelet transform (WT) of the k3-weighted EXAFS signal in
NCM@Y-2, there was obviously no change in the intensity and position
of Ni-O in pristine and discharge states when compared with the
coordination environment in which the Ni of NCM was markedly different (Fig. 2g, h) 17,38 . The results of EXAFS further confirmed that the
coupling of Y 3+ -O 2- -Ni 4+ electron cloud enhanced the stability and reusability of Ni during the charge-discharge process.

during the first cycle. Ni K-edge EXAFS WT images of (g) NCM and (h) NCM@Y-2
during the first cycle.

Electrochemical characterization
To verify the enhanced lithium-ion diffusion kinetics after Y2O3 modification, the cycling tests under high cut-off voltage were performed
on NCM and NCM@Y-2. Figures 3a and S9, shows that NCM@Y-2
delivered a high specific discharge capacity of 228 mAh·g −1 at 0.1C and
a coulombic efficiency of 89.5%, while that of NCM had only a relatively
specific discharge capacity of 221 mAh·g −1 and a coulombic efficiency
of 91.3%. The improvement in specific capacity was attributed to the
enhanced stability of the surface structure and the decrease in residual

Fig. 3 | Electrochemical performance. a Charge-discharge profile of NCM@Y-2
under different rate. b Rate performance of NCM, NCM@Y-1, NCM@Y-2, NCM@Y3. c Cycling performance of NCM, NCM@Y-1, NCM@Y-2, NCM@Y-3 under highvoltage of 4.5 V. d Voltage profile of NCM and NCM@Y-2. e calculated dQ/dV curves

lithium 39 . The reduction in columbic efficiency of NCM@Y-2 could be
related to lithium loss due to SEI film formation at high voltages. The
three pairs of redox peaks containing phase transitions from hexagonal to monoclinic (H1-M), monoclinic to hexagonal (M-H2), and
hexagonal to hexagonal (H2-H3) were observed in the cyclic voltammetry (CV) curves (Fig. S10) 40 . The reversibility of NCM@Y-2 was
higher than that of NCM after the initial charge/discharge, indicating
that the structural stability of high-nickel material was improved after
introducing Y2O3 in the system. In addition, a relatively small voltage
difference of 0.156 eV in NCM@Y-2 proved reduced polarization with
Y2O3 modification. Figure 3b shows the different discharge capabilities
at various rates of 0.1, 0.2, 0.5, 1, 2, 5, and 10 C under the range of
voltage from 2.75 V to 4.5 V of four samples. As for the NCM sample,
the discharge specific capacity continued to decrease as the cycle
number increased, especially at 10C, exhibiting only a lower discharge
specific capacity of 99 mAh·g −1 . In comparison, the capacity decay in
NCM@Y-2 was relatively slow and delivered a higher discharge specific
capacity of 145 mAh·g −1 at 10C. The improvement in rate performance
was attributed to the avoidance of undesirable phase transitions in the
bulk by Y 3+ -O 2- -Ni 4+ electron cloud coupling, and the construction of a
fast migration channel for Li + ions on the interface due to the LiYO2
coating’s stronger chemical bond with the particle surface.

during 200 cycles of NCM and NCM@Y-2. f Cycling stability test under the
high-temperature. g Fast-charing performance of NCM and NCM@Y-2. h A literature survey of the cycle number, rate, and capacity retention for various
half battery.

Except for the remarkably improved rate performance, the
cycling stability of NCM@Y-2 was also significantly enhanced. As
shown in Fig. 3c, comparing the NCM@Y-2 to the NCM which has a
reversible capacity of 200 mAh·g −1 and a capacity retention of 65%
after 200 cycles, the NCM@Y-2 showed a greater discharge capacity of
211 mAh·g −1 and enhanced cycling stability of 86% capacity retention.
Irreversible structural degradation usually results in voltage decay,
especially at high voltages. As shown in Fig. 3d, NCM@Y-2 maintained
a low voltage decay of 0.03 V compared to NCM, which revealed that
Y 3+ could stabilize the lattice oxygen and restrain the unfavorable
transformation of the layered to spinel or rock salt phase in the surface
structure. Besides, the dQ/dV curves were produced using the charge/
discharge profiles from 1st to 200th (Fig. 3e). It was clear that the
irreversibility of the redox peak was reduced in the NCM@Y-2, further
demonstrating that Y2O3-modified material could improve structural
stability. Especially at test environment of 55 °C, NCM@Y-2 could
produce a highly reversible capacity of 210 mAh·g −1 and enhance
cycling stability with of 84% capacity retention after 100 cycles. Such
well high-temperature performance demonstrated that the LiYO2
coating not only resisted corrosion from the electrolyte but also provided thermal insulation. The advantage of the Y2O3-modification
strategy was also shown in the cycling stability at 5 C of two samples.

