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Carbonate coprecipitation preparation of Li-rich layered oxides

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
using oxalate anion ligand as high-energy, high-power and
durable cathode materials for lithium-ion batteries
Long Xu,‡a Peiyu Hou,‡a Yantao Zhang,a Hongzhou Zhang,a Dawei Song,*a Xixi Shi,a Xiaoqing Wangb
and Lianqi Zhang*a
Rechargeable lithium-ion batteries (LIBs) present an urgent demand to develop cathode materials that combine high-
energy and high-power density with long cycle life. For meeting the demand, dual ligands (ammonia and oxalate anion) by
hydrate coprecipitation have been introduced to prepare spherical precursors for the above desired cathode in our
previous study, in which low efficient, toxic and volatile ammonia is still utilized as one of ligands and inert atmosphere is
needed due to high content of Mn. Thus, in this work, the feasibility of using oxalate anion as a single ligand by carbonate
coprecipitation for Li-rich layered oxides is investigated. Consequently, it delivers high volumetric energy density of about
2000 Wh L-1, high-power density of over 940 Wh L-1 at a current density of 1000 mA g-1, and superior cycling stability with
capacity retention of 98.1% after 80 cycles, much better than those of the Li-rich oxides prepared via ammonia ligand. Also,
it approaches the level for the sample prepared via dual ligands. The enhanced properties are likely ascribed to the smaller
primary particles and the possibly suppressed phase transformation from layered to spinel phases due to a large amount
of stacking faults, lower cation mixing and higher Mn oxidation state according to SEM,TEM, XRD and XPS experiments.
These findings demonstrate that oxalate anion is a desired ligand to prepare Li-rich layered oxides as high-energy, high-
power and durable cathode materials for LIBs.

focused on preparing microsized spherical secondary particles

1.Introduction assembled by nanostructured primary grains via a
coprecipitation route.19-25 These spherical particles are
Cathode materials play an increasingly important role in
1-3 available to achieve high volumetric energy density and long
rechargeable lithium-ion batteries (LIBs). LiCoO2 (LCO) is the
cycle life owing to high packing-density and low contact with
first commercialized cathode material for LIBs. It is widely used
electrolyte in contrast with those irregular particles or
due to its high volumetric energy density until now. However,
nanoparticles.26-29 Though the spherical particles can improve
LCO has some intrinsic limitations including toxicity, high cost,
its volumetric energy density, it is still hard to catch up with
rare cobalt element and instability at high upper cutoff
4-6 that of these commercialized layered oxides such as LiCoO2,
potentials. Therefore, investigation of candidate cathode
LiNi1/3Co1/3Mn1/3O2 and LiNi0.5Co0.2Mn0.3O2.30-34 To further
materials to replace LCO becomes imperative. Among these
improve the status, dual ligands (ammonia and oxalate anion)
materials, Li-rich manganese-based layered oxide is considered
which have a synergistic action on chelating transition-metal
as one of the most promising materials in view of large
7-16 ion, have been introduced to achieve high-packing precursors
reversible capacity and low cost. Unfortunately, the Li-rich
for Li-rich layered oxides in our previous study.25 As a result, it
materials usually present unsatisfied volumetric energy density,
delivers high volumetric energy density of over 2100 Wh L-1,
inferior cycling stability and rate capacity, and a gradual
17-19 superior cyclability and relatively stable median-voltage.
decline in discharge median-potential during cycles, which
Nevertheless, the dual ligand route still has some intrinsic
have hindered its commercialization.
drawbacks: (1) the low efficient, toxic and highly volatile
To overcome these shortages, much attention has been
ammonia is still utilized as one of ligands. The ammonia easily
volatilize to the air under the reaction condition of high
a.
Tianjin Key Laboratory for Photoelectric Materials and Devices, School of temperature (usually 50 °C) and high stirring rate.20-24 It should
Materials Science and Engineering, Tianjin University of Technology, Tianjin be noted that these ammonia volatilized into atmosphere
300384, China E-mail: songdw2005@mail.nankai.edu.cn (D.W. Song)
during reaction will be oxidized to NOx under air atmosphere,
tianjinzhanglq@163.com (L.Q. Zhang)
b.
School of Environment and Chemical Engineering, Tianjin Polytechnic University, which severely pollute water, soil and air.35 (2) the hydroxide
Tianjin 300387, China. coprecipitation route used above need rigorous inert
‡ L. Xu and P. Hou contribute equally to this work
Electronic Supplementary Information (ESI) available: [EELS spectra]. See
atmosphere protection to avoid the oxidation of Mn2+ during
DOI: 10.1039/x0xx00000x reaction process.24,25 Also, other coprecipitation conditions

