materials

Review
Optimization of Layered Cathode Materials for
Lithium-Ion Batteries
Christian Julien 1, *, Alain Mauger 2 , Karim Zaghib 3 and Henri Groult 1
1 Physicochimie des Electrolytes et Nanosystèmes Interfaciaux (PHENIX), Sorbonne Universités, UPMC Univ.
Paris 06, CNRS UMR 8234, 4 place Jussieu, Paris 75005, France; henri.groult@upmc.fr
2 Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), Sorbonne Universités,
UPMC Univ. Paris 06, CNRS UMR 7590, 4 place Jussieu, Paris 75005, France; alain.mauger@impmc.jussieu.fr
3 Institut de Recherche d’Hydro-Québec (IREQ), Stockage and Conversion d’Energie, 1800 Lionel-Boulet,
Varennes, QC J3X 1S1, Canada; zaghib.karim@ireq.ca
* Correspondence: christian.julien@upmc.fr; Tel.: +33-673-464-084

Academic Editor: Deepak Pant

Received: 2 May 2016; Accepted: 15 July 2016; Published: 19 July 2016

Abstract: This review presents a survey of the literature on recent progress in lithium-ion batteries,
with the active sub-micron-sized particles of the positive electrode chosen in the family of lamellar
compounds LiMO2 , where M stands for a mixture of Ni, Mn, Co elements, and in the family of
yLi2 MnO3 ‚(1 ´ y)LiNi 1 Mn 1 O2 layered-layered integrated materials. The structural, physical, and
2 2
chemical properties of these cathode elements are reported and discussed as a function of all the
synthesis parameters, which include the choice of the precursors and of the chelating agent, and as
a function of the relative concentrations of the M cations and composition y. Their electrochemical
properties are also reported and discussed to determine the optimum compositions in order to obtain
the best electrochemical performance while maintaining the structural integrity of the electrode lattice
during cycling.

Keywords: nanomaterials; layered compounds; cathodes; lithium-ion batteries

1. Introduction
Lithium-ion batteries (LiBs) are generally composed of two electrode compounds having an open
structure, which act as host frameworks for the insertion/de-insertion of Li+ ions and are the place of
charge transfer. The LiB prototype was composed of graphite as a negative electrode (often named
anode) and a transition-metal oxide (TMO), i.e., LiCoO2 , LiMn2 O4 , etc., as a positive electrode (often
named cathode), separated by the electrolyte that provides a transport medium for ions (Figure 1).
During the charge of the LiB charges, the Li+ ions are extracted from the cathode and inserted into
the anode, while the electrons pass through the outer circuit (load). Consequently, the effectiveness
of a lithium-ion cell is dependent on the availability of crystallographic sites for hosting Li+ ions, in
other words on the insertion mechanism and thereby on the transport properties of ions and electrons
in both electrode materials. Note that in the case of LiB with the graphite/TMO configuration, the
limiting factor comes from the cathode side [1], in which the redox reaction is described by:

LiMna Ob Ø Li1´x Mna `x Ob ` xLi` ` xe´ (1)

Materials 2016, 9, 595; doi:10.3390/ma9070595 www.mdpi.com/journal/materials

Materials 2016, 9, 595 2 of 26
Materials 2016, 9, 595 2 of 26

Figure1.
Figure 1. Schematic
Schematic figure
figureof
ofaaLi-ion
Li-ionbattery.
battery.LiCoO
LiCoO2 is
is used
used as
as aacathode
cathodeand
andgraphite
graphiteas
asan
ananode.
anode.
2

Conventional rechargeable Li batteries exhibit rather poor rate performance, even compared
As the transition metal entering the composition of the active element of the cathode is oxidized
with old technologies such as lead-acid [4]. Achieving high rate rechargeable Li-ion batteries
and reduced during the cell charge and discharge, respectively (Equation (1)), the cathode is primarily
depends ultimately on the dimension of the active particles for both negative and positive electrodes
involved in the cathode process and then in the electrochemical performance of the cell, i.e., potential,
[5]. One of the prospective solutions for the preparation of electrodes with high power density is the
specific capacity, energy density, rate capability, etc. [2,3].
choice of nanocomposite materials because the geometric design of the insertion compound is a
Conventional rechargeable Li batteries exhibit rather poor rate performance, even compared with
crucial intrinsic property from the viewpoint of structural stability and low kinetics of ions in oxide.
old technologies such as lead-acid [4]. Achieving high rate rechargeable Li-ion batteries depends
The theoretical capacity of a given electrode material, which influences the C-rate estimations,
ultimately on the dimension of the active particles for both negative and positive electrodes [5]. One of
is calculated by the following equation:
the prospective solutions for the preparation of electrodes with high power density is the choice of
nanocomposite materials because the geometric e  N A of the insertion compound is a crucial intrinsic
Qth  design (2)
property from the viewpoint of structural stability M 3.6 low kinetics of ions in oxide.
w and
The theoretical capacity of a given electrode material, which influences the C-rate estimations, is
where Qth is the theoretical specific capacity (mAh·g−1), Mw is the mass of the correlated component
calculated by the following equation:
(g·mol−1), and Z, NA, and e represent the numbereof ˆ electrons
NA involved in the reaction, Avogadro’s
number, and electronic charge, respectively. As M Q th “ an example, let us consider the theoretical capacity (2)
w ˆ 3.6
of the Li-rich layered material Li1.2Ni0.2Mn0.6O2 or 0.5(Li2MnO3)•0.5(LiNi0.5Mn0.5O2). Qth of Li2MnO3
where Qth is the theoretical specific −1capacity (mAh¨ g´−11 ), Mw is the mass of the correlated component
and LiNi0.5Mn0.5O2 are 458 mAh·g and 273 mAh·g , respectively. Taking into account the molar
(g¨ mol´1 ), and Z, NA , and e represent the number of electrons involved in the reaction, Avogadro’s
concentration of the compounds in the Li-rich electrode, the overall theoretical capacity is expected
number, and electronic charge, respectively. As an example, let us consider the theoretical capacity of
to be 378 mAh·g−1.
the Li-rich layered material Li1.2 Ni0.2 Mn0.6 O2 or 0.5(Li2 MnO3 )‚0.5(LiNi0.5 Mn0.5 O2 ). Qth of Li2 MnO3
The performance of electrode materials for Li-ion batteries reached today is the result of
and LiNi0.5 Mn0.5 O2 are 458 mAh¨ g´1 and 273 mAh¨ g´1 , respectively. Taking into account the molar
intensive research to reduce the size of particles to the nanoscale for three main reasons. One is the
concentration of the compounds in the Li-rich electrode, the overall theoretical capacity is expected to
increase of the effective contact area of the powder with the electrolyte. A larger effective contact
be 378 mAh¨ g´1 .
surface with the electrolyte means a greater probability to drain Li+ ions from the electrode, which
The performance
increases of electrode
the power density of thematerials for Li-ion
cell. Secondly, batteries particles
nano-sized reached today is the result
have larger surfaceof areas
intensive
and
research to reduce the size of particles to the nanoscale for three main reasons. One
exhibit superior charge transfer kinetics. Thirdly, a smaller particle size also reduces the diffusion is the increase of
the effective contact area of the powder with the electrolyte. A larger effective
pathway of Li+ ions to the interior of the particle, +which leads to a greater capacity at higher contact surface with
the electrolyte means
charge/discharge ratesa and
greater probability
therefore to drain
to a larger powerLi density
ions from theFormally,
[6,7]. electrode,the which increasestime
characteristic the
power density of the cell. Secondly, nano-sized particles have larger surface
(or Li+ migration time), τ, for the intercalation reaction is deduced from Fick’s law: areas and exhibit superior
charge transfer kinetics. Thirdly, a smaller particle size also reduces the diffusion pathway of Li+ ions
to the interior of the particle, which leadsτto= aL greater
2/4πD* (3)
capacity at higher charge/discharge rates and
therefore +
where L istothea larger power
diffusion density
length and [6,7].
D* theFormally,
chemicalthe characteristic
diffusion timeof(or
coefficient Li+Liions
migration
in the hosttime), τ,
lattice
for
[7].the
Forintercalation reaction
a given chemical is deduced
diffusion from Fick’s
coefficient of Lilaw:
+ ions, D*, the reduction of the size of the active

particles from micro- to nano-scale implies a decrease in the characteristic time τ for the intercalation
τ “ L2 {4πD* (3)
reaction by a factor of 106, which corresponds to an enhancement of rate capability of the electrode.
Nanoparticles, as well as more tailored nanostructures, are being explored and exploited to enhance
the rate capability, even for materials with poor intrinsic electronic conductivity such as olivine
Materials 2016, 9, 595 3 of 26

where L is the diffusion length and D* the chemical diffusion coefficient of Li+ ions in the host lattice [7].
For a given chemical diffusion coefficient of Li+ ions, D*, the reduction of the size of the active particles
from micro- to nano-scale implies a decrease in the characteristic time τ for the intercalation reaction by
Materials of 109,6 ,595
a factor 2016, which corresponds to an enhancement of rate capability of the electrode. Nanoparticles, 3 of 26
as well as more tailored nanostructures, are being explored and exploited to enhance the rate capability,
frameworks.
even for materials Therefore,
with poorin theintrinsic
presentelectronic
work, only materials under
conductivity such asthe form frameworks.
olivine of nano-sizedTherefore,particles
are investigated.
in the present work, only materials under the form of nano-sized particles are investigated.
Among the materials capable of delivering high reversible capacity, the layered rhombohedral
structures
structures (R3m( R3m space
space group)
group) that
that are
arepart
partofofthe thesolid-solution
solid-solutionseriesseriesLi(Ni
Li(Ni yMnCo
y Mn z zCo )O22 (called
1-y-z)O
1-y-z (called
NMC hereafter)were
NMC hereafter) werefirstfirstintroduced
introducedbyby Liu
Liu et etal.al.
[8].[8].
TheThe symmetric
symmetric LiNiLiNi
1/3
1/3Mn1/3
Mn 1/3
Co
Co 1/3O
O
1/3 2
2 compound
compound
was proposed
was proposed by by Ohzuku’s
Ohzuku’s group group in in 2001
2001 [9].
[9]. These
These materials
materials are are now
now widely
widely studied
studied as as alternative
alternative
4-volt
4-volt cathode
cathode materials
materials to to replace
replace LiCoO
LiCoO22,, exhibiting
exhibiting much much higher
highervoltage,
voltage,great
greatstructural
structuralstability,
stability,
and
and enhanced
enhanced safety safety even
even at at elevated
elevated temperature
temperature and and higher
higher reversible
reversible charge
charge capacity
capacity [10–12].
[10–12].
However, the electrochemical performance of NMCs, i.e., capacity
However, the electrochemical performance of NMCs, i.e., capacity retention and long life cycling, retention and long life cycling,
strongly dependononthethe
strongly depend composition,
composition, the the particle
particle morphology,
morphology, and
and the the deviation
deviation from thefrom idealthe ideal
rock-salt
rock-salt structure [13]. The reversible specific capacity of NMC was measured
structure [13]. The reversible specific capacity of NMC was measured to be 160 mAh¨ g in the cut-off to be ´160
1 mAh·g −1 in

the cut-off
potential rangepotential
of 2.5–4.4 range
V andof2002.5–4.4
mAh¨ gV and´ 1 in that200 mAh·gV [14].
of 2.8–4.6 −1 in that
In theofLi2.8–4.6 V [14]. In the
1´x Ni1/3 Mn1/3 Co1/3 O2
Li 1−xNi1/3Mn
cathode, Co1/3O2 cathode, the
the1/3charge/discharge charge/discharge
process occurs with differentprocess occurs withstates:
oxidation differentthe Nioxidation
2+ /Ni4+ states:
in the
the Ni 2+/Ni4+ in the range 0 ≤ x ≤ 2/3 and 3+ the couple
4+ Co 3+/Co4+ is activated in the range 2/3 ≤ x ≤ 1,
range 0 ď x ď 2/3 and the couple Co /Co is activated in the range 2/3 ď x ď 1, while the
while the electrochemically
electrochemically inactive Mninactive Mn4+anions
4+ ions play play anrole
important important role by
by stabilizing thestabilizing the electrode
electrode structure [15].
The schematic representation of the energy diagram vs. density of states for Lix Ni1/3 Mn1/3 Co1/3 O2for
structure [15]. The schematic representation of the energy diagram vs. density of states is
Li xNi1/3Mn
shown 1/3Co1/3O
in Figure 2 is three
2 for shownstates
in Figure 2 for (SOC).
of charge three statesDuringof charge (SOC).
the charge During
process, thethe charge
Fermi process,
level of the
the
hostFermi levelEFof, is
material, the host material,
lowered and for E , is lowered
a Fhigh degree of and for a high Edegree
delithiation of delithiation EF is pinned
F is pinned at the top of the O(2p)
at the top of the O(2p) band, which provides an intrinsic
band, which provides an intrinsic voltage limit for the cathode material [16]. voltage limit for the cathode material [16].

Figure
Figure 2.2.Schematic representation
Schematic of the energy
representation of thediagram
energyvs.diagram
density ofvs. states density
for LixNi1/3
ofMn 1/3Co1/3for
states O2
at
Lixdifferent
Ni1/3 Mn1/3charge
Co1/3states. The Fermi
O2 at different levelstates.
charge of theThecathode material
Fermi level is cathode
of the represented for is
material three state of
represented
charge.
for three(a) Fullofdischarge;
state charge. (a)(b) half
Full discharge;
discharge; (b)(c)half
fulldischarge;
charge. (c) full charge.