The discharge specific capacity of 156 mAh·g −1 in the NCM@Y-2
remained 135 mAh·g −1 after 400 cycles (Fig. 3g). More importantly, the
superiority of the Y2O3-modified strategy in long-cycle performance
was demonstrated. (Fig. 3h and Table S2). Moreover, the Y-modified
sample as cathode was also assembled in the coin full-cell. It was worth
that the results show that the Y-modified strategy had practical
application value (Fig. S11).

The GITT test and the CV test with different scan rates were
conducted to deeply investigate the effects of LiYO2 coating and Y 3+

doping on lithium-ion diffusion kinetics. Comparing the data on DLi
calculated by Formula S3, the NCM@Y-2 maintained a higher value of
DLi than the bare sample (Fig. S12) 41 . Similarly, the higher value of DLi
from CV testing in the Y2O3 modified sample was consistent with GITT
results, further accounting for the enhanced lithium-ion diffusion
kinetics by the Y2O3 modification strategy (Fig. S13 and Table S3).
Moreover, the role of Y2O3 modification in NCM@Y-2 was also evaluated by electrochemical impedance spectroscopy (EIS). Two semicircles of high /middle frequency and a straight line of low frequency
were observed in the impedance patterns, corresponding to interfacial
film resistance (Rf), charge-transfer resistance (Rct), and Warburg
impedance (Wo) (Fig. S14a) 42 . All impedance values were fitted by an
equivalent circuit, and the results are shown in Fig. S14b. Significantly,
the value of Rct in NCM@Y-2 on the 1st and 100th cycles were lower
than that of NCM, demonstrating that LiYO2 coating effectively reduces the interface impedance. Moreover, the improved Li + ion diffusion
coefficient in NCM@Y-2 was calculated by Formulas S5 and S6, consistent with the results of GITT and CV. (Fig. S14c, d).

Gas evolution process and phase transition
Considering the effect of Y 3+ on the structure, differential electrochemical mass spectrometry (DEMS) was further used to investigate
the gaseous reactants of NCM and NCM@Y-2. The oxidation of oxygen, while slightly increasing the energy density of high-nickel material, can exacerbate the irreversible loss of layered structures, such as
the migration into the Li layer or dissolution at the interface of
transition-metal ions. It was well known that electrolytes (e.g., EC
species) undergo intense electrochemical oxidation at high potentials
above 4.6 V, which drives the release of CO243,44. As shown in Fig. 4a, a

similar gas evolution trend of CO2 in both samples at a voltage of 4.7 V
was observed. For O2 release, there was no oxygen evolved below the
normal cutoff voltage (4.3 V). At the following voltage value of around
4.7 V, the emergence of oxygen was related to the 2p state of O as it
approached the Fermi level under high voltage 45,46 . The released oxygen from the lattice would promote the chemical oxidation of the
electrolyte and generate more CO247. It was precisely because of the