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including pH, stirring rate and ligand concentration need 2.1 Preparation of precursors and Li-rich cathode materials:
21
careful control. To synthesize the new precursors, stoichiometric NiSO4·6H2O,
As pointed out in our previous study and indicated in CoSO4·7H2O, and MnSO4·H2O (cationic ratio of Ni:Co:Mn=1:1:4)

Journal of Materials Chemistry A Accepted Manuscript

-1
Table 1, the oxalate ligand has stronger chelating ability to were dissolved with a concentration of 1.0 mol L as the
2+ 25
Mn in contrast to ammonia, resulting in a similar starting solution. Then the aqueous solution was pumped into
2+ 2+ 2+ 2+
precipitation rate of M (Ni , Co and Mn ) in the case of a continuously stirred tank reactor (CSTR, capacity of 10 L) and
2+ -1
oxalate ligand and possibly homogenous distribution of M reacted with 2 mol L Na2CO3 solution (aq) as the pH control
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-1
through a particle. However, because of using dual ligands, the agent and 0.02 mol L oxalate anion solution (aq) as the ligand
function of ammonia cannot be excluded out in our previous in the reactor under 50 °C and contant pH of 8.0, leading to
work. Recently, the facile carbonate coprecipitation method is the new carbonate precursors (Ni1/6Co1/6Mn4/6)CO3 with
proposed to prepare spherical precursors for Li-rich layered atomic level uniformity of elemental distribution. To compare
19,20,34
oxides. To completely clarify effect of oxalate ligand and with this sample, the same stoichiometric carbonate
also avoid using the protective gas, in this work we aim to precursors were also prepared via a similar coprecipitation
-1
investigate the feasibility of using oxalate anion as a single route, in which 0.2 mol L ammonia solution (aq) acted as
ligand to synthesize spherical precursors via a facile carbonate ligand. Then, the both obtained precursor particles were
coprecipitation route for Li-rich layered oxides. A possible filtered, washed, and dried in vacuum. In previous studies, it
schematic route of coprecipitation using oxalate anion ligand was found that the sample with Li/M=1.4 displayed higher
to prepare spherical particles of Li-rich materials is illustrated discharge capacity, superior cycling stability and improved rate
36,37
in Scheme 1. properties. Thus, the mixtures of as-prepared precursor
particles and stoichiometric ratio Li2CO3 (Li/M=1.4) powders
Table 1 Equilibrium reactions and constants of transition-metal ions and
ligands in the solution.
were preheated at 750 °C (2 h) and then at 850 °C (10 h) in a
furnace under air to form Li-rich layered oxides
log K Li1+x(Ni0.139Co0.139Mn0.556)O2.
Equilibrium reaction
K Ni Mn Co
M2++NH3 [M(NH3)]2+ K1 2.81 1.00 2.10 2.2 Materials characterization: Precursors were collected at the
M2++2NH3 [M(NH3)2]2+ K2 5.08 1.54 3.67 end of coprecipitation experiment and the particle size
M2++3NH3 [M(NH3)3]2+ K3 6.85 1.70 4.78
distribution was measured with a particle size analyzer (OMEC,
M2++4NH3 [M(NH3)4]2+ K4 8.12 1.30 5.53
M2++5NH3 [M(NH3)5]2+ K5 8.93 - 5.75 LS-POP(6)). The total chemical compositions and surface state
M2++6NH3 [M(NH3)6]2+ K6 9.08 - 5.14 of Li-rich oxides were detected by Inductively Coupled Plasmas
M2++C2O42- M(C2O4) K1 5.30 3.97 4.79 Spectrometer (ICP, SPS 7800, Seiko Instruments) and X-ray
M2++2C2O42- [M(C2O4)2]2- K2 7.64 5.80 6.70 photoelectron spectroscopy with a monochromatic Al Kα X-ray
M2++3C2O42- [M(C2O4)3]4- K3 8.50 - 9.70
MCO3 M2++CO32- Ksp -8.18 -10.65 -12.89
source (XPS, Thermo Scientific), respectively. The packing
density is measured by tap-density tester (ZS-201). The
structure and morphology of the samples were detected using
X-ray diffraction (XRD, Rigaku D/MAX-2500), scanning electron
microscopy (SEM, Hitachi S4800), transmission electron
microscopy (TEM, FEI Tecnai F20). EELS spectra were recorded
using a FEI Cs-corrected Titan microscope running at an
accelerating voltage of 200 kV. EELS spectra were collected in
TEM mode with a Gatan Imaging Filter using a dispersion of 0.3
eV per channel. The EELS spectra of the O K edge are
normalized to the middle peak of the O K edge for easy
comparison, while the Mn, Ni, and Co L edges are normalized
38
to their corresponding L3 peaks for comparison. Reitveld
refinement was applied for data analysis using the WinplotR
package.
2.3 Electrochemical measurements: For fabrication of cathode
electrodes, the prepared materials were mixed with acetylene
black and PVDF (80:10:10 in weight) in NMP. The obtained
slurry was coated onto Al foil and dried at 110 °C for a day,
followed by a roll-pressing. After drying, positive disks of 0.785
2
cm area were punched out to assemble the coin cells. The
Scheme 1 Co-precipitation synthesis of spherical carbonate precursors using oxalate electrodes consisted of a similar active material loading of 4.5-
anions as ligand via anion-exchange reaction. -2
5.0 mg cm . Prior to use, the electrodes were dried again at
60 °C for half a day in a vacuum oven. The electrodes were
electrochemically characterized using a 2032 type of coin cell
2.Experimental with lithium foil as the anode and 1 M LiPF6 in ethylene