In this work,
In this work, nanostructured
nanostructured NMC NMC cathode
cathode materials
materials with
with different
different chemical
chemical configurations
configurations
(see ternary
(see ternary phase
phase diagram,
diagram, Figure
Figure 33 were
were synthesized
synthesized by by wet-chemical
wet-chemical methods.
methods. As the
As the
electrochemical performance of NMC materials is extremely dependent on
electrochemical performance of NMC materials is extremely dependent on the synthesis methodthe synthesis method
and parameters,we
and parameters, wereport
reportthethe influence
influence of the
of the recipe,
recipe, the particle
the particle sizemorphology,
size and and morphology,
and theand the
sample
sample composition on electrochemical properties of NMC electrode materials.
composition on electrochemical properties of NMC electrode materials. In addition to the cationIn addition to the
cation mixing (structural defect), the crystallinity, phase purity, particle morphology, grain
mixing (structural defect), the crystallinity, phase purity, particle morphology, grain size, and surface size, and
surface area depend
area depend on the synthesis
on the synthesis method, method,
and theyand theyan
all play allimportant
play an important roleand
role in ionic in electronic
ionic and
electronic transport [17]. A series of mixed transition-metal oxides LiNiwMnyCozO2 samples is
investigated for which the following parameters affecting their structural and electrochemical
properties are considered: (i) effect of particle size; (ii) effect of the cation mixing; (iii) adjustment of
the transition-metal/lithium ratio of the precursor; (iv) effect of chelating agent used in the synthesis;
(v) effect of the synthesis recipe; (vi) slight deviation of the cobalt content in the symmetric NMC
Materials 2016, 9, 595 4 of 26

transport [17]. A series of mixed transition-metal oxides LiNiw Mny Coz O2 samples is investigated for
which the following parameters affecting their structural and electrochemical properties are considered:
(i) effect of particle size; (ii) effect of the cation mixing; (iii) adjustment of the transition-metal/lithium
ratio of the precursor; (iv) effect of chelating agent used in the synthesis; (v) effect of the synthesis
recipe; (vi) slight deviation of the cobalt content in the symmetric NMC compound; and (vii) Li-rich
Materials 2016, 9, 595 4 of 26
integration in layered powders.

Figure 3. Ternary phase

Figure phase diagram
diagram ofofthe
themixed
mixedtransition-metal
transition-metaloxides
oxidesLiNi
LiNi
wwMn
MnyyCo O22 (w + y ++ zz == 1)
CozzO 1)
formed by the LiCoO
formed -LiNiO22-LiMnO
LiCoO22-LiNiO -LiMnO22solid
solid solutions.
solutions. The
Thecompounds
compoundsstudied
studiedin in this
this work
work are are
marked in
marked in red. The
The samples
samples are
are noted (w'y'z') where w’
(w’y’z’) where w' == 10w, y’
y' == 10y and z’
z' == 10z.

2.
2. Experimental
Experimental

2.1. Synthesis
2.1. Synthesis Procedures
Procedures
Layered compounds
Layered compoundswere were synthesized
synthesized by either
by either solid-state
solid-state reaction reaction or wet chemistry
or wet chemistry (“chimie
(“chimie douce”).
douce”). These solutionThese solution
methods methods
consistconsist of acidification
of acidification of aqueous
of aqueous solution
solution ofofthe
the starting
starting
compounds was
compounds wasused usedtoto prepare
prepare the the
layeredlayered cathode materials.
cathode The acidification
materials. is generally
The acidification realized
is generally
by usingby
realized carboxylic acids. Three
using carboxylic acids.classes
Three can classesbe considered according
can be considered the synthetic
according process:process:
the synthetic sol-gel,
co-precipitation,
sol-gel, and combustion
co-precipitation, and combustion [18–20]. The synthesis
[18–20]. The synthesisroutes for the
routes different
for the samples
different samples areare
as
follows: (1)(1)LiNi Co O and NMC powders were prepared by solid-state reaction at 850 ˝C
as follows: LiNi0.55
0.55 Co 0.45 2
0.45 2 and NMC powders were prepared by solid-state reaction at 850 °C in
in air
air as as shown
shown elsewhere[21];
elsewhere [21];(2) (2)LiNi
LiNi0.55 Co
0.55 Co O2Onano-powders
0.45
0.45 2 nano-powders weresynthesized
were synthesizedby by hydrothermal
hydrothermal
method using
method usingacetate
acetate raw rawmaterials [22]; (3)[22];
materials a series (3)of amixed
seriestransition-metal oxides LiNiw Mnyoxides
of mixed transition-metal Coz O2
(w +wMn
LiNi y +yCoz =zO1)2 (wwere+ y synthesized
+ z = 1) wereby the co-precipitation
synthesized method. This
by the co-precipitation consists
method. of consists
This a hydroxide of a
route usingroute
hydroxide transition-metal
using transition-metal hydroxidehydroxide and lithium andcarbonate as startingasmaterials,
lithium carbonate as reported
starting materials, as
elsewhereelsewhere
reported [23]. (4) Li[23].1+x (Ni
(4)1/3 LiMn1+x(Ni Co
1/31/3Mn 1/31/3)1-x
CoO powders
1/32)1-xO2 powders werewereprepared
preparedby a hydroxide route route
by a hydroxide using
an aqueous
using an aqueoussolution in which
solution in which the pH thewas pH controlled
was controlled with with
care using
care usingsimultaneously
simultaneouslyNaOH NaOHand
NH4NH
and OH4OH fed fed
intointo
the reactor;
the reactor; (5) a(5)series of symmetric
a series of symmetric LiNi 1/3 Mn
LiNi 1/3Mn Co
1/31/3 Co 1/3O2 powders was
1/3 was prepared
prepared
by the
by the precipitation
precipitation technique
technique using using metal
metal acetates
acetates as as raw
raw materials
materials and and succinic
succinic acid
acid as
as a chelating
chelating
agent. Different
agent. Different acidacid to to metal-ion
metal-ion molar ratios RR were
molar ratios were used
used to to study
study thethe effect
effect of
of this parameter
parameter on on
the structural
the structural properties
properties of of the
the final
final product;
product; (6) (6) A A series
series of NMC powders powders were were synthesized
synthesized by by
co-precipitation assisted
co-precipitation assisted by by single
single dicarboxyl
dicarboxyl (oxalic) (oxalic) and and complexed
complexed dicarboxyl
dicarboxyl (tartaric)
(tartaric) acid;
acid; (7)
(7) aa
series of LiNi
series LiNi0.33+δ
0.33+δMnMn0.33+δ CoCo
0.33+δ 0.33-2δ O2 O
0.33-2δ 2 with
with different
different values
values of of
δ δwaswasobtained
obtainedby bythe
the sol-gel
sol-gel route
route
assisted by
assisted by citric
citric acid
acid (tricarboxyl)
(tricarboxyl) in in keeping
keeping the the pHpH ofof the solution
solution in the range 5–6; (8) Li-rich
Li(Li1/3-2x/3
Li(Li NixNi
1/3-2x/3 Mn x Mn
2/3-x/3 )O2 (0)O
2/3-x/3 ≤ 2x (0 ď x powders
≤ 0.5) ď 0.5) powders were synthesized
were synthesized by a citrate–gel
by a citrate–gel methodmethod using
using acetate
acetate
salts. salts.acid
Citric Citric
wasacid was dropped
dropped wisely to wisely to the solution
the solution under continuous
under continuous stirringstirring
for 6 h for
with 6 hmolar
with
molar1:1
ratio ratio 1:1+of
of (Li Ni(Li + Ni +6H
+ Mn):C Mn):C
8O7 to6 H O
adjust
8 7 totheadjust
pH the
value pH
to value
7–8 to
with 7–8 with
ammonium ammonium
hydroxide. hydroxide.
All final
products were obtained by sintering the powders at an optimum sintering temperature of
T = 900 °C in air for a few hours.

2.2. Characterizations
The structure of the samples was investigated using X-ray diffractometer (XRD) (PANalytical
Materials 2016, 9, 595 5 of 26

All final products were obtained by sintering the powders at an optimum sintering temperature of
T = 900 ˝ C in air for a few hours.

2.2. Characterizations
The structure of the samples was investigated using X-ray diffractometer (XRD) (PANalytical
X’Pert, Lelyweg, The Netherlands) using nickel-filtered Cu-Kα radiation. The diffractograms were
taken at room temperature in the 2θ range 10˝ –80˝ . Thermogravimetry (TG) analysis was performed
using a Pyris1 instrument analyser (Perkin-Elmer, Sheffield, UK) to monitor the weight loss/gain and
heat treatment processes under a flow of dry air with a 10 ˝ C/min heating rate. The specific surface
area was analysed by the Brunauer–Emmett–Teller (BET) method using Micromeritics ASAP 2010 in
which the N2 gas adsorption was employed. The morphology and composition of the samples were
investigated by scanning electron microscopy ZEISS model ULTRA 55 (Jena, Germany), equipped with
an energy-dispersive X-ray spectrometer (EDX). HRTEM images were obtained using an electronic
microscope JEOL model JEM-2010 (Pleasanton, CA, USA). The magnetic measurements (susceptibility
and magnetization) were performed with two fully automated SQUID magnetometers (Quantum
Design MPMS-5S, San Diego, CA, USA) in the temperature range 4–300 K, as described elsewhere [24].

2.3. Electrochemical Tests

Electrochemical tests were conducted on CR2025-type coin cells. The positive electrodes were
constituted of 80 wt % active material, 10 wt % carbon black as conductive material and 10 wt %
polyvinylidene fluoride (PVDF) in N-methyl pyrrolidinone (NMP) solvent, mixed and ground to form
a homogeneous slurry. The slurry was then spread onto an aluminium foil current collector and dried
at 80 ˝ C for 2 h to remove the solvent before being pressed. The cathode loading was in the range
5–7 mg¨ cm´2 . The cells were assembled in a glove box (moisture and oxygen content ď5 ppm) under
argon atmosphere using lithium sheet as the counter electrode, Celgard 2300 film (MTI, Richmond, CA,
USA) as the separator, and 1 mol¨ L´1 LiPF6 in ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1)
solution as electrolyte (LP30, Merck, Darmstadt, Germany). The galvanostatic charge–discharge curves
were performed using a potentiostat/galvanostat (VMP3 Bio-Logic, Claix, France) in the potential
range 2.0–4.8 V.

3. Results and Discussion

3.1. The Effect of Particle Size

The main drawback of layered of TMOs is their poor discharge rate capability due to low intrinsic
electronic and ionic conductivity. Thus, at high current densities, i.e., J > 1C rate (the rate is denoted
C/n, where C is the theoretical cathode capacity and a full discharge occurs in n hours), the poor
electrochemical performance is attributed to the low electron transport of the material and the slow
Li-ion kinetics within the grains. The currently adopted approach to get high rate capability is to reduce
the diffusion path length of charge species by minimizing the particle size of the active phase [25].
For instance, Okubo et al. [26] have observed an excellent high-rate capability, i.e., 65% of the 1C rate
capability at 100C, in nanocrystalline LiCoO2 with an appropriate particle size of 17 nm. In this context,
based on the Li-ion diffusion coefficient D* « 2.5 ˆ 10´12 cm2 ¨ s´1 , the discharge process of 100 s
requires particle size L = 100 nm against 1 h for L = 2 µm. Thus, 100-nm sized particles can be fully
charged/discharged even at 10C rate (1.4 A¨ g´1 ). It was also demonstrated that control of the particle
size is obtained via synthetic methods such as sol-gel [27], hydrothermal process [28], etc. As an
example of the particle size effect, LiNi0.55 Co0.45 O2 (NCO) compounds were investigated. Figure 4
shows the HRTEM images of NCO particles and the discharge capacity curves of the corresponding
Li//LiNi0.55 Co0.45 O2 coin-type cells as a function of C-rate. The cathode material (a) prepared by
hydrothermal method has nanometric particles, 100–150 nm average size, while the micron-sized
material, 1.5–2.0 µm particle size, was prepared by a two-step co-precipitation technique. An obvious
Materials 2016, 9, 595 6 of 26

difference in the electrochemical performance is observed. The Li cell with nano-sized particles
allows a specific capacity 150 mAh¨ g´1 for 1C discharge rate, which is twice the capacity of the cell
with micro-sized particles. The excellent rate capability makes nano-LiNi0.55 Co0.45 O2 suitable for
high-power LIBs. Note that battery cycle life is favored by the architecture of the cathode material
at the sub-micron scale, which allows the accommodation of volume changes caused by Li+ ions
insertion/extraction
Materials 2016, 9, 595 into/from the single particle due to faster stress relaxation. 6 of 26

Figure HRTEM
Figure 4. HRTEM images
images of 0.55
of LiNi LiNiCo0.55 Co
0.45O 0.45 O2 layered
2 layered powderspowders with particle
with different different particle
sizes: sizes:
ca. 100–150
ca.
nm (a) and 1.5–2.0 µm (b) and discharge profiles as a function of C-rate for Li//LiNi0.55Co0.45for
100–150 nm (a) and 1.5–2.0 µm (b) and discharge profiles as a function of C-rate O2
Li//LiNi
coin-type0.55 Co0.45
cells withO2two
coin-type
cathode cells with two
materials of cathode materials
100 nm and 2 µm of 100 nm
particle andThe
size. 2 µm
goodparticle size. The
crystallinity of
good crystallinity
powders is shown of by
powders is shown
the electron by the electron
diffraction diagramdiffraction diagram
(inset); (c) (inset);
discharge (c) discharge
curves for 100–150curves
nm;
for
(d)100–150
dischargenm; (d) discharge
curves for 1.5–2.0curves
µm. for 1.5–2.0 µm.