gas evolution of oxygen in the bare sample that there was a difference
in CO2 concentration between the two samples. Thus, the smaller CO2
peak value signifies that the Y2O3-modified strategy can effectively
anchor lattice oxygen to avoid structural degradation. Meanwhile, the
result was also confirmed by the electron paramagnetic resonance
(EPR) test (Fig. S15). Figure 4c, d shows the O K-edge and Ni L-edge
spectra by testing soft X-ray absorption spectroscopy (sXAS). The preedge region (light-green rectangular), and the energies of ~535 eV
(light-yellow rectangular) were detected in cycling-NCM and cyclingNCM@Y-2, corresponding to TM 3d-O 2p hybridized states and lithium
carbonate, respectively 48,49 . It was clear that a signal of relatively less
lithium carbonate and more oxygen signal was observed in the
NCM@Y-2. In Ni L-edge spectra, the surface of the cycling NCM sample
contained more Ni 2+, which was not conducive to the stability of the
layered structure 50 . The XRD tests were performed for cycled samples
(Fig. S16). As shown in Table S4, the lower degree of Li + /Ni 2+ mixing in
the cycled NCM@Y-2 proved that ordered structure was maintained
effectively. In addition, the in-depth XPS test was used to detect the
deeper chemical composition. The O 1s spectra exhibited two distinct
peaks, which may be attributed to the presence of lattice oxygen and

the band associated with the dissolution of the electrolyte (C=O bond)
(Fig. 4e, f) 51 . The fitting results show that the lattice oxygen concentration on the surface of the bare sample was relatively less than
that of the Y2O3-modified sample, and the growth rate was also kept at
a low level. In the Ni 2p spectra, it was noted that the concentration
difference on the surface of NCM between Ni 2+ and Ni 3+ was not
obvious. The higher concentration of Ni 3+ gradually appeared after
etching into the bulk (Fig. 4g, h). As for NCM@Y-2, although the Ni 2+

concentration on the surface was higher than that of NCM, the ratio of
Ni 2+ /Ni 3+ decreased more rapidly as the etching depth increased,
revealing that the irreversible phase transition in the surface-to-bulk of
second particles was inhibited under the charge supplement
mechanism of Y 3+ ions, thus improving the structure stability of highnickel material.

Structure and interface stability
To assess the effect of Y2O3-modification on phase transition, in-situ
XRD analysis was performed during the first charge-discharge process. Figure 5a shows that the (003) peak first migrated to a small
angle as the charge reaction progressed (voltage below 4.2 V). This
was mainly because Li + extracted from the lithium layer caused
increased repulsion in the oxygen layer 11,52 . As the voltage exceeded
4.2 V, the shift of the (003) peak toward a higher 2θ was observed
due to the transfer of electrons from the lattice oxygen to the highly
oxidized nickel, and the resulting sharp contraction of the transition
metal layer spacing occurred 38 . In Figs. S17 and 5b, a higher peak shift
(1.31°), maximum contraction in the c-axis lattice (5.4%), and a larger
lattice volume change (8%) were observed in the NCM, which led to
particle breakage and a rapid decrease in capacity under severe
stress accumulation 53 . As for NCM@Y-2, in addition to reducing the
charge depletion of oxygen anions, the modified strategy also alleviated the large electrostatic repulsion interaction due to the
decrease in the concentration of highly reactive Ni 4+ species. Time-offlight secondary ion mass spectrometry (TOF-SIMS) was utilized in
study the distribution of surface species of NCM and NCM@Y-2 after
200 cycles (Fig. 5c, d). The organic fragments from CH2+ represented
the decomposition of carbonate solvents. LiO + and LiF − fragments
derives from Li2O and LiF precipitates from decomposition of lithium
salts 54 . A NiF3− fragment was identified in relation to the product from

the reaction of transition metal with HF on the surface 55 . In general,
the half-strength of fragment normalization could evaluate the
thickness of CEI film 56 . By contrast, the thickness was obviously
reduced in the Y-modified sample. To prove the superiority of the
Y2O3-modified strategy, TEM tests were performed on the two electrodes after long-term cycle. The thickness of CEI film was distinctly
different between the cycled electrodes at the different cycle numbers (Fig. S18). Moreover, low by-product concentration in
Y-modified sample from 3D reconstruction and chemical images
demonstrated that the cathode-interface degradation reactions
induced by interface corrosion were effectively alleviated. The significant differences in the concentration of all species further support that view (Figs. S19, S20).