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carbonate/diethyl carbonate (3:7 in volume) as the electrolyte. which small particles were consumed gradually in the favor of
The cells were preliminarily charged and discharged in the larger particles to minimize surface free energy via dissolution-
+ 34,40
range of 2.0-4.8 V (versus Li/Li ) at 25 °C at a constant currentrecrystallization. Correspondingly, spherical precursors

Journal of Materials Chemistry A Accepted Manuscript

-1 -1
density of 20 mA g for the initial two cycles and 50 mA g for were achieved because the spherical particles have lower free
subsequent cycles. energy compared with other morphologies. We believe that
the growth mechanism using oxalate anion ligand is similar to
that using ammonia ligand. XRD results evidence both
3.Results and discussion
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precursors have a typical structure of layered MnCO3 as

42
3.1 Morphology and structure of precursors indicated in Fig. 2(b) and (d). Through the comparison of
2+ 2+
equilibrium reactions and constants of M -ammonia and M -
A facile carbonate coprecipitation route is utilized to prepare
oxalate complexes in Table 1, oxalate anion ligand has stronger
the desired precursors that serve as the sources for lithiation. 2+ 2+
chelating ability with Co and Mn and more balanced
Scanning electron microscopy (SEM) images of the both 2+
chelating level with M compared with common ammonia
precursors are displayed in Fig. 1. It is obvious that both
ligand. As a result, the precursors prepared via oxalate anion
precursors have a spherical morphology and present
ligand perhaps have more homogeneous elemental
monodisperse secondary particles in Fig. 1(a) and (c). However,
distribution.
the primary grains show clear discrepancy for both precursors.
The secondary particles prepared via oxalate anion ligand are
assembled by nano-sized primary grains from Fig. 1(b), while (b)

large sheet-like primary grains except for nano-sized ones are

(104)
Intensity
observed on the surface of the secondary particles synthesized
via ammonia ligand in Fig. 1(d). Furthermore, the aimed

(116)
(012)

(113)
(110)
spherical particles can be achieved at even 0.02 M oxalate

(202)

(122)
(024)

(214)
(300)
anion in comparison with 0.2 M ammonia solution. Hence, the
introduced oxalate anion is probably a green and high efficient 10 20 30 40 50
2θ (degree)
60 70 80

ligand to prepare manganese-based spherical precursors.

(d)

Intensity

(104)

(116)
(012)

(113)
(110)

(202)

(122)
(024)

(214)
(300)
10 20 30 40 50 60 70 80
2θ (degree)

Fig. 2 Particle size distribution and XRD results of precursors prepared via oxalate anion
(a), (b) and ammonia (c), (d) ligand.