3.2.
3.2. The
The Effect
Effect of
of Cationic
Cationic Mixing
Mixing
In
In this
thissection,
section,wewereport
reportthe
theproperties
propertiesofofmixed
mixedtransition-metal
transition-metaloxidesoxidesLiNi w Mn
LiNi wMn y Co
yCo z zOO22 as
as
4-volt
4-volt cathode
cathode materials
materials forfor Li-ion
Li-ion batteries,
batteries, for
for which
which the
the electrochemical
electrochemical features
features are
are correlated
correlated
with
with structure
structure and morphology of of active
activeparticles.
particles.Special
Special attention
attention is is given
given to the
to the influence
influence of
of the
the cation mixing between +
Li and 2+
cation mixing between Li and
+ Ni Ni
2+ ions
ions on theoncrystallographic
the crystallographic (3b)ofsites
(3b) sites the of the layered
layered lattice lattice
due to
due to the
the fact thatfact
thethat
ionicthe ionicofradius
radius Ni2+ (0.69 Å)2+close
of Ni (0.69toÅ) close
that of Lito that Å)
+ (0.76 in +an(0.76
of Li Å) in an
octahedral octahedral
environment.
environment. A partial
A partial occupation occupation
of Li(3b) of Li(3b) sites
sites generates generates
a disorder, a disorder,
so-called “cation so-called
mixing”,“cation
in the mixing”,
structure
in thedamages
that structurethethat damages the electrochemical
electrochemical performance [29–31].performance
Figure 5[29–31].
presents Figure 5 presents
the SEM imagesthe of SEM
three
images of threeprepared
NMC samples NMC samples prepared
by solid-state by solid-state
reaction at 850 °Creaction at 850
in air with ˝ C in air with
composition 333, composition
442, 532. The
333, 442,morphology
surface 532. The surface
of NMCmorphology
particles of NMC particles
displays powdersdisplays
formed by powders
aggregatesformed by aggregates
of primary particles, of
which appear
primary as small
particles, which column-shaped
appear as small particles. Typical dimensions
column-shaped of the dimensions
particles. Typical small columned of theparticle
small
are 0.5 µmparticle
columned × 2 µm for
are the 333 ˆ
0.5 µm compound.
2 µm for theThe333
SEM images of samples
compound. The SEM442 and 532
images display spherical
of samples 442 and
secondary
532 display powders
spherical formed
secondaryby aggregates
powders formedof primary particles,ofwhich
by aggregates primaryappear as small
particles, cubic-shaped
which appear as
particles.
small The formation
cubic-shaped of spherical
particles. secondary
The formation particlesecondary
of spherical is beneficial for achieving
particle a high
is beneficial tap density
for achieving a
and tap
high energy density.
density In addition,
and energy it should
density. be noted
In addition, that, be
it should in noted
cathode materials,
that, in cathode thematerials, the Li+
Li+ ion diffusion
notdiffusion
ion only depends
not onlyondepends
the sizeonoftheprimary particlesparticles
size of primary but on butthe on
morphology
the morphology and porosity
and porosity of the of
secondary
the secondary particles.
particles.
Materials 2016, 9, 595 7 of 26
Materials 2016, 9, 595 7 of 26
Materials 2016, 9, 595 7 of 26

Figure 5. SEM images of NMC samples: (a) 333; (b) 442; and (c) 532 compounds prepared by
Figure5.5.SEM
SEM images
images of NMC samples: (a)(b)
333;
442;(b) 442; andcompounds
(c) 532 compounds prepared by
Figure
solid-state reaction at of
850NMC
°C insamples:
air. (a) 333; and (c) 532 prepared by solid-state
solid-state reaction
˝ at
reaction at 850 C in air.850 °C in air.
Structural investigations (X-ray diffraction and Raman spectroscopy) show that the samples
Structural investigations (X-ray diffraction and Raman spectroscopy) show that the samples
calcined at 850 investigations
Structural °C exhibit the(X-ray typicaldiffraction
rhombohedral and Ramanα-NaFeO R3m S.G)
2 structure ( show
spectroscopy) that without
the samples any
calcined at 850 ˝°C exhibit the typical rhombohedral α-NaFeO2 structure ( R3m S.G) without any
other impurity
calcined at 850 phases.
C exhibit XRDthe data were rhombohedral
typical refined by the α-NaFeORietveld method,
structureusing(R3m the structural
S.G) without model
any
other impurity phases. XRD data were refined by the Rietveld 2method, using the structural model
(Li1-δNi
other δ)3b(LiδNiphases.
impurity x-δMnyCo 1-x-y)3adata
XRD O2 (seewere details
refinedin [32]).
by theThe resultsmethod,
Rietveld are shown usingin Figure 6 and the
the structural data
model
(Li1-δNiδ)3b(LiδNix-δMnyCo1-x-y)3aO2 (see details in [32]). The results are shown in Figure 6 and the data
refinements
(Li 1-δ Niδ )3b (Liare
δ Nilisted
x-δ Mnyin CoTable
1-x-y )3a1.
O The(seecation
detailsmixing
in [32]).corresponds
The results are to shown
an antisite defect
in Figure 6 andnoted NiLi,
the data
refinements are listed2+in Table 1. 2The +cation mixing corresponds to an antisite defect noted NiLi,
which means that Ni occupies
refinements are listed in2+Table 1. The cation a Li site that is compensated for by the opposite,
mixing corresponds to an antisite defect noted Ni , which i.e., Li’Ni,
which means2+that Ni occupies
+ a Li+ site that is compensated for by the opposite, Li i.e., Li’Ni,
corresponding
means that Ni tooccupies
a Li ionaon
+
Lia Ni 2+ site preferentially
site that is compensated close
for byto it,
thetoopposite,
result in ai.e.,
neutral
Li’Ni ,Ni Li + Li’Ni pair,
corresponding
corresponding
+ ion to a2+Li+ ion on a Ni2+ site preferentially close to it, to result in a neutral NiLi + Li’Ni pair,
with
to a Lione Nion2+ ion on
a Ni a
site3b site plus
preferentially one Li
close+ on a 3a site. The fraction of Li+ on 3a sites, which is the
to it, to result in a neutral Ni +
Li + Li’ Ni pair, with one Ni2+
with one Ni2+ ion on a 3b +site plus one Li+ on a 3a site. The fraction of Li on 3a sites, which is the
concentration
ion on a 3b siteof such
plus oneantisite
Li on defects,
a 3a site.isThe called
fraction of Li+ as
η. Indeed, on expected, the concentration
3a sites, which is the concentrationof Ni(3b) of
concentration of such +antisite defects, is called η. Indeed, as expected, the concentration of Ni(3b)
defects
such and then
antisite the Li
defects, /Ni
is called2+ cation mixing is less (η = 1.56%) for the 333 compound. The c/a value is
η. Indeed, as expected, the concentration of Ni(3b) defects and then the
defects
+ /Ni2+ and then the Li+/Ni2+ cation mixing is less (η = 1.56%) for the 333 compound. The c/a value is
related
Li tocation
the degreemixing of is
trigonal
less (η distortion,
= 1.56%) fora the higher
333 cation
compound.orderingThe being achieved
c/a value when
is related to c/a
the>degree
4.899.
related to the degree of trigonal distortion, a higher cation ordering being achieved when c/a > 4.899.
The evolution of this ratio with z in Table 1 indicates that the substitution
of trigonal distortion, a higher cation ordering being achieved when c/a > 4.899. The evolution of this of Co for Mn in
The evolution of this ratio with z in Table 1 indicates that the substitution of Co for Mn in
LiNiwwith
ratio MnyCo z inzO 2 promotes
Table 1 indicatesthe formation of the layered
that the substitution of Colattice
for Mn[30]. Thew Mn
in LiNi trigonal
y Coz O distortion
2 promotes c/atheis
LiNiwMnyCozO2 promotes the formation of the layered lattice [30]. The trigonal distortion c/a is
largest for the 333 compound and lowest for the 532 one, which
formation of the layered lattice [30]. The trigonal distortion c/a is largest for the 333 compound and indicates that a smaller
largest for the 333 compound and lowest for the 532 one, which indicates that+ a 2+smaller
concentration
lowest for the 532of Ni results
one, which in indicates
a better layered ordering
that a smaller and smaller of
concentration concentration
Ni results inofa betterLi /Ni layered
cation
concentration of Ni results in a better layered ordering and smaller concentration of Li+/Ni2+ cation
mixing. and smaller concentration of Li+ /Ni2+ cation mixing.
ordering
mixing.

Observed Observed
333 Observed 532
Calculated Calculated
Observed 442 Calculated 532 Observed
333 Difference Observed Difference
Calculated
Calculated 442 Difference
Calculated
Difference Difference
Difference
(a.u.)
(a.u.)

(a.u.)

(a.u.)
(a.u.)

(a.u.)

Intensity
Intensity

Intensity

Intensity
Intensity

Intensity

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
10 20 30 theta40(degree/CuK
Two 50 60
) 70 80 10 20 30 theta40(degree/CuK
Two 50 60
) 70 80 10 20 30 theta40(degree/CuK
Two 50 60
) 70 80
Two theta (degree/CuK) Two theta (degree/CuK) Two theta (degree/CuK)
(a) (b) (c)
(a) (b) (c)
Figure 6.
Figure 6. Rietveld
Rietveld refinement
refinement patterns
patterns of NMC samples:
of NMC samples: (a)
(a) 333;
333; (b) 442; (c)
(b) 442; 532 synthesized
(c) 532 synthesized byby
Figure 6. Rietveld refinement patterns of NMC samples: (a) 333; (b) 442; (c) 532 synthesized by
solid-state reaction. The cross marks show observed XRD intensities and the solid line
solid-state reaction. The cross marks show observed XRD intensities and the solid line (red) represents (red)
solid-state reaction. The cross marks show observed XRD intensities and the solid line (red)
represents intensities.
calculated calculated intensities.
The curve atThe
the curve at(blue)
bottom the bottom (blue) is between
is the difference the difference between and
the calculated the
represents calculated intensities. The curve at the bottom (blue) is the difference between the
calculated and observed intensities
observed intensities on the same scale.on the same scale.
calculated and observed intensities on the same scale.
The cation mixing would attract oxygen ions from adjacent oxygen layers, thereby locally
The
The cation
cation mixing
mixing would
would attract
attract oxygen
oxygen ions
ions from
from adjacent
adjacent oxygen
oxygen layers,
layers, thereby
thereby locally
locally
shortening the oxygen–oxygen distance between neighbouring MO2 (M = TM ions on 3b layer) slabs.
shortening
shortening the oxygen–oxygen
oxygen–oxygendistance
distancebetween
betweenneighbouring
neighbouring MOMO2 (M2 (M
= TM= ions
TM ions
on 3bon 3b layer)
layer) slabs.
Moreover, the Li-ions migrating between two neighbouring octahedral sites in the same lithium
slabs. Moreover,
Moreover, the Li-ions
the Li-ions migrating
migrating between
between twotwo neighbouring
neighbouring octahedralsites
octahedral sitesin
in the
the same lithium
lithium
layer are also required to pass through an empty tetrahedral site. The decrease in the oxygen–oxygen
layer
layerare
arealso
alsorequired
requiredtotopass
passthrough
throughan anempty
emptytetrahedral
tetrahedralsite.
site.The
The decrease
decreaseinin the
the oxygen–oxygen
oxygen–oxygen
distance would increase the activation energy for the Li-ion motion [32]. Furthermore, the Ni2+ 2+(3b)
distance
distance would
would increase
increase the
theactivation
activationenergy
energyfor
forthe
theLi-ion
Li-ionmotion
motion[32].
[32].Furthermore,
Furthermore,the theNi
Ni2+(3b)
(3b)
ions would exert a strong electrostatic repulsion on the Li ions and drastically hamper their
ions would exert a strong electrostatic repulsion on the Li ions and drastically hamper
ions would exert a strong electrostatic repulsion on the Li ions and drastically hamper their their reinsertion.
reinsertion. The sample with a higher concentration of cation mixing would induce very high Li
The sample with
reinsertion. The asample
higher with
concentration
a higher of cation mixing
concentration ofwould
cationinduce
mixingvery highinduce
would Li diffusion barrier
very high Li
diffusion barrier in less-ordered materials, resulting in its relatively worse electrochemical
diffusion barrier in less-ordered materials, resulting in its relatively worse electrochemical
performance. For 442 and 333 compounds, the charge compensation is achieved by stabilization of
performance. For 442 and 333 compounds, the charge compensation is achieved by stabilization of
Materials 2016, 9, 595 8 of 26

in less-ordered materials, resulting in its relatively worse electrochemical performance. For 442
and 333 compounds, the charge compensation is achieved by stabilization of Ni2+ , Mn4+ , and Co3+ .
Due to the excess of nickel-ion in the 532 compound, the charge neutrality requires the oxidation of
Ni2+ (0.2 mol per chemical formula) to Ni3+ . The amount of cation mixing estimated from magnetic
measurements is consistent with the XRD results.
Materials 2016, 9, 595 8 of 26

Table 1. Lattice parameters a, c, c/a of NMC materials, synthesized by solid-state reaction. V is the
Ni2+, Mn4+, and Co3+. Due to the excess of nickel-ion in the 532 compound, the charge neutrality
volume of the unit cell. L is the mean lattice coherence length. The last column is the ratio of the
requires the oxidation of Ni2+ (0.2 mol per chemical formula) to Ni3+. The amount of cation mixing
intensities of the XRD lines labelled by their Miller indexes and R = (I006 + I102 )/I101 . The parameter η
estimated from magnetic measurements is consistent with the XRD results.
reveals the site-exchange rate of Ni2+ (3b) cation mixing.
Table 1. Lattice parameters a, c, c/a of NMC materials, synthesized by solid-state reaction. V is the
Sample a (Å)
volume of the the mean c/a
unit cell. L cis(Å) V (Å3 ) length.
lattice coherence L (nm)
The lastIcolumn
003 /I104 is theRratio ofηthe
(%)
intensities 2.8833(2)
550 of the XRD lines labelled by
14.3251(2) their Miller
4.948 indexes and
119.08(9) R = (I006 + 1.197
59.9 I102)/I101. The parameter
0.420 η
6.70
41{2reveals
41{2 1 the2.8766(8)
site-exchange14.3005(5)
rate of Ni2+(3b) cation mixing.
4.971 118.33(2) 65.5 1.209 0.418 5.31
532
Sample
2.8732(2)
a (Å)
14.2684(4)
c (Å)
4.966
c/a
102.01(2)
V (Å3)
61.6
L (nm)
1.252
I003/I104
0.415
R
3.34
η (%)
442
550 2.8685(1) 14.3251(2)
2.8833(2) 14.2655(3) 4.973
4.948 101.65(1)
119.08(9) 64.6
59.9 1.425
1.197 0.401
0.420 2.97
6.70
4333
½4½1 2.8604(2) 14.3005(5)
2.8766(8) 14.2376(2) 4.977
4.971 100.88(2)
118.33(2) 72.3
65.5 1.456
1.209 0.387
0.418 1.56
5.31
334
532 2.8622(3) 14.2684(4)
2.8732(2) 14.2455(7) 4.977
4.966 116.70(2)
102.01(2) 63.8
61.6 1.450
1.252 0.395
0.415 1.77
3.34
1{4 442
1{41{2 2.8628(5) 14.2655(3)
2.8685(1) 14.2259(6) 4.981
4.973 116.86(6)
101.65(1) 62.0
64.6 1.452
1.425 0.390
0.401 0.70
2.97
333 2.8604(2) 14.2376(2) 4.977 100.88(2) 72.3 1.456 0.387 1.56
334 2.8622(3) 14.2455(7) 4.977 116.70(2) 63.8 1.450 0.395 1.77
Figure
¼¼½7 displays
2.8628(5)the 14.2259(6)
typical discharge
4.981 profiles
116.86(6)of different
62.0 Li//NMC
1.452 cells
0.390 with
0.70 cathodes
synthesized by the solid-state reaction method. The electrochemical tests were carried out at discharge
rate C/5 Figure 7 displays
in the voltage the typical
window discharge
2.8–4.6 V vs. Li 0 /Li+ . of
profiles Thedifferent Li//NMC
dependence cellsspecific
of the with cathodes
capacity on
synthesized by the solid-state reaction method. The electrochemical
the composition is clearly seen. We observe smooth discharge curves with an average voltage tests were carried out at near
discharge rate C/5 in the voltage window 2.8–4.6 V vs. Li0/Li+. The dependence of the specific
3.80 V. The best result is obtained for the symmetric 333 compound, which exhibits a small irreversible
capacity on the composition ´1 is clearly seen. We observe smooth discharge curves with an average
capacity lossnear
voltage (5.5 mAh¨
3.80 V.gThe) at theresult
best first cycle, against
is obtained for 22
themAh¨ g´1 for
symmetric 333the LiNi0.5 Mnwhich
compound, 0.5 O2 exhibits
electrode.
a The
discharge
small irreversible capacity loss (5.5 mAh·g ) at the first cycle, against 22 mAh·g for theThese
curves show the typical one-step behaviour
−1 characteristic of these layered compounds.
−1