In the SEM images after long-term cycling, it was clear that the
second particle in the NCM sample contained an irreversible crack. In
contrast, the second particles in NCM@Y-2 were intact, intuitively
manifesting the positive effect on Y2O3 modification (Fig. S21). A
transmission electron microscopy test after cycling the battery was
further conducted to verify the effect of NCM@Y-2. In Fig. 5f, the
thick rock salt phase (Fm-3m) in NCM could be visualized in the
internal structure, while the structural damage of NCM@Y-2 after
cycling was relatively weak (Fig. 5g). Moreover, the transition-metal
concentration of the cycling samples is also shown in Fig. S22, where
the difference in content was significant. It was concluded that the
interlayer coupling between lithium layer and transition metal layer
induced by Y2O3 modification improved the structural stability.

Fig. 4 | Gas evolution and phase transition investigation. O2 and CO2 gas evolution during the first three cycles from (a) NCM and (b) NCM@Y-2. c O-K edge and
(d) Ni-L edgeof XASspectraafter cycling of NCM and NCM@Y-2. High-resolution O

Meanwhile, the LiYO2 coating effectively protected the surface of
secondary particles and avoided interface corrosion by electrolyte
infiltrated into the primary particle gap. In terms of thermal failure,
the results of differential scanning calorimetry (DSC) on NCM@Y-2
were consistent with high-temperature performance. Specifically,
after introducing Y2O3, an onset temperature was increased from 234
to 238 °C, and heat production was decreased by 74% (Fig. S23).

1s spectra from surface to bulk of (e) NCM and (f) NCM@Y-2. High-resolution
Ni 2p spectra of (g) NCM and (h) NCM@Y-2.

Theoretical calculations
To verify the above Y2O3-modification mechanism, density functional
theory (DFT) was carried out. All calculations were performed on the
(104) stable crystal plane in NCM. Based on the optimized structure of
the bare sample and LiYO2 coated NCM (Fig. 6a), the projected density
of states (PDOS) was calculated to investigate the effect of LiYO2
coating. From Fig. S24a, more electronic states in LiYO2 coated NCM

Fig. 5 | Surface structural degradation analysis. Operando XRD patterns of (a)
NCM@Y-2. b Lattice parameters (c axis and volume) as functions of voltage during
the initial charge process for the NCM and NCM@Y-2 electrodes at charge cut-off

were clearly observed, which indicated that the conductive path of the
NCM widens after coating LiYO2. In addition, the result was further
confirmed by the enlarged picture of the position of the Fermi levels
(Fig. S24b). Thus, LiYO2 coated NCM would provide better rate performance under the influence of enhanced conductivity. In previous
research, the loss of lattice oxygen was strongly correlated with transition metal ion transfer and led to structural changes 57 . Subsequently,
the possible substitution sites doped in Y 3+ were considered by calculating the formation energy and are shown in Fig. S25. The calculated
results show that the formation energies in positions Ni, Co, Mn, and Li
were −3.3734, −5.9129, −3.7818, and −7.5786, respectively (Fig. 6a).
Notably, the lowest formation energy of Y 3+ in Li position demonstrated that Y 3+ was most likely to replace Li position.

In addition to being the pillar ion to support the lithium layer after
lithium was extracted, Y 3+ also had multi-electron properties (vs. Li + ).
The local electronic structure was studied by using valence charge
density difference (VCDD) and Bader charge analysis. Figure 6b, c show
the electron cloud changes near the Li position, and the Y position that
replaced Li, respectively. The adjacent oxygen atoms around the Y
position were observed to accept more charge. In addition, the charge

voltages of 4.5 V. The depth profiles curve of (c) NCM and (d) NCM@Y-2.
e Integrated yield of different species in both samples. High-resolution TEM
image and selected area image for cycled (f) NCM and (g) NCM@Y-2 electrode.