3.2 Morphology and structure of Li-rich oxides

Fig. 1 SEM images of the carbonate precursors prepared via oxalate anion (a), (b) and
ammonia (c), (d) ligands.
Particle size distribution and X-ray diffraction (XRD) results
of both precursors are shown in Fig. 2. Particle size distribution
curves reveal a normal distribution, in which the average
particle size (D50) is 10.06 and 22.47 μm for the precursors
prepared via oxalate anion ligand and ammonia ligand,
respectively. The growth mechanisms of spherical precursors
using ammonia ligand were widely investigated in previous
33,34,39-41
reports. It was generally believed that the micro-sized
monodisperse spherical hydroxide/carbonate precursors self-
assembled from nano-sized primary particles, were depended
on the coalescence and Ostwald-ripening mechanisms, in
The mixtures of as-prepared precursors and stoichiometric
lithium sources are calcined at 850 °C to form Li-rich layered
oxides. SEM images and high resolution transmission electron
microscopy (HRTEM) images of both Li-rich oxides are
displayed in Fig. 3. Li-rich oxides achieved via oxalate anion
ligand (termed as “O-Li-rich oxides”) still remains
monodisperse spherical or ellipsoid secondary particles from
Fig. 3(a) and (b). Large particles of above 10 μm and small
particles of below 5 μm are found in Fig. 3(a), the co-exsitence
of small and large secondary particles contributes to high
packing density because small particles can fill the gaps of
large particles stacking. On the contrary, Li-rich oxides
prepared via ammonia ligand (termed as “A-Li-rich oxides”)
only present large spherical particles (up to 15 μm ) in Fig. 3(e)
and (f). As a result, O-Li-rich oxides have higher high-packing
-3 -3
density (2.02 g cm ) than A-Li-rich oxides (1.90 g cm ). High-
packing density is essential to obtain high volumetric energy
density.

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Fig. 3 SEM images of O-Li-rich oxides (a-c) and A-Li-rich oxides (e-g). HRTEM images of O-Li-rich oxides (d) and A-Li-rich oxides (h).

As to O-Li-rich oxides, the primary grains turn to polyhedral rich layered oxides. The low and broadened superstructure
morphology with size of 100-150 nm shown in Fig. 3(c). around 2θ=20–25° means the increase in the amount of
Whereas, polyhedral and plate-like primary grains with size of stacking faults.48 It is concluded that O-Li-rich oxides have a
200-400 nm are observed in Fig. 3(g) for A-Li-rich oxides, which large amount of stacking faults.
are much larger than that of O-Li-rich oxides. We believe that
the plate-like primary grains originate from the sheet-like 25000 2000

primary grains in precursors. The smaller primary grains (a) 1500

Observed
Intensity (A.U.)

20000 Calculated
generally denote higher reversible capacity and more excellent 1000
Observed-Calculated
rate properties due to the shorter path for Li+ migration and 500
Bragg Position
15000
Intensity (A.U.)

electron transfer. From HRTEM images in Fig. 3(d) and (h), a 0

20 21 22 23 24 25
2 Theta (°)
continuous interference fringe spacing of the (003) plane with
10000
distance about 0.47 nm is found for both Li-rich oxides, which
is available for Li+ migration during electrochemical process.
5000
XRD is utilized to analyze the crystal structure of both Li-rich
oxides and the results are revealed in Fig. 4. The main 0
diffraction peaks could be indexed to a layered structure with
R 3 m space group. And the clear split between the adjacent -5000
peaks of (006)/(102) and (018)/(110) suggests a typical layered
structure for both oxides.43 On one hand, the additional weak 10 20 30 40 50 60 70 80
2 Theta (°)
reflections of around 2θ=20–25° are attributed to the short-
25000 2000
ranged superstructure due to the ordering of Li, Ni, Co, and (b) 1500
Observed
Intensity (A.U.)

Mn cations in the transition- metal layers for Li-rich oxide10,44- 20000 1000
Calculated
47
It can be seen from the insert in Fig. 4 that the observed 500 Observed-Calculated
weak diffraction peaks at around 2θ=20–25° for A-Li-rich 0 Bragg Position
15000 20 21 22 23 24 25
Intensity (A.U.)