results illustrate
LiNi 0.5Mn0.5O the drastic change
2 electrode. due tocurves
The discharge the introduction of a fraction
show the typical one-stepofbehaviour
Co in thecharacteristic
LiNiy Mny Coof1-2y O2
lattice. The 333 cell discharged at C/5 delivers a reversible capacity of ca. 180 mAh¨ g´1 with aofcapacity
these layered compounds. These results illustrate the drastic change due to the introduction a
fraction of Co in the LiNi yMnyCo1-2yO2 lattice. The 333 cell discharged at C/5 delivers a reversible
retention of 88% after 50 cycles, while 72% is obtained for the 550 compound. The negative effects
capacity of ca. 180 mAh·g−1 with a capacity retention of 88% after 50 cycles, while 72% is obtained for
of cation mixing η and decrease of the oxygen–oxygen distance on the electrochemical properties,
the 550 compound. The negative effects of cation mixing η and decrease of the oxygen–oxygen
which we have discussed above, is well evidenced by comparing the results in Figure 7 and in Table 1.
distance on the electrochemical properties, which we have discussed above, is well evidenced by
For instance,
comparing thethe
capacity
results delivered
in Figure 7by andthein442 sample
Table 1. Forisinstance,
smaller the
thancapacity
that of delivered
the 333 sample, because
by the 442
the concentration
sample is smaller of antisite
than thatdefects
of the 333η issample,
larger.because the concentration of antisite defects η is larger.

Figure 7. Typical discharge profiles of different Li//NMC cells with cathodes synthesized by the
Figure 7. Typical discharge profiles of different Li//NMC cells with cathodes synthesized by the
solid-state reaction route at 850 °C. The electrochemical test were carried out at discharge rate C/5 in
solid-state reaction route at 850 ˝ C. The electrochemical test were carried out at discharge rate C/5 in
the voltage window 2.8–4.6 V vs. Li0/Li+.
the voltage window 2.8–4.6 V vs. Li0 /Li+ .
As a typical example of an electrochemical test, Figure 8 presents the discharge profiles as a
function of C-rate for the Li//LiNi0.4Mn0.4Co0.2O2 coin cell cycled in the potential range 2.5–4.4 V vs.
Li0/Li+. This is a typical illustration of the rate capability of the 442 compound grown by wet
Materials 2016, 9, 595 9 of 26

As a typical example of an electrochemical test, Figure 8 presents the discharge profiles as a

Materials 2016, 9, 595 9 of 26
function of C-rate for the Li//LiNi0.4 Mn0.4 Co0.2 O2 coin cell cycled in the potential range 2.5–4.4 V
vs. Li0 /Li+ . This is a typical illustration of the rate capability of the 442 compound grown by
chemistry, which is considered as having the highest capacity and maintaining its capacity on
wet chemistry, which is considered as having the highest capacity and maintaining its capacity on
cycling [33–36]. The cell discharged at C/25 delivers a reversible capacity of 160 mAh·g−1, with a
cycling [33–36]. The cell discharged at C/25 delivers a reversible capacity of 160 mAh¨ g´1 , with a
coulombic efficiency of 88% at the first cycle. These data are similar to those reported by Tran et al.
coulombic efficiency of 88% at the first cycle. These data are similar to those reported by Tran et al.
for LiNi0.425Mn0.425Co0.15O2 [34]. Upon further cycling, the capacity retention remains quite stable
for LiNi0.425 Mn0.425 Co0.15 O2 [34]. Upon further cycling, the capacity retention remains quite stable
despite a rather large amount (2.71%) of2+ Ni2+ antisites in the lithium interslab space of the 442
despite a rather large amount (2.71%) of Ni antisites in the lithium interslab space of the 442 material.
material. The continuous fall of the capacity against the increasing current density is attributed to the
The continuous fall of the capacity against the increasing current density is attributed to the low
low electronic conductivity of 1.4 × 10−4 S·cm−1 for LiNi0.4Mn0.4Co0.2O2 [35]. The good electrochemical
electronic conductivity of 1.4 ˆ 10´4 S¨ cm´1 for LiNi0.4 Mn0.4 Co0.2 O2 [35]. The good electrochemical
performance has also been pointed out by Tsai et al. [37] from X-ray absorption spectroscopy. The
performance has also been pointed out by Tsai et al. [37] from X-ray absorption spectroscopy. The
inhibition of structure distortion during the delithiation and lithiation cycle originates from a
inhibition of structure distortion during the delithiation and lithiation cycle originates from a balance
balance of the repulsive force and the size effect in the layered compound. Upon further cycling, the
of the repulsive force and the size effect in the layered compound. Upon further cycling, the capacity
capacity retention remains quite stable despite a rather large amount (ca. 3%) 2+
of Ni2+ in the interslab
retention remains quite stable despite a rather large amount (ca. 3%) of Ni in the interslab site of
site of the 442 material. Cycling with the upper potential of 4.5 V, the cell delivered a capacity of
the 442 material. −1Cycling with the upper potential of 4.5 V, the cell delivered a capacity of about
about 170 mAh·g´ 1
at a specific current of 40 mA·g
´ 1
−1 (C/15). The tests of electrochemical performance
170 mAh¨ g at a specific current of 40 mA¨ g (C/15). The tests of electrochemical performance
and limit of discharge rate in NMC were obtained from the Peukert plot (insert in Figure 8), which
and limit of discharge rate in NMC were obtained from the Peukert plot (insert in Figure 8), which
revealed that the 442 compound delivers almost half of the initial capacity at 2C rate.
revealed that the 442 compound delivers almost half of the initial capacity at 2C rate.

Figure 8.8.Discharge
Dischargeprofiles
profilesvs.
vs.specific
specificcapacity
capacity
of of
thethe Li//LiNi0.4Mn
Li//LiNi Mn0.4Co
Co0.2O 2 cells between 2.5 and
Figure 0.4 0.4 0.2 O2 cells between 2.5 and
4.4 V at various C-rates. The inset shows the rate capability of the 442 compound.
4.4 V at various C-rates. The inset shows the rate capability of the 442 compound.

The open-circuit curve or the discharge profile at low rate (solid line at C/25 in Figure 8) for the
The open-circuit curve or the discharge profile at low rate (solid line at C/25 in Figure 8) for the
Li//LiNi0.4Mn0.4Co0.2O2 cell can be modelled by the equation:
Li//LiNi0.4 Mn0.4 Co0.2 O2 cell can be modelled by the equation:
i
 oˆ RT xi RT 
E x    ÿEi i  ln
RT x
 K i xi  ˙
RT (4)
E pxqn“ 1  EioF` x maxln  xi i F ` K i xi (4)
F xmax ´ xi F
n “1
The fitting parameter Ki reveals the interactions between the inserted Li+ and the available sites
of the
Thehost. Theparameter
fitting parameterKiKreveals
is a lateral interactionbetween
the interactions parameterthe that
inserted Li+ and the
is introduced toavailable
representsites
the
effects
of of theThe
the host. interactions
parameterin Ka two-dimensional
is a lateral interaction process: K > 0 forthat
parameter a repulsive interaction,
is introduced K = 0 forthe
to represent an
absence
effects ofof
the any interaction,
interactions in 0a >two-dimensional
K > −4 for attractive interaction
process: between
K > 0 for a repulsivethe intercalation
interaction, Ksites, K =an
= 0 for −4
is a critical
absence state,
of any while for0K> <K−4
interaction, thefor
> ´4 interactions
attractive are so intensive
interaction between thatthe they lead to thesites,
intercalation existence
K = ´4of
two-phase
is reactions.
a critical state, while for K < ´4 the interactions are so intensive that they lead to the existence of
For NMC
two-phase insertion compounds, we consider two redox processes labelled by the index I = 1,2.
reactions.
The first process is associated to the valence change of the nickel ions: Ni2+ → Ni3+ → Ni4+. The first
step of delithiation extends from the lithium concentration of lithium on 3b sites:
xmax,1 = 1 (5)
Materials 2016, 9, 595 10 of 26

For NMC insertion compounds, we consider two redox processes labelled by the index I = 1,2.
The first process is associated to the valence change of the nickel ions: Ni2+ Ñ Ni3+ Ñ Ni4+ . The first
step of delithiation extends from the lithium concentration of lithium on 3b sites:

xmax,1 “ 1 (5)

until the Ni ions have been converted into Ni3+ , in which case x = 1 ´ y. In Equation (5), we have
neglected the amount of lithium on the 3a sites, which is justified by the fact that the concentration of
antisites is few per cent only. Then, Ni3+ ions can be converted to Ni4+ until x = 1 ´ 2y, where all the
nickel ions have been converted in the Ni4+ valence state. At this concentration a second redox process
Co3+ Ñ Co4+ begins, which extends from

xmax,2 “ 1 ´ 2y (6)

down to x = 0, where all the cobalt ions have been converted to the tetravalent state. Note we have
implicitly assumed that the different processes do not overlap. This has been justified in [38], where
we have shown from the analysis of magnetic measurements that the concentration y1 of Ni3+ at the
concentration xmax,2 does not exceed 2%, which is the uncertainty in the determination of y1 .
The best fit (Figure 8) for the 442 cathode material is obtained with two redox processes with
standard potential E0,1 = 3.731 V and E0,2 = 3.955 V and interaction factor K1 = ´3.75 and K2 = ´2.98.
Since the interaction is smaller than the critical case Kc = ´4 we are not in the case of a two-phase
regime, and indeed there is no plateau in the curves in Figures 7 and 8. Table 2 lists the electrochemical
parameters of NMC materials studied in Figure 8.

Table 2. Electrochemical parameters of NMC materials calculated from Equation (4) at low rate of
C/20. (1 ´ 2y) is the cobalt concentration in the LiNiy Mny Co1-2y O2 structure.

Cathode (1 ´ 2y) E0,1 (V) ´K1 E0,2 (V) ´K2

550 0.00 3.737 3.82 3.869 3.12
41{2 41{2 1 0.10 3.734 3.75 3.903 2.98
442 0.20 3.731 3.75 3.955 2.98
333 0.33 3.722 3.71 3.932 3.00
334 0.40 3.717 3.78 3.921 3.01

However, we know from Table 1 that the cation mixing decreases linearly with the concentration
of cobalt 1 ´ 2y from η = 7% for (1 ´ 2y) = 0 to 0.7% for (1 ´ 2y) = 0.5. While the increase of cation
mixing has important effects on the electrochemical properties that we have evidenced in Figure 8 for
instance, we find here that it has very little effect on the parameters in Table 2. The reason is that the
increase of the cobalt concentration increases the electrical conductivity and the correlated decrease of
the cation mixing increases the ionic conductivity, hence the beneficial impact on the electrochemical
properties. On the other hand, the parameters in Table 2 are parameters of the redox reactions that are
only sensitive to the average crystallographic environment of the nickel and cobalt ions, which is not
significantly disturbed by few % cation mixing in the lattice.

3.3. Adjustment of the Li/M Ratio

Another way to optimize an electrode active material consists in the adjustment of one parameter
of the synthesis, namely the lithium/transition metal molar ratio in Li1+x (NMC)1-x O2 (NMC = 333)
to minimize the cation mixing [30]. Two independent experimental procedures are used to estimate
the cation mixing (η): structural refinements of XRD patterns made by the Rietveld method, which
accurately determine the M occupancy between slabs of the layered lattice; (ii) magnetic measurements,
which are powerful to check the quality of material and structural properties at the nano-scale [39]
of samples synthesized by the co-precipitation method from a hydroxide precursor assisted by
Materials 2016, 9, 595 11 of 26

ammonium and sodium hydroxides [40]. The elemental titration carried out by ICP of the two
samples prepared by a hydroxide route with nominal Ψ = Li/M ratio (Ψ = 1.05 and 1.10) shows the
technological composition of Li-rich Li1+x (Ni1/3 Mn1/3 Co1/3 )1-x O2 with x = 0.02 and 0.04, respectively.
Note that the Li/M ratios of the samples are (1 + x)/(1 ´ x) = 1.04 and 1.08, respectively, close to the
nominal ratio Ψ. This gives evidence that the amount of Li that has evaporated during the synthesis is
very small
Materials 2016,(1%–2%
9, 595 only), and comparable to the case when the samples are prepared by the Pechini 11 of 26
method [40]. The morphology of particles is shown in Figure 9. The SEM micrograph displays powders
formed
as small,by agglomeratesparticles
column-shaped of primary particles,
of typical which appear
dimension 0.5 µm as
× 2small,
µm. Thecolumn-shaped
HRTEM imageparticles
shows the of
typical dimension of
good crystallinity 0.5the ˆ 2 µm. The
µmindividual HRTEM image
nanoparticles. shows lattice
Apparent the good crystallinity
fringes of the individual
can be observed and the
nanoparticles.
width of 0.472 nm Apparent
between lattice
latticefringes
fringescan be observed
is consistent withand
thethe width of 0.472
interspacing of thenm between
(003) planes lattice
of the
fringes
layeredisstructure
consistentR3with the interspacing
m space group. of the (003) planes of the layered structure R3m space group.

Figure 9. SEM (a) and HRTEM (b) images of Li1.04Ni0.32Mn0.32Co0.32O2 powders synthesized the
Figure 9. SEM (a) and HRTEM (b) images of Li1.04 Ni0.32 Mn0.32 Co0.32 O2 powders synthesized the
co-precipitation method from
co-precipitation method from hydroxide
hydroxide precursor
precursor assisted
assisted by
by ammonium
ammonium andand sodium
sodiumhydroxides.
hydroxides.