transfer in NCM and Y 3+ -doped NCM is illustrated in Fig. 6d. Obviously,
the increase in the charge number of labeled oxygen further proved
that the dopant anchors the latticeoxygen by transferring more charge
to the adjacent oxygen. As is well known, calculated DOS was a vital
tool to distinguish the different orbital hybridization and d-orbital
splitting in the crystal field. The integral overlap of the Y 3d and O 2p
bands indicated that there is certain interaction (Fig. 6f). From
Fig. 6e, g, the Ni 3d band approached the O 2p band after half the
lithium ions were removed. Meanwhile, the Ni 3d band near the center
of the O 2p band increased with the decrease in lithium concentration,
indicating enhanced covalence between Ni and O. In general, there was
a redistribution of covalency-induced charge in Ni and O because of
the Ni 3d-O 2p hybrid state, which resulted in the instability of lattice
oxygen 58 . However, for the Y doped sample, the overlapping integral
area in the Ni 3d and O 2p bands was relatively small during the delithiation process. In addition, Ni 3d orbital splitting was utilized to
investigate specific valence states of Ni, and the results are shown in
Fig. 6i–l. The Ni 4+ oxidation state was observed near the Fermi level in
the two samples under the charging state (Fig. 6k, l). It was found that
the Y doped NCM was dominated by a large amount of Ni 3+ and a small

Fig. 6 | Density functional theory calculations. a Calculated formation energies
for Y cation doped at the different substitution sites in NCM. VCDD of (b) NCM and
(c) Y doped NCM. d Charge transfer number for different atoms of NCM and

contribution of Ni 4+, while the NCM was the opposite. Indeed, Y 3+ was
not only used to stabilize the lattice oxygen. The electrons accumulated at the oxygen sites were transferred to the nickel in a highvalence state under restore coupling, which led to a decrease in nickel
activity in the charging process.

Discussion
In summary, the Y2O3-modification strategy can optimize the surface
structure and enhance interface stability of high-nickel materials by
inhibiting oxygen loss and transition metal ion transfer at high voltage.
Based on the characterization results of XRD, STEM-HADDF, and DFT,
it is demonstrated that Y 3+ substitutes Li + and becomes an electron
donor in the lithium layer. The characterization of XAS and DFT further
proves that the mechanism of Y 3+ -O 2- -Ni 4+ electron cloud coupling
improves structural stability by stabilizing the lattice oxygen and
reducing highly active nickel. Therefore, compared with the bare
sample, the rate performance, cycle stability, and particularly high
temperature performance of the modified sample show significant
enhancement at high cut-off voltage.

Methods
Material and method
Firstly, Ni0.83Co0.12Mn0.05(OH)2 was provided by CNGR Advanced
Material Co., Ltd. Then the anhydrous ethanol dispersion of Y2O3 was
prepared. 4 g of Ni0.83Co0.12Mn0.05(OH)2 was added to the above
solution and stirred until the ethanol evaporated. Finally, to obtain Y 3+

modified Ni0.83Co0.12Mn0.05O2, dried Ni0.83Co0.12Mn0.05(OH)2@Y2O3
were mixed with excess LiOH (99.99%, Aladdin) and calcined
at 480 and 780 °C for 4 and 15 h, respectively. Herein, the as-prepared
samples were named NCM@Y-1, NCM@Y-2, and NCM@Y-3,

NCM@Y-2. DOS of Ni and O in e NCM, f Y doped NCM, g NCM with delithiation, and
h Y doped NCM with delithiation. Projected DOSs Ni at different state of i NCM, j Y
doped NCM, k NCM with delithiation, and l Y doped NCM with delithiation.

corresponding to the addition of Y2O3 at 1, 1.5, and 2% wt in the system.
In comparison, no precursor mixed with Y2O3 anhydrous ethanol was
named NCM.

Physical characterization
The elemental oxidation state was examined by X-ray photoelectron
spectroscopy (XPS, Thermo Scientific ESCALAB Xi+) with an Al Kα rays
(hv = 1486.6 eV) as the excitation source. The crystal structure and
lattice parameter for all samples were analyzed by powder X-ray diffraction (XRD, D8-ADVANCE) employing Cu Kα radiation at a scanning
rate of 12°·min −1 . In-situ XRD patterns were acquired to survey the
phase change of samples during the first cycle. The surface morphology and coating thickness of all samples were visualized by scanning
electron microscopy (SEM, ZEISS Sigma 300) and transmission electron microscopy (TEM, FEI Talos F200X G2). The contents of transition
metal elements were captured by ICP-OES (Thermo Fisher iCAP PRO).
The thermal stability was analyzed with the differential scanning
calorimeter (DSC, PerkinElmer STA 8000) test, equipped with a temperature range of 30 °C to 300 °C under the Ar atmosphere. The Ni Kedge was performed at the beamline of SSRF (Shanghai). The O K-edge
and Ni L-edge were characterized by the beamlines MCD-A and MCD-B
(Soochow Beamline for Energy Materials) at national synchrotron
radiation laboratory (NSRL, Hefei). The gas evolution was employed by
differential electrochemical mass spectrometry (DEMS). The loss of
lattice oxygen was investigated by an electron paramagnetic resonance (EPR) test (Bruker EMX PLUS).