2 Theta (°)

oxides are sharp in comparison with that of O-Li-rich oxides,

indicating a stronger characteristic Li2MnO3-like structure. On 10000
the other hand, the additional weak reflections of around
2θ=20–25° are also considered as the development of an 5000
additional Li2MnO3-like component in Li-rich oxides. If we use
two structure model to refine the structure of the obtained 0
materials, indicating that A-Li-rich oxides have more Li2MnO3-
like component. Xia et al.49 have revealed that structural -5000

defects in the crystal structure of the Li2MnO3 component play 10 20 30 40 50 60 70 80

an important role in the electrochemical performance of Li- 2 Theta (°)

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Fig. 4 Rietveld refinement of powder X-ray diffraction for (a) O-Li-rich oxides and (b) A-
Li-rich oxides based on the LiNi0.33Co0.33Mn0.33O2 (R 3 m) and Li2MnO3 (C2/m) phases.
The inset highlights the superlattice peaks in the 2θ=20–25°.

Journal of Materials Chemistry A Accepted Manuscript

Table 2 The refined lattice parameters, degree of Li/Ni mixing, phase ratio, the area ratio of (003)/(104) and R factors for both Li-rich oxides before charging.

Samples a-axis/Å c-axis/Å Ni in Li layer C2/m phase I(003)/I(104) Rp Rwp

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R 3 m phase
A-Li-rich oxide 2.8513(2) 14.233(1) 9.9% 87.18% 12.82% 1.11 9.18% 13.4%
O-Li-rich oxide 2.8511(6) 14.240(8) 4.4% 94.06% 5.94% 1.24 7.26% 11.1%

Rietveld refinement of both Li-rich oxides is performed to

achieve accurate parameters and the results are listed in Table
2. The refined results of both oxides can match well with the
mixture of a compound of a-NaFeO2 layered structure
LiNi0.33Co0.33Mn0.33O2 (R 3 m) and monoclinic Li2MnO3 (C2/m). It
is clear that O-Li-rich oxides show slight expansion of c-axis,
about 14.240 Å compared with 14.233 Å of A-Li-rich oxides. The
+
larger c-axis is beneficial for Li migration, especially at high
2+ +
current density. The refined doping of Ni in the Li site (3a)
has significant discrepancy, 4.4% and 9.9% for O- and A-Li-rich
50
oxides, respectively. Yu et al. have demonstrated that there
are obvious anisotropic stress and smaller inter-slab space of
+ 2+
the unit cell associated with greater Li /Ni mixing in layered
oxides via first principles calculations. Additionally, the
distortion force in the unit cell of the material with large
+ 2+
Li /Ni mixing increases sharply during the discharge process.
These issues are highly related to the reversible capacity, cycle
stability and rate performance of layered oxide materials. In
general, the value of I(003)/I(104) indicates the degree of cation
51
mixing in the Li-layers. The I(003)/I(104) intensity ratio in A-Li-
rich oxides is 1.11, implying a relatively larger degree of cation
mixing. As to O-Li-rich oxides, the value of I(003)/I(104) increases
to 1.24, which reveals the lower cation mixing. The low Li/Ni
mixing and high I(003)/I(104) (>1.20) for O-Li-rich oxides indicate
well-defined layered crystalline structure, which is favorable
8,52
for improving the electrochemical properties.
The accurate molar ratio of Li/Ni/Co/Mn in both Li-rich
oxides is measured using inductively coupled plasma atomic
emission spectrometry (ICP-AES) to explore the possible origin
for the observed differences above. From Table 3, the molar
ratios of Li/Ni/Co/Mn are 1.169/0.138/0.140/0.556 in O-Li-rich
oxides and 1.156/0.133/0.142/0.555 in A-Li-rich oxides,
respectively. A-Li-rich oxides have lower Li and Ni content than
Table 3 Molar ratio of Li/Ni/Co/Mn in both Li-rich oxides measured by ICP-AES.
Samples Li Ni Co Mn
A-Li-rich oxide 1.156 0.133 0.142 0.555
O-Li-rich oxide 1.169 0.138 0.140 0.556
3.3 Electrochemical performances
As expected, O-Li-rich oxides have improved discharge specific
capacity and Li+ intercalation/deintercalation stability in
contrast to that of A-Li-rich oxides, as illustrated in Fig. 5. O-Li-
rich oxides show larger initial discharge capacity (275.7 mAh g-
1
) than A-Li-rich oxides (266.5 mAh g-1) in Fig. 5(a) and (c). After
80 cycles, O-Li-rich oxides maintain capacity of 248.6 mAh g-1
and retention of 98.1%, but A-Li-rich oxide electrode maintains
low capacity of 216.2 mAh g-1 and retention of 87.9%. To
synthetically evaluate the stability of reversible capacity and
discharge median-potential as well as the level of packing-
density, volumetric energy density of both Li-rich oxides is
calculated and displayed in Fig. 5(b). O- and A-Li-rich oxides
deliver high volumetric energy density of 1964 and 1809 Wh L-
1
in the initial cycle respectively, which have approached to
that of Li-rich oxide prepared via dual ligands.21 After 80 cycles,
O-Li-rich oxides have volumetric energy retention of 93.3%
(1675 Wh L-1), but A-Li-rich oxides suffer from a severe
volumetric energy density fading, displaying volumetric energy
density of only 1304 Wh L-1 and low volumetric energy
retention of 74.7%. Moreover, after 80 cycles, A-Li-rich oxides
exhibit a gradual drop in discharge plateau while O-Li-rich
oxides reveal relatively steady curves from Fig. 5(d), which
demonstrates that O-Li-rich oxides have relatively stable
median-potential during long cycles.
300
Volumetric energy density (Wh L )