If u is the concentration of Ni*Li + Li’Ni pair defects, the detailed chemical formula is then
If u is the concentration of Ni* + Li’ pair defects, the detailed chemical formula is then
(Li1-uNiu)3b(Lix+uNi(1-x)/3-uMn(1-x)/3Co(1-x)/3)Li3aO2 forNiRietveld analysis: both x and u were refined, from
(Li1-u Niu )3b (Lix+u Ni(1-x)/3-u Mn(1-x)/3 Co(1-x)/3 )3a O2 for Rietveld analysis: both x and u were refined,
which the fraction η of Li on 3a sites has been deduced. The crystallographic parameters are listed in
from which the fraction η of Li on 3a sites has been deduced. The crystallographic parameters are
Table 3. In particular, y is found to be lower in sample Li1.04Ni0.32Mn0.33Co0.33O2, a result in good
listed in Table 3. In particular, y is found to be lower in sample Li1.04 Ni0.32 Mn0.33 Co0.33 O2 , a result in
agreement with the value obtained from analysis of magnetic measurements.
good agreement with the value obtained from analysis of magnetic measurements.
Table 3. Crystallographic parameter of Li1+x(NMC)1-xO2 materials. ηR and ηM reveal the site-exchange
Table 3. Crystallographic parameter of Li1+x (NMC)1-x O2 materials. η R and η M reveal the site-exchange
rate of Ni2+
2+(3b) cation mixing estimated from Rietveld refinements and magnetometry, respectively.
rate of Ni (3b) cation mixing estimated from Rietveld refinements and magnetometry, respectively.
(1 + x) a (Å) c (Å) c/a V (Å3) L (nm) ηR (%) ηM (%)
(1 + x) 1.02 a (Å) c (Å)
2.8650(1) 14.2252(2) c/a
4.975 V (Å3 )
101.31(2) L (nm)
59.4 1.98η R (%) 1.88 η M (%)
1.02 1.042.8650(1)
2.8603(2)14.2252(2)
14.241(2) 4.975
4.979 100.90(3)
101.31(2) 55.9
59.4 1.43 1.98 1.50 1.88
1.04 2.8603(2) 14.241(2) 4.979 100.90(3) 55.9 1.43 1.50
Figure 10 displays the discharge capacity of the Li1+x(NMC)1-xO2 cathode materials as a function
of the cycle10number
Figure displayswith increasing
the discharge discharge
capacity of therate
Li1+xfrom
(NMC) C/12 to 10C. The electrode material
1-x O2 cathode materials as a function
prepared with a Li excess of 4% exhibits the best performance
of the cycle number with increasing discharge rate from C/12 to 10C. The at high C-rate. These
electrode electrochemical
material prepared
features
with a Li show
excess that
of 4%the cationthe
exhibits mixing has a slightateffect
best performance on the These
high C-rate. discharge behaviour features
electrochemical attributed
showto
kinetic hindrance from Ni 2+(3b) ions in the Li layer. Note the superior discharge capacity of the 333
that the cation mixing has a slight effect on the discharge behaviour attributed to kinetic hindrance from
compound
Ni compared
2+ (3b) ions in the Li to thatNote
layer. of 442 one,
the since the
superior increase
discharge in the Co
capacity content
of the in NMC favours
333 compound the Li
compared
+
to
motion
that in the
of 442 one,crystal lattice
since the by improving
increase the electronic
in the Co content in NMC conductivity
favours theof Li+the electrode.
motion in theIncrystal
conclusion,
lattice
a larger excess of lithium in the product counteracts the cation mixing (smaller
by improving the electronic conductivity of the electrode. In conclusion, a larger excess of lithium value of y) and thusin
reduces
the the counteracts
product concentration theofcation
ferromagnetic Mn4+(3a)–Ni
mixing (smaller
2+(3b) interactions. This is actually a general
value of y) and thus reduces the concentration of
trend in layered
ferromagnetic Mn compounds,
4+ (3a)–Ni2+ (3b)since it has been This
interactions. observed also ina Li
is actually 1+x(Ni0.5
general Mn0.5)in
trend O2 [41]. compounds,
1-xlayered

since it has been observed also in Li1+x (Ni0.5 Mn0.5 )1-x O2 [41].
Materials 2016, 9, 595 12 of 26
Materials 2016, 9, 595 12 of 26

Figure 10.
10. Electrochemical
Electrochemical performance
performance of of Li
Li1+x(NMC) 1-xO2 electrode materials as a function of
Figure 1+x (NMC)1-x O2 electrode materials as a function of
synthetic parameters. The specific capacity of the Li cells is plotted for
synthetic parameters. The specific capacity of the Li cells is plotted for different
different C-rates.
C-rates.

3.4. Effect of the Chelating Agent

3.4. Effect of the Chelating Agent
With a large amount of un-removable Ni ions in the Li(3b) site that block the Li diffusion
With a large amount of un-removable Ni ions in the Li(3b) site that block the Li diffusion pathways,
pathways, the Li+-ion mobility in the host lattice is negatively affected. For example, it was reported
the Li+ -ion mobility in the host lattice is negatively affected. For example, it was reported that
that the chemical diffusion coefficient of Li in LiNi0.5Mn0.5O2 (i.e., 3 × 10−10 cm2·s−1) is lower than in
the chemical diffusion coefficient of Li in LiNi0.5 Mn0.5 O2 (i.e., 3 ˆ 10´10 cm2 ¨ s´1 ) is lower than
LiCoO2 (i.e., 5 × 10−9 cm2·s−1) resulting in the intrinsically low rate capability of this electrode material
in LiCoO2 (i.e., 5 ˆ 10´9 cm2 ¨ s´1 ) resulting in the intrinsically low rate capability of this electrode
[42,43]. In this section, we investigated the effect of the transition-metal/chelating agent molar ratio,
material [42,43]. In this section, we investigated the effect of the transition-metal/chelating agent molar
R (with 0.5 ≤ R ≤ 5) on the structural and electrochemical properties of the symmetric 333 NMC
ratio, R (with 0.5 ď R ď 5) on the structural and electrochemical properties of the symmetric 333 NMC
materials synthesized by the co-precipitation method assisted by succinic acid (dicarboxyl C4H6O4).
materials synthesized by the co-precipitation method assisted by succinic acid (dicarboxyl C4 H6 O4 ).
The TG/DTA profiles for the mixed precursor of NMC material synthesized via R = 0.5 are
The TG/DTA profiles for the mixed precursor of NMC material synthesized via R = 0.5 are
presented in Figure 11. Several weight loss stages are observed in this TG curve. The first mass loss
presented in Figure 11. Several weight loss stages are observed in this TG curve. The first mass loss
stage occurs at T < 300 °C, which can be assigned to the loss of absorbed water, the residual ethanol,
stage occurs at T < 300 ˝ C, which can be assigned to the loss of absorbed water, the residual ethanol, the
the dehydration of metal acetate, and the crystal water. The anhydrous metal acetate can be
dehydration of metal acetate, and the crystal water. The anhydrous metal acetate can be decomposed
decomposed into both metal oxide and gases such as carbon mono- and di-oxide by further thermal
into both metal oxide and gases such as carbon mono- and di-oxide by further thermal treatment
treatment in air [13]. The weight loss in the second step is observed around 355 °C, which
in air [13]. The weight loss in the second step is observed around 355 ˝ C, which corresponds to the
corresponds to the decomposition of succinic acid and acetate ions xerogel. For R = 2, the combustion
decomposition of succinic acid and acetate ions xerogel. For R = 2, the combustion temperature has
temperature has decreased to 342 °C, which produces smaller crystallites. A weight loss of 72.4%
decreased to 342 ˝ C, which produces smaller crystallites. A weight loss of 72.4% occurs during these
occurs during these two stages because of the oxidation–decomposition reaction. It appears that
two stages because of the oxidation–decomposition reaction. It appears that tartaric acid acts as a fuel
tartaric acid acts as a fuel in the pyrolysis of the gel precursor, favouring the decomposition of
in the pyrolysis of the gel precursor, favouring the decomposition of acetate ions. After 450 ˝ C, there is
acetate ions. After 450 °C, there is little weight loss, so in this work we choose 450 °C as the heating
little weight loss, so in this work we choose 450 ˝ C as the heating temperature for the pre-calcination.
temperature for the pre-calcination.
Figure 12a shows the typical Rietveld fit of the XRD pattern for the sample R = 2. The refinement
was performed using the model (Li1-δ Niδ )3b (Liδ Nix-δ Mny Co1-x-y )3a O2 [34]. Indeed, the concentration
of Ni(3b) defects and then the site-exchange rate of the Li+ /Ni2+ cation mixing is as low as 1.26% for
the R = 2 compound, as presented in Figure 12b. With the highest c/a ratio and the smallest unit
volume cell, the R = 2 sample exhibits the best layered structure. These results follow the variation
of the crystallographic parameters (Table 4). The minimum of site-exchange rate corresponds to a
minimum of the unit-cell volume and a maximum of degree of trigonal distortion given by the c/a
ratio that indicates a higher cation ordering being achieved.

(a) (b)
Figure 11. (a) TG/DTA profile for the precursor of NMC synthesized by the co-precipitation
technique using metal acetates as raw materials and succinic acid as a polymeric agent with a chelate
to metal ion molar ratio R = 0.5 (a) and R = 2 (b). With R = 2, the combustion temperature is lowered
to 342 °C.
 treatment in air [13]. The weight loss in the second step is observed around 355 °C, which
concentration of Ni(3b) defects and then the site-exchange rate of the Li+/Ni2+ cation mixing is as low
corresponds to the decomposition of succinic acid and acetate ions xerogel. For R = 2, the combustion
as 1.26% for the R = 2 compound, as presented in Figure 12b. With the highest c/a ratio and the
temperature has decreased to 342 °C, which produces smaller crystallites. A weight loss of 72.4%
smallest unit volume cell, the R = 2 sample exhibits the best layered structure. These results follow
occurs
the variationthese
during of thetwo stages because
crystallographic of the oxidation–decomposition
parameters (Table 4). The minimumreaction. It appears
of site-exchange that
rate
tartaric
corresponds to a minimum of the unit-cell volume and a maximum of degree of trigonal distortion of
acid acts as a fuel in the pyrolysis of the gel precursor, favouring the decomposition
acetate
Materials givenions.
2016, 9,by After
595the 450 °C,
c/a ratio thatthere is little
indicates weight
a higher loss,ordering
cation so in this work
being we choose 450 °C as the heating
achieved. 13 of 26
temperature for the pre-calcination.
Table 4. Structural data of the LiNi1/3Mn1/3Co1/3O2 samples synthesized at different values of R. a, c
are the lattice parameters, V is the volume of the unit cell, and L the coherence length (crystallite
size). The coherence length is the arithmetic average of the length given by the Scherrer law applied
to three main XRD lines. The two next lines are relative intensities of the XRD lines that provide
insight on the concentration of Ni2+(3b) defects. The other X-ray Rietveld refinement parameters are
reported in the last lines. S(MO2) = 2(⅓-zoxy)c is the thickness of the metal–O2 planes, I(LiO2) =
c/3-S(MO2) is the thickness of the interslab space; other notations are conventional.

Crystal Data R = 0.5 R = 1.0 R = 2.0 R = 3.0 R = 4.0

a (Å) 2.8680(2) 2.8671(2) 2.8602(1) 2.8675(2) 2.8684(3)
c (Å) 14.2588(3) 14.2593(2) 14.2458(2) 14.2589(4) 14.2619(3)
c/a 4.9716(4) 4.9734(4) 4.9807(2) 4.9726(5) 4.9720(6)
V (Å 3) 101.57(2) 101.51(2) 100.92(1) 101.53(2) 101.62(2)
L (Å) (a) ≈570 ≈540 ≈490 (b)
≈550 ≈610
I (003)/I(104) 1.440 1.614 1.728
Figure 11. (a) TG/DTA profile for the precursor of NMC synthesized by the co-precipitation 1.558 1.423
(a) TG/DTA
Figure 11.(I(006) profile for the precursor of NMC synthesized by the co-precipitation technique
technique+using I(102))/Imetal
(101) 0.482
acetates 0.427
as raw materials and succinic0.378 0.438
acid as a polymeric 0.459
agent with a chelate
using metalS(MOacetates 2) (Å) as raw materials and succinic acid as a polymeric agent with a chelate to metal ion
to metal ion molar ratio R = 2.126(2)
0.5 (a) and R = 2.120(5)
2 (b). With R = 2.109(3)
2, the combustion2.123(3)
temperature2.126(2)
is lowered
R = 0.5
molar ratio I(LiO
to 342 °C.
(a)
2) (Å) and R = 2 (b).
2.627(2)With R = 2, the
2.633(6) combustion
2.640(3) temperature is
2.630(3) 2.628(3) ˝ C.
lowered to 342
η (%) 2.96 2.04 1.26 2.90 3.0

Figure 12 (a) Rietveld refinement patterns of NMC synthesized at R = 2 via wet chemical method
Figure 12. (a) Rietveld refinement patterns of NMC synthesized at R = 2 via wet chemical method
(Rp = 9.8%). The plus marks show observed X-ray diffraction intensities and the solid line (in red on
(Rp = 9.8%). The plus marks show observed X-ray diffraction intensities and the solid line (in red on the
the web version) represents calculated intensities. The curve at the bottom (in blue on the web
web version) represents
version) calculated
is the difference betweenintensities. Theand
the calculated curve at theintensities
observed bottom (in blue
on the on the
same web
scale; version) is
(b) The
the difference between
concentration the calculated
of Ni(3b) and observed
defects (site-exchange intensities
rate of the Li+/Ni2+on the same
cation scale;
mixing) (b) The of
as a function concentration
the R
of Ni(3b)parameter for the symmetric
defects (site-exchange NMC
rate the Li+ /Ni2+ cation mixing) as a function of the R parameter for
of compounds.
the symmetric NMC compounds.
The study of the morphology clearly proved that the NMC synthesized with R = 2 presents the
best crystallinity, consistent with the XRD results. The chelating agent (in our case carboxylic acid)
Table 4. Structural data of the LiNi1/3 Mn1/3 Co1/3 O2 samples synthesized at different values of R. a, c
determines the acidity of the solution. The R value must be large enough to obtain a weak acid
are solution
the lattice
necessary to theVcrystallization
parameters, is the volumeofofthe
theoxide
unit cell, and LHowever,
material. the coherence
it mustlength (crystallite
be small enough size).
to
The coherence length is the arithmetic average of the length given by the Scherrer law applied to three
main XRD lines. The two next lines are relative intensities of the XRD lines that provide insight on the
concentration of Ni2+ (3b) defects. The other X-ray Rietveld refinement parameters are reported in the
last lines. S(MO2 ) = 2(1 {3 -zoxy )c is the thickness of the metal–O2 planes, I(LiO2 ) = c/3-S(MO2 ) is the
thickness of the interslab space; other notations are conventional.