Electrochemical measurement
The half-cells were made by slurry containing 80% wt active material,
10% wt Super P, 10% wt PVDF, and appropriate NMP and then drying at

105 °C. Dred circular electrodes with an area density of 2.5 mg·cm −2 and
Li disks were employed as cathodes and anodes to assemble CR2032
coin cells, respectively. For coin full-cell, the area density of the cathode increases to 3.5 mg·cm −2, and the Li disk was replaced by natural
graphite. Among them, the graphite anode used was pre activated for 5
cycles to obtain. Electrolyte was dominated by 1 M LiPF6 dissolved in
EC/EMC (3:7 by volume). Battery testing system (CT-4008T) was
employed to test the rate and cycling performance at 2.75–4.3/4.5 V
under the room-temperature. Electrochemical workstation (CHI 604e)
was carried out to record the data of cyclic voltammetry (CV) and
electrochemical impedance spectroscopy (EIS).

DFT calculation
The Vienna ab initio simulation package (Vasp) was utilized to perform
spin-polarized density functional theory calculations within on-site
Coulomb interaction (DFT + U). The d-orbital electrons of Ni, Co, and
Mn ions were characterized by the U value (6.7, 4.91, and 4.64 eV) and
the same J value (0 eV).

The projector-augmented wave (PAW) approach was used to
signify core-valence interactions. The exchange-correlation function
was obtained by the generalized gradient approximation (GGA) of
Perdew-Burke-Ernzerhof (PBE). The plane wave basis expansion’s
energy cutoff was set to 500 eV. Optimized structures were obtained
by minimizing the forces on each ion using the conjugate gradient
algorithm where the value was 0.02 eV/Å. Then, the cutoff convergence energy in self-consistent calculations was 10 −5 eV.

The (104) surface of the layered LiNiO2 was simulated by a
supercell that contained 50 Li, 50 Ni, and 100O atoms, with two surfaces separated by a 15 Å vacuum layer. Mn&Co-doped LiNiO2 (104)
surface was obtained by randomly replacing Ni atoms in LiNiO2 (104)
surface (Mn:Co:Ni atom ratio 1:1:8). The structural models used for the
calculations are shown in the following paragraphs.

Data availability
The data that support the findings detailed in this study are available in
the article and its Supplementary Information or from the corresponding authors on request. Source data are provided with
this paper.

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Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (No. U22A20420, 22478039), Key project of Jiangsu
Provincial Basic Research Program (BK20243032), and Jiangsu Province
Engineering Research Center of Intelligent Manufacturing Technology
for the New Energy Vehicle Power Battery.

Author contributions
Shijie Wang conceived the experiment and carried out data analysis.
Kang Liang and Hongshun Zhao conducted the SEM and TEM experiments and related data analysis. Min Wu and Junfeng He carried out the
hard-XAS and soft-XAS experiments. Peng Wei and Xiaobing Huang
operated the in-situ XRD and DEMS measurements. Zhengping Ding
performed FIB-TEM and TOF-SIMS experiments. Jianbin Li conducted
theoretical calculation. Yurong Ren supervised all aspects of the
research. All the authors discussed and commented on the manuscript.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary information The online version contains
supplementary material available at
[https://doi.org/10.1038/s41467-024-52768-7.](https://doi.org/10.1038/s41467-024-52768-7)

Correspondence and requests for materials should be addressed to
Yurong Ren.

Peer review information Nature Communications thanks Taehoon Kim
and the other, anonymous, reviewer(s) for their contribution to the peer
review of this work. A peer review file is available.

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