(a) (b)
-1
Discharge capacity (mAh g )

2000
-1

O-Li-rich oxides. The lower Ni element in A-Li-rich oxides is

2+ 250
believed to be caused by strong chelating ability between Ni 1600

and ammonia (log K=9.08, listed in Table 1), which leads to

2+ 2+ 200 1200
O-Li-rich oxides
some Ni still remaining in the form of M -ammonia O-Li-rich oxides
A-Li-rich oxides A-Li-rich oxides
complexes after coprecipitation reaction. The balanced 800
150
chelating ability of ligand plays a significant role in achieving 0 10 20 30 40 50
Cycle (n)
60 70 80 0 10 20 30 40
Cycle (n)
50 60 70 80

the stoichiometric ratio of metal ions in designed materials.

However, the difference in the content of Li may be
understood due to experimental error during ICP
measurement.

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5.0 5.0 5.0 5.0
(c) Current density: 20 mA g
-1
(d) Current density: 50 mA g
-1
(c) 4.5
(d)
4.5 4.5

Potential (V vs Li/Li )
Potential (V vs Li/Li )
4.5 A-Li-rich oxides
Potential (V vs Li/Li )

+
+
Potential (V vs Li/Li )
+

+
O-Li-rich oxides 4.0
4.0
4.0 4.0
1st cycle 3.5

Journal of Materials Chemistry A Accepted Manuscript

3.5
3.5 3.5 80th cycle
3.0 3.0
-1
3.0 3.0 1000 mA g
-1 -1 1000 mA g 20 mA g
-1
20 mA g
2.5 2.5