Crystal Data R = 0.5 R = 1.0 R = 2.0 R = 3.0 R = 4.0

a (Å) 2.8680(2) 2.8671(2) 2.8602(1) 2.8675(2) 2.8684(3)
c (Å) 14.2588(3) 14.2593(2) 14.2458(2) 14.2589(4) 14.2619(3)
c/a 4.9716(4) 4.9734(4) 4.9807(2) 4.9726(5) 4.9720(6)
V (Å 3 ) 101.57(2) 101.51(2) 100.92(1) 101.53(2) 101.62(2)
L (Å) «570 «540 «490 «550 «610
I(003) /I(104) 1.440 1.614 1.728 1.558 1.423
(I(006) + I(102) )/I(101) 0.482 0.427 0.378 0.438 0.459
S(MO2 ) (Å) 2.126(2) 2.120(5) 2.109(3) 2.123(3) 2.126(2)
I(LiO2 ) (Å) 2.627(2) 2.633(6) 2.640(3) 2.630(3) 2.628(3)
η (%) 2.96 2.04 1.26 2.90 3.0
Materials 2016, 9, 595 14 of 26

The study of the morphology clearly proved that the NMC synthesized with R = 2 presents the
best crystallinity, consistent with the XRD results. The chelating agent (in our case carboxylic acid)
Materials 2016, 9, 595 14 of 26
determines the acidity of the solution. The R value must be large enough to obtain a weak acid solution
necessary
avoid direct to action
the crystallization
with the rawofmaterials
the oxide(acetates
material.orHowever, it must
nitrates). That beessence
is in small enough
the reasonto avoid
why
direct
there is an optimum value for this parameter. Figure 13 displays the SEM and HRTEM images ofisthis
action with the raw materials (acetates or nitrates). That is in essence the reason why there an
optimum
sample. The value for this
patterns parameter.
provide evidence Figure 13 displays
for the structural the SEM and
quality of theHRTEM
samples images of this
examined. sample.
Image (a)
The patterns provide evidence for the structural quality of the samples
shows the representative SEM pattern of NMC powders that indicates a material containing examined. Image (a) shows
the representative
spherical SEM patternasofconfirmed
shape crystallites, NMC powders by thethatbright-field
indicates a material containing spherical
low-magnification TEM. Primaryshape
crystallites, as confirmed by the bright-field low-magnification TEM. Primary
particles of ~0.3–0.5 µm size are regularly distributed. However, at a smaller scale (image µm particles of ~0.3–0.5 b),
size are regularly
relatively clear facetsdistributed. However,
can be observed at asurface
at the smaller ofscale
some(image
primary b),particles.
relatively Theclear facetspattern
HRTEM can be
observed
of an NMC at the surface
particle of some
(image primary
c) shows particles.
a set of acute The HRTEM
parallel pattern
fringes of an NMC
extending particle
to the (image
particle edge.c)
shows a set of acute parallel fringes extending to the particle edge.
Careful observation indicates that the fringes show a spacing distance of 0.472 nm, which Careful observation indicates that
the fringes show
corresponds to thea spacing
spacingbetween
distance(003) of 0.472 nm,
lattice whichthat
planes corresponds
diffract thetoX-rays
the spacing
at anglebetween
2θ = 18.7°.(003)
It
lattice planes that diffract the X-rays at angle 2θ = 18.7 ˝ . It is worth noting that the good morphology
is worth noting that the good morphology of the R = 2 sample is considered to be favourable for
of the R = 2high
obtaining sampletap isdensity
considered
and to be favourable
enhancing for obtaining high
the electrochemical tap densityi.e.,
performance, andimproving
enhancing the the
electrochemical
kinetics of lithium performance,
ions. i.e., improving the kinetics of lithium ions.

Figure 13.
Figure 13. (a,b)
(a,b) SEM
SEM images
images of
of NMC
NMC synthesized
synthesized atat R
R== 22 via wet chemical
via wet chemical method
method at
at different
different
magnifications; (c) HRTEM image showing the fringe system corresponding to the spacing
magnifications; (c) HRTEM image showing the fringe system corresponding to the spacing between between
(003) lattice
(003) lattice planes
planes in
in the R3mspace
the R3m spacegroup.
group.

Figure 14 presents the initial discharge profiles of NMC samples sintered at 900 °C for 15 h,
Figure 14 presents the initial discharge profiles of NMC samples sintered at 900 ˝ C for 15 h,
synthesized with an acid to metal ion ratio at 0.5 ≤ R ≤ 3.0. The charge and discharge processes were
synthesized with an acid to metal ion ratio at 0.5 ď−1R ď 3.0. The charge and discharge processes
carried out at a constant current density of 16 mAh·g (0.1 C rate) in the potential range of 2.8–4.4 V
were carried out at a constant current density of 16 mAh¨ g´1 (0.1 C rate) in the potential range
vs. Li0/Li+ at room0 temperature. As expected from the structural investigations, the NMC R = 2
of 2.8–4.4 V vs. Li /Li+ at room temperature. As expected from the structural investigations, the
material displays the best performance. Its lower cationic disorder results in its higher discharge
NMC R = 2 material displays the best performance. Its lower cationic disorder−1results in its higher
capacity. The first charge and discharge capacity are 184 and 172 mAh·g , respectively. The
discharge capacity. The first charge and discharge capacity are 184 and 172 mAh¨ g´1 , respectively.
irreversible capacity loss in the first cycle is 12 mAh·g−1 and´1the coulombic efficiency is 93.5%. After
The irreversible capacity loss in the first cycle is−112 mAh¨ g and the coulombic efficiency is 93.5%.
four cycles, the discharge capacity is 168 mAh·g and 97.7% of the first discharge capacity has been
After four cycles, the discharge capacity is 168 mAh¨ g´1 and 97.7% of the first discharge capacity
retained. Therefore, the rather small coherence length of the lattice does not affect the good
has been retained. Therefore, the rather small coherence length of the lattice does not affect the good
electrochemical performance. The electrochemical storage energy and intercalation mechanism in
electrochemical performance. The electrochemical storage energy and intercalation mechanism in
NMC in the potential range limited to 2.80–4.45 V are attributable to the Ni2+2+/Ni4+
4+redox reaction pair.
NMC in the potential range limited to 2.80–4.45 V are attributable to the Ni /Ni redox reaction pair.
Materials
Materials 2016,
2016, 9,
9, 595
595 15
15 of
of 26
26
Materials 2016, 9, 595 15 of 26

Figure 14. Initial discharge profiles of synthesized NMC sample sintered at 900 °C for 15 h,
Figure 14.Initial
Figure 14.
synthesized Initial discharge
withdischarge
chelate profiles
toprofiles
metal of synthesized
of synthesized
ion ratio at 0.5 ≤NMC NMC
samplesample
R ≤ 3.0. sinteredsintered
at 900 ˝ Catfor900
15 h,°Csynthesized
for 15 h,
synthesized
with chelate with chelate
to metal to metal
ion ratio ionďratio
at 0.5 at 0.5 ≤ R ≤ 3.0.
R ď 3.0.
3.5. Effect of the Synthesis Recipe
3.5.
3.5. Effect
Effect of
of the
the Synthesis
Synthesis Recipe
Recipe
The synthesis parameters such as the nature of the chelating agent and the annealing
The
temperature synthesis
The synthesis parameters
can strongly influence
parameters suchsuch
asthe
theasgrowth
the nature
nature process
of ofofthe
NMC
the chelating chelating
andagent
particles
agent and
the and their
thus
annealingthetemperature
annealing
structure
temperature
and morphology.
can strongly can strongly
As anthe
influence influence
example,
growth Figure the growth
process15ofpresents process of NMC
the Peukert
NMC particles particles
plotstheir
and thus and
that structurethus
show the and their
differencestructure
in the
morphology.
and morphology.
electrochemical As an example,
performance of Figure
LiNi 15
Mn presents
Co O the Peukert
electrodes plots that
synthesizedshow
As an example, Figure 15 presents the Peukert plots that show the difference in the electrochemical
1/3 1/3 1/3 2
the
using difference
a in the
wet-chemical
electrochemical
method assisted performance
by 1/3oxalic of
(singleLiNi 1/3Mn1/3Co1/3O2 electrodes synthesized using a wet-chemical
Co1/3 Odicarboxyl)
performance of LiNi Mn1/3 2 electrodesand tartaric using
synthesized (complexed dicarboxyl)
a wet-chemical acid.assisted
method It was
method
by oxalicassisted
reported that theby
(single oxalic (single
chelating
dicarboxyl) agent dicarboxyl)
(carboxylic-based
and tartaric and tartaric
(complexed acid) (complexed
provoked
dicarboxyl) dicarboxyl)
acid.decomposition
It was reportedacid.
duringIt was
that the
reported
synthesis
chelating ofthat the chelating
oxide(carboxylic-based
agent agent
powders and the acid) (carboxylic-based
gel precursor
provoked acid)
wasdecomposition provoked
burning because decomposition
the decomposed
during the synthesis during
acetate the
ions
of oxide
synthesis
acted
powders of
as and oxide
an oxidizer powders and the
[44]. The was
the gel precursor gel precursor
wet-chemical was
synthesis
burning because burning because
the techniques
decomposed the decomposed
areacetate
based ions acetate
on acted
the sample ions
as an
acted
oxidizeras[44].
preparation an via
oxidizer
The [44]. polymerization
inorganic
wet-chemical The wet-chemical
synthesis synthesis
reactions
techniques techniques
in solution.
are based The
on the samplearepreparation
based on
methods theinorganic
consist
via sample
of an
preparation reaction
acidification
polymerization viareactions
inorganic
using polymerization
organic (carboxylic)
in solution. The methods reactions
acids
consistin solution.
as of
complexing The methods
agents
an acidification consist
(chelate)
reaction of
likeorganic
using an
citric,
acidification
succinic,
(carboxylic) reaction
oxalic,
acidsand using organic
tartaric acids
as complexing (carboxylic)
including
agents the like
(chelate) acids
–COOH– as complexing
citric, carboxyl agents
groupsand
succinic, oxalic, (chelate)
thattartaric
act as fuel like
acidsduring citric,
includingthe
succinic,
the –COOH– carboxyl groups that act as fuel during the formation process of electrode powders. the
formation oxalic,
process and oftartaric acids
electrode including
powders. the –COOH– carboxyl groups that act as fuel during
formation process of electrode powders.

Figure
Figure 15.15. Peukert
Peukert plotsplots showing
showing the
the difference
difference in
in the
the electrochemical
electrochemical performance
performance of of
Figure
LiNi 1/3Mn15.
1/3CoPeukert plots showing
1/3O2 electrodes theusing
synthesized difference in the
wet-chemical electrochemical
method assisted by performance
oxalic and of
tartaric
LiNi1/3 Mn1/3 Co1/3 O2 electrodes synthesized using wet-chemical method assisted by oxalic and
LiNi
acid.1/3 Mn1/3 Co 1/3 O 2 electrodes synthesized using wet-chemical method assisted by oxalic and tartaric
tartaric acid.
acid.
Processing at high temperature is usually necessary to oxidize the TM ions under an oxygen
Processing at
Processing at high
high temperature is usually necessary to oxidize
oxidize the
the TM
TM ions under an
an oxygen
atmosphere to obtain a temperature
high degree is
ofusually necessary
crystallinity. to
However, the annealingions underneeds
process oxygen
to be
atmosphere
atmosphere to
to obtain
obtain a
a high
high degree
degree of
of crystallinity.
crystallinity. However,
However, the
the annealing
annealing process
process needs
needs to be
to be
carefully conducted because high temperature favours (i) the growth of large crystallites, which is
carefully conducted because high temperature favours (i) the growth of large crystallites, which is
Materials 2016, 9, 595 16 of 26

carefully conducted
Materials 2016, 9, 595 because high temperature favours (i) the growth of large crystallites, which 16 of 26is not
desirable for use in high power density applications requiring nano-sized particles and (ii) a loss of
notoxide,
lithium desirable
Li2for use in
O, due tohigh power density
its volatility applications
that induced requiring nano-sized
sub-stoichiometric particles
powders. and (ii)
Figure 16 ashows
loss the
of lithium oxide, Li 2O, due to its volatility that induced sub-stoichiometric powders. Figure 16 shows
variation of the initial capacity loss of LiNi1/3 Mn1/3 Co1/3 O2 material synthesized by the tartaric acid
the variation of the initial capacity loss of LiNi1/3Mn1/3Co1/3O2 material synthesized by the tartaric
route as a function of the annealing temperature, Ta . The electrodes were cycled at C/20 (~10 mA¨ g´1 ).
acid route as a function of the annealing temperature, Ta. The electrodes were cycled at C/20
The minimum −1 of capacity loss is obtained for T « 900 ˝ C, which corresponds to an optimized particle
(~10 mA·g ). The minimum of capacity loss ais obtained for Ta ≈ 900 °C, which corresponds to an
with optimized
good crystallinity
particle with andgood
morphology forand
crystallinity electrode function,
morphology but alsofunction,
for electrode to an ordered
but alsolattice
to an with
minimum
ordered cation
latticemixing.
with minimum cation mixing.