2.5 O-Li-rich oxides (76.0%) 2.5 O-Li-rich oxides 2.0

2.0
A-Li-rich oxides (79.0%) A-Li-rich oxides
2.0 2.0 0 50 100 150 200 250 300 0 50 100 150 200 250 300
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0 50 100 150 200
-1
Capacity (mAh g )
Fig. 5 Specific capacity (a), volumetric energy density (b), 1st (c) and 80th charge-
discharge curves of both Li-rich oxides. The median-potential is denoted as the
potential when discharged to 50% of the cathode capacity. The volumetric energy
density is calculated based on the packing-density, discharge specific capacity and
median-potential.
Rate property of cathode materials is an important factor in
cells, especially for the large cells in PHEVs and EVs. Rate
capacity and volumetric energy density and discharge median-
potential of both Li-rich oxides at different current densities
are presented in Fig. 6. Both Li-rich oxides show similar
capacity and discharge median-potential at low current
densities of 20 and 50 mA g-1 in Fig. 6(a) and (b). However, O-
Li-rich oxides indicate larger capacity, higher volumetric energy
density and more stable discharge median-potential at current
density of over 100 mA g-1, especially at high current densities
of 500 and 1000 mA g-1, than those of A-Li-rich oxides. At 1000
mA g-1, O-Li-rich oxides deliver about 140 mAh g-1 (940 Wh L-1)
compared to 105 mAh g-1 (600 Wh L-1) of A-Li-rich oxides.
Importantly, O-Li-rich oxides have steady median-potential of
about 3.6 V, while a gradually declining median-potential is
detected for A-Li-rich oxides as current densities increase in Fig.
3(b). The stable and high median-potential is an indispensable
factor for high energy density.8 Furthermore, A-Li-rich oxides
have short discharge plateau of above 3.5 V at high current
densities of 200, 500 and 1000 mA g-1 in Fig. 6(d), whereas
normal plateau is achieved for O-Li-rich oxides in Fig. 6(c).
These results confirm that O-Li-rich oxides have enhanced rate
properties compared with A-Li-rich oxides. It is believed that
the enhanced rate performances of O-Li-rich oxides are
possibly attributed to the smaller nanosized primary grains and
secondary particles, the better layered characteristic and
uniform distribution of Ni, Co, and Mn cations.
-1 -1
250 300 350 0 50 100 150 200 250 Capacity (mAh g ) Capacity (mAh g )
-1
Capacity (mAh g )
Fig. 6 Rate capabilities (a), comparison of discharge median-potential (b) and discharge
curves (c), (d) of both Li-rich layered oxides at different current densities.
3.4 Further understanding the origin of enhanced properties in O-
Li-rich oxides
Electron energy loss spectroscopy (EELS) is utilized to
investigate its fine structure. The EELS spectra of the core
edges of O K, Mn L, Co L and Ni L is revealed in Fig. 7(a) and
Fig. S1. The detailed O K edge comparison normalized to O K
middle peak is shown in Fig. 7(b), in which the pre-peak and
middle peak located at around 529.6 and 540.8 eV respectively
while the third peak varies. The pre-peak is attributed in
manganese oxides to transitions from 1s core state to oxygen
54
2p states hybridized with manganese 3d orbitals. This peak
intensity can be consequently related to the transition metal
55
oxidation state. It is clear that O pre-peak of O-Li-rich oxides
moves to slightly higher energy lost and its intensity also is
somewhat stronger than that of A-Li-rich oxides from the
insert image in Fig. 7(b), indicating slightly higher transition
metal oxidation state in O-Li-rich oxide. The third O peak is
induced by multiple scattering within oxygen shells. It has
been proved that its position can be correlated to the
interatomic distances between oxygen atoms, varying
inversely with the O−O bond length in transiZon metal
56
oxides. Obviously, the third O peak of A-Li-rich oxides shifts
to a higher energy loss from Fig. 7(b), which means shorter
first-neighbor O−O distances in A-Li-rich oxides. Moreover, Mn
L3/L2 intensity ratio of A-Li-rich oxides is higher than that of O-
Li-rich oxides in Fig. 7(c), while Co L3/L2 and Ni L3/L2 intensity
ratios remain identical (Fig. S2). The higher Mn L3/L2 intensity
ratio implies a slightly decrease in Mn oxidation state, which is
in accordance to the results of O K peak mentioned above. In
other words, a little lower Mn oxidation state, perhaps Mn ,
3+

Investigation of the origin of enhanced properties in O-Li- exists in A-Li-rich oxides. This is possibly associated with slight
rich oxides is valuable for designing and developing high- difference of compositions for two samples.
performance layered cathode materials for LIBs. Then, the
further investigations of the reasons via EELS and XPS are (a) Mn L A-Li-rich oxides
carried out in combination with the above data and previous
Intensity (A.U.)

O pre-peak O-Li-rich oxides

studies in the following section. OK

400
2000
Co L Ni L
(a) O-Li-rich oxides (b)
Discharged median-voltage (V)
Volumetric energy density (Wh L )
Discharge capacity (mAh g )

-1
-1

A-Li-rich oxides 3.6

300 1500 -1
20 mA g -1
50 mA g -1
100 mA g -1
-1 200 mA g
20 mA g 3.2
200 50 mA g
-1 1000 500 mA g
-1
500 600 700 800 900
100 mA g
-1
Energy lost (eV)
200 mA g
-1
O-Li-rich oxides 1000 mA g
-1
-1 500
O-Li-rich oxides 500 mA g 2.8 A-Li-rich oxides
100 A-Li-rich oxides -1
1000 mA g
0
0 3 6 9 12 15 18 0 3 6 9 12 15 18
Cycle (n) Cycle (n)

6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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 Please do not adjust margins
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DOI: 10.1039/C5TA04157K
Journal Name ARTICLE

A-Li-rich oxides Mn L3
(b) OK O-Li-rich oxides (c)
Norm. Intensity (A.U.) 540.8 eV Raw
Mn 2p

Norm. Intensity (A.U.)

O pre-peak A-Li-rich oxides Mn L2 Sum
529.6 eV O-Li-rich oxides Peak1

Journal of Materials Chemistry A Accepted Manuscript

A-Li-rich oxide
(a) Peak2

Norm. Intensity (A.U.)

O-Li-rich oxide O pre-peak

Background

Intensity (A.U.)
520 525 530 535
Energy lost (eV)

500 520 540 560 580 600 620 630 640 650 660
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Energy lost (eV) Energy lost (eV) 4+ 3+

2p3/2 Mn 642.7 eV 2p3/2 Mn 641.6 eV
Fig. 7 EELS spectra of the core edges of O K, Mn L, Co L and Ni L of both pristine Li-rich
layered oxides (a), O K edge comparison normalized to O K middle peak at about 540.8
eV (b) and Mn L edge comparison normalized to Mn L3 peak (c). (b)

To further reveal the Mn valence state, XPS is performed

and results are displayed in Fig. 8. Additionally, previous
650 648 646 644 642 640 638 636 634
investigations have demonstrated that the surface structure
Binding energy (eV)
and element valence state also play a significant role in Li-rich
Fig. 8 XPS spectra of Mn 2p in (a) O-Li-rich oxides and (b) A-Li-rich oxides before
layered oxides.57-59 The Mn 2p3/2 spectrum shows that both charging.
Mn3+ and Mn4+ coexist for two samples, because two major
peaks with binding energies of 641.6 and 642.7 eV are
observed, which are close to the values of Mn3+ in Mn2O3 and 4.Conclusions
Mn4+ in LiNi0.5Mn0.5O2.13,60 However, A-Li-rich oxides have a
large amount of Mn3+ on the surface in contrast to O-Li-rich The green, high efficient and low cost ligand oxalate anion is
oxides. Verde et al.57 have certified that the surface introduced as a single ligand to prepare spherical carbonate
chemistries upon cycling are relevant to the capacity loss and precursors for Li-rich layered oxide. It deliver a high volumetric
voltage fading. The existence of Mn3+ can improve the electric energy density of about 2000 Wh L-1, a high-power density of
transmission and weaken the Li-O bond in crystal structure.59 over 940 Wh L-1 at high current density of 1000 mA g-1, and
This is in favor of the occurrence of phase transition from superior cycling stability with capacity retention of 98.1%
layered to spinel phases due to the existence of Mn3+, resulting within 80 cycles, indicating much better performances than
in the capacity degradation and potential drop during cycles.61- the Li-rich oxide prepared via ammonia ligand. The
64
In addition, Xia et al.65 believe that migration of transitional performances also approaches to the level for sample
metal ions such as Ni2+/3+ and Mn3+/4+ at high potential is also a prepared via a dual ammonia and oxalate anion ligand route.
major cause for the phase transition from layered to spinel The improved properties are believed to come from the
phases. Transitional metal ions have enough energy at high smaller primary particles and the possibly suppressed phase
voltage to stride across the transitional state and then migrate transformation from layered to spinel phases due to a large
to Li vacancies, which leads to spinel formation. Gao et al.8 amount of stacking faults, lower cation mixing and higher Mn
state that the structural defects including stacking faults and oxidation state. These results have demonstrated the
disordered area are beneficial for stabilizing the cycle life, feasibility of using oxalate anion as a single ligand to prepare
possibly because these crystal defects suppress the migration spherical precursors via a facile carbonate coprecipitation
of transition metal ions. As mentioned above, O-Li-rich oxides route for Li-rich layered oxides as high-energy density, high-
have a large amount of stacking faults. Hence, the phase power density and durable cathode materials. The findings
transition from layered to spinel phase during cycles in O-Li- also provide a new insight for developing Li-rich layered oxides
rich oxides will be more suppressed than in A-Li-rich oxides with superior properties for LIBs.
according to valence state of Mn and structural defects.

Acknowledgements
This work was financially supported partly by National 863
Program of China (2013AA050906), NSFC (51272175,
21301127, 21503148).

Notes and references

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DOI: 10.1039/C5TA04157K

Carbonate coprecipitation preparation of Li-rich layered oxides using

Journal of Materials Chemistry A Accepted Manuscript

oxalate anion ligand as high-energy, high-power and durable cathode

materials for lithium-ion batteries

Published on 10 September 2015. Downloaded by UNIVERSITY OF NEBRASKA on 18/09/2015 02:18:33.

Long Xu, Peiyu Hou, Yantao Zhang, Hongzhou Zhang, Dawei Song, Xixi Shi, Xiaoqing Wang
and Lianqi Zhang

TOC

A green, high efficient and low cost ligand oxalate anion is successfully introduced to prepare

spherical precursors for high-energy, high-power and durable cathode materials.