Figure 16. Initial capacity loss of LiNi1/3Mn1/3Co1/3O2 electrodes cycled at C/20 as a function of the
Figure 16. Initial capacity loss of LiNi1/3 Mn1/3 Co1/3 O2 electrodes cycled at C/20 as a function of the
annealing temperature.
annealing temperature.
3.6. Effect of Small Deviation of Co Content
3.6. Effect of Small Deviation of Co Content
In this section, we investigate the deviation of the local environment of cations for different
In this section,
compositions LiNiwe0.33+δinvestigate
Mn0.33+δCo0.33-2δthe
O2 deviation
(0.025 ≤ δ ≤of the local
0.075) environment
synthesized by sol-gelofcitrate
cations forNote
route. different
that the use
compositions LiNiof0.33+δ
citric
Mnacid0.33+δ(tricarboxyl)
Co O
0.33-2δ 2 is beneficial
(0.025 ď δ ďto generate
0.075) a gel
synthesized instead
by of
sol-geloxalic acid
citrate route.
(dicarboxyl), which produces a precipitate. Single phased oxides
Note that the use of citric acid (tricarboxyl) is beneficial to generate a gel instead of oxalic acid with the typical layered
rhombohedral
(dicarboxyl), whichstructure
produceswere obtained after
a precipitate. Singlefiring at 900
phased °C forwith
oxides 24 h.
theFigure
typical17 layered
displaysrhombohedral
the TEM
images (a–c) of NMC samples with an average particle size of about 200–350 nm, indicating that each
structure were obtained after firing at 900 ˝ C for 24 h. Figure 17 displays the TEM images (a–c) of NMC
particle is composed of a few crystallites (<L> = 70 nm). The change of particle morphology is clearly
samples with an average particle size of about 200–350 nm, indicating that each particle is composed
evidenced by the TEM pictures; we observed octahedron-like (δ = 0.025) and spherical like particles
of a few
(δ = crystallites
0.05 and 0.075). (<L>An= HRTEM70 nm). imageThe change
(Figureof particle
17d) of a NMC morphology
nanoparticleis clearly
displays evidenced
bright- and by the
TEM dark-band
pictures; we observed
contrasts withoctahedron-like
widths of a few nm. (δ =In0.025) and spherical
each band like particles
contrast, there is a fringe(δ = 0.05 with
contrast and a0.075).
An HRTEM
spacing imageof 0.47 (Figure
nm that17d) of a NMC
corresponds nanoparticle
to the inter-planar displays
spacingbright- and dark-band
of the (003) hexagonal plane.contrastsThe with
widths of a few nm. In each band contrast, there is a fringe contrast
electron diffraction pattern (inset) confirms the crystallization in the R3m rhombohedral structure.with a spacing of 0.47 nm that
corresponds to theininter-planar
The regularity spacing
the lattice fringes of the
implies that(003) hexagonalis plane.
no dislocation detected The electron
in the layered diffraction
structure. As pattern
envisaged
(inset) confirmsfrom our HRTEM studies,
the crystallization in the theR3mlocalized
rhombohedral domain-like features
structure. Theareregularity
only observedin theinlattice
nano-scale.
fringes implies that The nospecific surface is
dislocation area SBET slightly
detected in thechanged
layered with the increasing
structure. As envisagedcobalt from
content ourfrom
HRTEM
2.42 to 2.76 m 2·g−1, which confirms the particles’ size evolution evidenced by TEM analysis.
studies, the localized domain-like features are only observed in nano-scale. The specific surface area
Rietveld refinements of XRD patterns show that the cation mixing is lower than 2.2% in all
SBET slightly changed with the increasing cobalt content from 2.42 to 2.76 m2 ¨ g´1 , which confirms the
samples owing to the stabilization of the layered structure by the cobalt. XRD results suggest that the
particles’ size evolution evidenced by TEM analysis.
deformation of a lattice is associated with the substitution of (Ni, Mn) for Co, which is only local in
Rietveld
nature. Onrefinements
another hand,ofthis XRDlocalpatterns
deformation show that the
generates cation
local strainmixing
fields thatis are
lower than 2.2%
responsible for ain all
samples owing to the stabilization of the layered structure by the cobalt.
broadening of the XRD lines. Indeed, as the cobalt concentration decreases, the width of the XRD XRD results suggest that the
deformation of a lattice
lines increases, so that isthe
associated
splitting with
of thethe substitution
(006)/(102) of (Ni, Mn)
and (108)/(110) Bragg forlines
Co, could
whichbeisobserved
only local in
nature.
for On another This
all samples. hand, thissurprising
is not local deformation
since cobalt generates local strain
tends to stabilize fields thatlayered
the hexagonal are responsible
structure. for a
The deviation
broadening of the XRDfrom stoichiometry,
lines. Indeed, δ,asgenerates
the cobalt a strain, adding todecreases,
concentration the microscopic
the widthstrainofinthetheXRD
unit lines
cell due to replacement of transition-metal ions in the intralayer block
increases, so that the splitting of the (006)/(102) and (108)/(110) Bragg lines could be observed for all and to the cationic disorder,
i.e., defects
samples. This iscreated by Ni2+ ions
not surprising in the
since interlayer
cobalt tends space. The profile
to stabilize of the Bragg
the hexagonal lines is
layered thus the The
structure.
combination of the Scherrer’s equation for crystallite size and the Bragg’s law for diffraction,
deviation from stoichiometry, δ, generates a strain, adding to the microscopic strain in the unit cell due
according to the equation
to replacement of transition-metal ions in the intralayer block and to the cationic disorder, i.e., defects
Materials 2016, 9, 595 17 of 26

created by Ni2+ ions in the interlayer space. The profile of the Bragg lines is thus the combination of
the Materials
Scherrer’s2016,equation
9, 595 for crystallite size and the Bragg’s law for diffraction, according to the17
equation
of 26

Materials 2016, 9, 595 17 of 26

2 2
2 2 2 K λ
A E
2 e 2 sin Kθ `
2 2 2
2B cos
2
θ
“ 16
B cos   16 e sin   2 22 L2 (7) (7)
2 2 2 K  2 L
B cos   16 e sin   2
(7)
B isBthe L
wherewhere is thefull-width
full-widthatathalf-maximum
half-maximum (fwhm) (fwhm)ininradian,
radian, θ is θ is
thethe diffraction
diffraction angle,
angle, and K and is aK is
a near-unity L 2
near-unity constant related to crystallite shape. The crystallite size L and micro-strain local <e > are<e >
where constant
B is the related
full-width to
at crystallite
half-maximum shape.
(fwhm) The
in crystallite
radian, θ is size
the and
diffraction micro-strain
angle, and K local
is2 a
near-unityby
are determined
determined constant
by usingrelated
Equation to crystallite shape.the
(7). Indeed,
Indeed, Thestrain
the crystallite
strain (<e 2 >)
size 1/2
1/2 Lincreases
and micro-strain
increases importantly 2> are
local <ewith with
using Equation (7). (<e 2>) importantly the the
determined
stoichiometry
stoichiometry by
deviation using
deviation δ, asEquation
shown
δ, as (7). Indeed,
shownininFigure
Figure18. the
18.On strain
On the (<e 2>)1/2 increases importantly with the
the other hand,
hand,we wefind
findthat L ≤L80
that6060≤ ď 80 nm
ď nm for for
stoichiometry deviation δ, as shown in Figure 18. On the other hand, we find that 60 ≤ L ≤ 80 nm for
all the
all the samples,
samples, so so that
that thethereplacement
replacementof of cobalt
cobalt does
does not
notsignificantly
significantly affect thethe
affect coherence
coherencelength.
length.
all the samples, so that the replacement of cobalt does not significantly affect the coherence length.
ThisThis is further
is further evidence
evidence thatthat
the theLiCoO
LiCoO2 -like
This is further evidence that the LiCoO
2-like framework
framework isisdisturbed
disturbedbyby the incorporation
the incorporation
2-like framework is disturbed by the incorporation of a great
of aofgreat
a great
quantity
quantityquantityof Mn
of Mn of and and
Ni Ni ions
ions [45].
[45].
Mn and Ni ions [45].

Figure 17.TEM
(a–c) (a–c) images
TEM images of individual
of individual LiNi0.33+δMn
LiNi Mn0.33+δCo 0.33-2δO2 nanoparticles with δ = 0.025,
Figure 17. 0.33+δ 0.33+δ Co0.33-2δ O2 nanoparticles with δ = 0.025,
0.05, and 0.075, respectively; (d) HRTEM image of a nanoparticle (δ = 0.025) showing lattice fringes
0.05,Figure
and 0.075, respectively;
17. (a–c) TEM images (d)ofHRTEM image
individual LiNiof a nanoparticle
0.33+δ Mn0.33+δCo0.33-2δ(δ
O2=nanoparticles
0.025) showing
withlattice fringes
δ = 0.025,
consistent with the interspacing of the (003) planes of the R3m layered structure.
0.05, and 0.075, respectively; (d) HRTEM image of a nanoparticle
consistent with the interspacing of the (003) planes of the R3m layered structure. (δ = 0.025) showing lattice fringes
consistent with the interspacing of the (003) planes of the R3m layered structure.

Figure 18. Evolution of the strain (<e2>)1/2 with the deviation from stoichiometry δ in
LiNi0.33+δMn0.33+δCo0.33-2δO2 samples synthesized by the sol-gel method.

Figure
Figure 18. 18. Evolution
Evolution of of the
the strain
strain (<e
(<e22>)
>)1/2 with
1/2
withthe
thedeviation
deviationfrom
fromstoichiometry δ in
stoichiometry δ in
LiNi 0.33+δMn0.33+δCo0.33-2δO2 samples synthesized by the sol-gel method.
LiNi0.33+δ Mn0.33+δ Co0.33-2δ O2 samples synthesized by the sol-gel method.
electrode microstructure and morphology. Moreover, the high crystallinity of material improves its
performance because insertion and de-insertion processes occur along specific crystallographic sites
and directions.
The electrochemical tests showed that the positive electrode of composition δ = 0.025 displays a
good electrochemical performance associated with the high stability of the layered framework. The
Materials 2016, 9, 595 18 of 26
discharge capacity decreases from 210 (C/12), 150 (1C) to 69 mAh·g−1 (10C) when cycled in the
potential window 2.0–4.6 V vs. Li0/Li+, which shows that this material is well suited to develop
high-powered
As mentioned batteries
above, at the
the electrochemical
industrial scale performance
for use in fastofcharge/discharge devices,to
materials is subordinate e.g.,
theHEV, due
electrode
to its small concentration
microstructure and morphology. of cation mixingthe
Moreover, andhigh
high structural of
crystallinity integrity
material[21]. Capacity
improves retention of
its performance
CE1: 82.3%
because and CE
insertion 2: 95.2%
and was obtained
de-insertion processes with this along
occur electrode, which
specific delivered a gravimetric
crystallographic capacity
sites and directions.
197.8The mAh·g −1 at 90% DOD
electrochemical at C/5
tests rate. that
showed The the
ratepositive
performance of Li//NMC
electrode cells is depicted
of composition δ = 0.025 as Peukert
displays a
plots electrochemical
good in Figure 19. We observed a associated
performance large decreasewith inthethe discharge
high stability capacity for high
of the layered values ofThe
framework. Co
substitution
discharge (δ = 0.075),
capacity which from
decreases is related with the150
210 (C/12), increasing
(1C) to cationic
69 mAh¨mixing [46]. when cycled in the
g´1 (10C)
Notewindow
potential in Section 3.2 the
2.0–4.6 samples
V vs. Li /Liwere
0 + prepared
, which showswith δ = 0.
that this Amongis them
material the (442)
well suited sample
to develop
delivered discharge capacity at C/5 is about 170 mAh·g −1. On the other hand, the samples in this
high-powered batteries at the industrial scale for use in fast charge/discharge devices, e.g., HEV, due
section
to wereconcentration
its small prepared with ofδcation
≠ 0. This is a significant
mixing differenceintegrity
and high structural between[21].
the 444 electrode
Capacity material
retention of
(Section
CE 1 : 82.3%3.2) with
and CE the
2 : δ =
95.2%0.075
was in the
obtainedpresent
with section,
this which
electrode, delivered
which only
delivered 110
a mAh·g −1 at C/5. This
gravimetric capacity
resultmAh¨
197.8 confirms
g´1 that
at 90% theDODdeviation
at C/5 of rate.
δ from Thezero
rateresults in a degradation
performance of Li//NMC of the
cellselectrochemical
is depicted as
properties,
Peukert plotsbecause
in Figure it induces a strain afield
19. We observed largeand a localin deformation
decrease the dischargeofcapacity
the lattice quantified
for high values ofin
Figure
Co 18.
substitution (δ = 0.075), which is related with the increasing cationic mixing [46].

250

LiNi0.33+Mn0.33+Co0.33-2O2
200
Capacity (mAh/g)

150

100

50 =0.025
=0.050
=0.075
0
0. 01 0.1 1 10 100
C-rate

Figure
Figure 19.19. Peukert
Peukert plots
plots forfor Li//LiNi
Li//LiNi 0.33+δMn 0.33+δCo
0.33+δ 0.33+δ Co 0.33-2δO2O
0.33-2δ cells.
2 cells.

3.7. Layered-Layered Integrated Materials

Note in Section 3.2 the samples were prepared with δ = 0. Among them the (442) sample delivered
discharge capacity at C/5 1 . On the other hand, the samples in this section were
g´energy
In order to meet theis demand
about 170for mAh¨
high density batteries, it is necessary to develop
prepared
high-capacitywith cathode
δ ‰ 0. This is a significant
materials that are difference betweengood
safe and present the 444 electrode material
electrochemical (Section 3.2)
performance. For
with the = 0.075 in the present section, which delivered only 110 mAh¨ g ´1 at C/5. This result
such a purpose, Li-rich oxides with the layered-layered integrated (LLL) configuration of
δ
confirms
composition thatyLi
the2MnO
deviation
3•(1 −ofy)LiMO
δ from 2zero results
, where M in a degradation
stands for Mn orofathe electrochemical
mixture of Mn with properties,
another
because
transition it metal
induces a strain
that can befield and asubstituted
partially local deformation
for Mn,ofaretheoflattice quantified
particular in Figure
interest. The LLI 18.materials
have been the subject of extensive works that have been reviewed in [47]. However many problems
3.7.
still Layered-Layered
have to be solved.Integrated Materials
Current debates on structure and reaction mechanism, problems on
electrochemical properties, and
In order to meet the demand for keys to the future
high studydensity
energy of thesebatteries,
materialsithave been reviewed
is necessary by Yu
to develop
and Zhou [48].cathode materials that are safe and present good electrochemical performance. For such
high-capacity
In the following,
a purpose, we report
Li-rich oxides experiments
with the on Li(Niintegrated
layered-layered xLi(1/3-2x/3)Mn
(LLL) )O2, which canof
(2/3-x/3)configuration becomposition
rewritten in
two-component
yLi 2 MnO3 ‚(1 ´ y)LiMOnotation as yLiM
2 , where 2MnO 3•(1for
stands − Mny)LiNi Mn½O2; of
or a½mixture it Mnofferswithseveral
anotheradvantages over
transition metal
that can be partially substituted for Mn, are of particular interest. The LLI materials have been the
subject of extensive works that have been reviewed in [47]. However many problems still have to be
solved. Current debates on structure and reaction mechanism, problems on electrochemical properties,
and keys to the future study of these materials have been reviewed by Yu and Zhou [48].
In the following, we report experiments on Li(Nix Li(1/3-2x/3) Mn(2/3-x/3) )O2 , which can be rewritten
in two-component notation as yLi2 MnO3 ‚(1 ´ y)LiNi 1 Mn 1 O2 ; it offers several advantages over
2 2
Materials 2016, 9, 595 19 of 26

conventional cathode ´1 , good structural stability,

Materials 2016, 9, 595 materials: a specific capacity as high as 250 mAh¨ g 19 of 26
and high capacity retention at high voltage cutoff [49]. The choice of Ni doping is justified by the
conventional
fact that Ni playscathode materials:
a positive role ainspecific
the O2capacity
´ ions’ as high as 250
oxidation tomAh·g
−1, good structural stability,
O2 [50]. By extracting the Li ions
with and high capacityoxygen
a concomitant retention at hightovoltage
release form acutoff
layered[49]. MnO
The choice
2
of Ni doping
component at is justified
ca. 4.6–4.8 by the fact
V vs. Li0 /Li+ ,
that Ni plays a positive role in the O2− ions’ oxidation to O2 [50]. By extracting the Li ions with a
the Li2 MnO3 component is considered to have two functions: (i) the stabilization of the electrode
concomitant oxygen release to form a layered MnO2 component at ca. 4.6–4.8 V vs. Li0/Li+, the
structure and (ii) the enhancement of the discharge capacity. In this section we report the study of
Li2MnO3 component is considered to have two functions: (i) the stabilization of the electrode
yLi2 MnO ´ y)(LiNi
3 ‚(1 and
structure Mn0.5 O2 ) samples
(ii) the0.5enhancement with y =capacity.
of the discharge 0.0, 0.3Inand this0.5 synthesized
section we reportby thecitrate
study of sol-gel
method. These
yLi2MnO 3•(1oxides
− y)(LiNi are0.5Mn
commonly viewed
0.5O2) samples withasy integrated
= 0.0, 0.3 and composites of layered
0.5 synthesized Li2 MnO
by citrate sol-gel3 with
method.C/2m
monoclinic Thesesymmetry
oxides areand layered viewed
commonly LiNi0.5 Mn 0.5 O2 withcomposites
as integrated rhombohedral R3m symmetry.
of layered Li2MnO3 with
Figure
monoclinic20 shows the morphology
C/2m symmetry and layeredof LiNi
the 0.5
LLL samples
Mn0.5 with y = 0.0, 0.3,
O2 with rhombohedral R3mand 0.5 synthesized by
symmetry.
a citrate–gel method
Figure 20 shows usingtheacetate salts.ofThese
morphology the LLL TEM images
samples reveal
with highly
y = 0.0, 0.3, andordered single crystalline
0.5 synthesized by a
citrate–gel
particles methodshape
with regular using and
acetate salts. Thesefor
morphology TEMall images reveal All
the samples. highly
theordered
powders single crystalline
consist of primary
particles
particles smallerwiththan
regular 500shape
nm.and Themorphology
particles offortheall Li
the1.134
samples. All0.566
Ni0.3 Mn the Opowders consist of primary
2 sample are smaller in size
particles smaller than 500 nm. The particles of the Li 1.134Ni0.3Mn0.566O2 sample are smaller in size
(~150 nm) and nearly monodisperse; however, a slight tendency to agglomerate is observed by SEM
(~150 nm) and nearly monodisperse; however, a slight tendency to agglomerate is observed by SEM
measurements (not shown here). The HRTEM micrograph (image d) shows that the Li1.2 Ni0.2 Mn0.6 O2
measurements (not shown here). The HRTEM micrograph (image d) shows that the Li1.2Ni0.2Mn0.6O2
powders are formed of well-crystallized hexagonal-shaped particles. The crystal faces are well defined
powders are formed of well-crystallized hexagonal-shaped particles. The crystal faces are well
and the distribution
defined of particlesofisparticles
and the distribution uniform. is uniform.

Figure 20. HRTEM images of Li-rich cathode materials yLi2MnO3•(1 − y)(LiNi0.5Mn0.5O2). (a) y = 0.0
Figure 20. HRTEM images of Li-rich cathode materials yLi2 MnO3 ‚(1 ´ y)(LiNi0.5 Mn0.5 O2 ).
(LiNi0.5Mn0.5O2); (b) y = 0.3 (Li1.134Ni0.3Mn0.566O2); (c) y = 0.5 (Li1.2Ni0.2Mn0.6O2); (d) image magnification
(a) y = 0.0 (LiNi0.5 Mn0.5 O2 ); (b) y = 0.3 (Li1.134 Ni0.3 Mn0.566 O2 ); (c) y = 0.5 (Li1.2 Ni0.2 Mn0.6 O2 ); (d) image
for Li1.2Ni0.2Mn0.6O2 showing the hexagonal shape of nanoparticles.
magnification for Li1.2 Ni0.2 Mn0.6 O2 showing the hexagonal shape of nanoparticles.
In the inset (image d), one observes well-defined fringes corresponding to the typical α-NaFeO2
layered structure
In the inset (imagewith interplanar
d), one observesdistance of about
well-defined 0.47 corresponding
fringes nm, which is tothethe
distance
typicalofα-NaFeO
the 2
close-packed
layered structure with(003) interplanar
planes of thedistance
rhombohedral
of about R30.47
m lattice (or theis(001)
nm, which planes of of
the distance thethe
monoclinic
close-packed
(003) C2/m
planeslattice).
of theThese fringes are observed
rhombohedral over (or
R3m lattice the the
whole region,
(001) planeswhich means
of the that the pure
monoclinic C2/m single
lattice).
layered structured phase is built up throughout the careful synthesis recipe of wet chemistry.
These fringes are observed over the whole region, which means that the pure single layered structured
Analysis of XRD patterns show that the ch/ah ratio increases linearly with the Li concentration. This
phase is built up throughout the careful synthesis recipe of wet chemistry. Analysis of XRD patterns
effect is attributable to the increase of concentration of Mn4+ ions, the ionic radius of which (0.54 Å) is
showsmaller
that the ch /a
than h ratio
that of Niincreases linearly
2+ (0.69 Å) in withcoordination.
octahedral the Li concentration. This effect is attributable to the
increase of concentration of Mn 4+ ions, the ionic radius of which (0.54 Å) is smaller than that of Ni2+
Figure 21 presents the electrochemical tests of Li//Li(NixLi(1/3-2x/3)Mn(2/3-x/3))O2 coin cells cycled at
(0.69 C/10
Å) inrate
octahedral
(30 mA·gcoordination.
−1) in the potential range 2.0–4.8 V vs. Li0/Li+. The initial discharge capacity of the

Figure
LiNi0.5Mn 210.5O
presents
2 electrodetheis electrochemical
approximately 181testsmAh·g of−1 Li//Li(Ni x Li(1/3-2x/3)
with a capacity loss of 39MnmAh·g )O2 coin
−1, while
(2/3-x/3) high cells
cycleddischarge
at C/10 capacities
rate (30of 230
mA¨ and ´ 1
g 253) mAh·g −1 are obtained
in the potential for Li1.134
range Ni0.3Mn
2.0–4.8 V0.556
vs.O2 and 0
Li Li + . 0.2Mn
1.2Ni
/Li The0.6Oinitial
2

discharge capacity of the LiNi0.5 Mn0.5 O2 electrode is approximately 181 mAh¨ g´1 with a capacity
Materials 2016, 9, 595 20 of 26

loss Materials
of 39 mAh¨ g´1 , while high discharge capacities of 230 and 253 mAh¨ g´1 are obtained
2016, 9, 595 20 of 26 for
Li1.134 Ni0.3 Mn0.556 O2 and Li1.2 Ni0.2 Mn0.6 O2 samples, respectively. Upon increasing the lithium
samples, the
enrichment, respectively.
coulombic Upon increasing
efficiency thethe
after lithium enrichment,
2nd cycle slightlythe coulombic
increases efficiency
from 98.6% after the On
to 99.5%.
2nd cycle slightly increases from 98.6% to 99.5%. On the contrary, the irreversible
the contrary, the irreversible capacity loss in the first cycle slightly increases from 20 to 23 mAh¨ capacity loss in the g´1
first cycle slightly increases from 20 to 23 mAh·g−1 with the Li-rich oxides, i.e., Li1.134Ni0.3Mn0.556O2 and
with the Li-rich oxides, i.e., Li1.134 Ni0.3 Mn0.556 O2 and Li1.2 Ni0.2 Mn0.6 O2 , respectively. For all the
Li1.2Ni0.2Mn0.6O2, respectively. For all the cells, the first irreversible capacity associated with the high
cells, the first irreversible capacity associated with the high voltage plateau is due to the activation
voltage plateau is due to the activation of the Li2MnO3 component with extraction of lithium and
of the Li2 MnO
oxygen 3 component
release with 4.5
at approximately extraction of lithium
V. For subsequent andtheir
cycles oxygen release
coulombic at approximately
efficiency is stabilized, 4.5 V.
For subsequent
in contrast with cyclesthe their coulombic
behaviour efficiency
of the LiNi 0.5Mn0.5Ois2 stabilized,
electrode. The in contrast
potential with theshow
profiles behaviour
that theof the
LiNiinitial
0.5 Mn0.5 O2 electrode.
discharge capacityThe potential
located profiles
in the range showmAh·g
230–260 that the
−1 is initial
retaineddischarge
at 200–220capacity
mAh·g−1 located
after in
the range 230–260
30 cycles, while mAh¨
the g ´1 is retainedcompound
stoichiometric at 200–220LiNi mAh¨ 0.5Mng´ 1 2 only30displays
0.5Oafter cycles, while the stoichiometric
an initial discharge
capacityLiNiof 180 mAh·g ´1
0.5 O2. only displays an initial discharge capacity of 180 mAh¨ g .
−1
compound 0.5 Mn

Figure
Figure 21.21. Charge–discharge
Charge–dischargeprofiles of Li//Li(Ni
profiles of xLiLi//Li(Ni
(1/3-2x/3)Mn(2/3-x/3) )O2 coin cells:
x Li(1/3-2x/3) (a) LiNi
Mn(2/3-x/3) )O0.5Mn0.5O2;
2 coin cells:
(b) Li 1.134Ni0.3Mn0.556O2; and (c) Li1.2Ni0.2Mn0.6O2. Cycles were carried out at C/10 rate (30 mA·g−1)
(a) LiNi0.5 Mn0.5 O2 ; (b) Li1.134 Ni0.3 Mn0.556 O2 ; and (c) Li1.2 Ni0.2 Mn0.6 O2 . Cycles were carried
inC/10
out at the potential
rate (30range
mA¨2.0–4.8
g´1 ) inV the
vs. Li 0/Li+.
potential range 2.0–4.8 V vs. Li0 /Li+ .

The charge–discharge reactions of a Li-rich electrode are described by the activation of the two
The charge–discharge
components LiNi0.5Mn0.5Oreactions
2 and Li2MnOof a3 Li-rich
as followselectrode
[51]. Letare described
us consider theby theofactivation
case Li1.2Ni0.2Mnof the
0.6O2, two

components
otherwise LiNi 0.5 Mn
written as0.5 O2 2and
0.5Li MnOLi 2 MnO3 0.5
3•0.5LiNi asMnfollows
0.5O2. [51]. Let us consider the case of Li1.2 Ni0.2 Mn0.6 O2 ,

otherwise(1)written as 0.5Li
First step of chargeMnO reaction by Mn 2 . the R3m phase with a regular Li extraction
0.5 Oof
activation
‚0.5LiNi +
2 3 0.5
from the 3b site of the layered lattice:
(1) First step of charge reaction by activation of the R3m phase with a regular Li extraction from +

the 3b site of the2MnO

0.5Li layered lattice:
3•0.5LiNi0.5Mn0.5O2 → 0.5Li2MnO3•0.5Li0.5Ni0.5Mn0.5O2 + 0.5Li+ + 0.5e−. (8)
(2) Second
0.5Li step of charge reaction by activation of Li2MnO3 inducing loss of Li+and oxygen
-
2 MnO3 ‚0.5LiNi0.5 Mn0.5 O2 Ñ 0.5Li2 MnO3 ‚0.5Li0.5 Ni0.5 Mn0.5 O2 ` 0.5Li ` 0.5e . (8)
release at the end of the charge i.e., potential above 4.5 V:
(2)0.5Li
Second
2MnOstep of 0.5
3•0.5Li charge
Ni0.5Mn0.5O2 → (0.5
reaction by activation
− α)Li2MnOof Li2 MnO
3•αMnO 3 inducing
2•0.5Li loss
0.5Ni0.5Mn of2 +Li2αLi
0.5O and+ +oxygen release
(9)
at the end of the charge i.e., potential above 2αe 4.5
− + 0.5αO
V: 2.

0.5Li2 MnO3 ‚0.5Li0.5 Ni0.5 Mn0.5 O2 Ñ p0.5 ´ αqLi2 MnO3 ‚αMnO2 ‚0.5Li0.5 Ni0.5 Mn0.5 O2 ` 2αLi+ ` 2αe- ` 0.5αO2 . (9)
Materials 2016, 9, 595 21 of 26

Materials 2016, 9, 595 21 of 26

(3) Discharge process by the insertion of the R3m phase and formation of the new LiMnO2
lithiated phase:
(3) Discharge process by the insertion of the R3m phase and formation of the new LiMnO2
lithiated phase:
p0.5 ´ αqLi2 MnO3 ‚αMnO2 ‚0.5Li0.5 Ni0.5 Mn0.5 O2 ` p0.5 ` αqLi+ ` p0.5 ` αqe- Ñ p0.5 ´ αqLi2 MnO3 ‚αLiMnO2 ‚0.5LiNi0.5 Mn0.5 O2 . (10)
(0.5 − α)Li2MnO3•αMnO2•0.5Li0.5Ni0.5Mn0.5O2 + (0.5 + α)Li+ + (0.5 + α)e− → (10)
(0.5 − α)Li2MnO3•αLiMnO2•0.5LiNi0.5Mn0.5O2.
Figure 22 illustrates the first charge–discharge profile of a Li//Li1.2 Ni0.2 Mn0.6 O2 cell cycled at
C/10, showingFigure 22
theillustrates
mechanism the first charge–discharge
of the activation of profile
Li2 MnOof a3 Li//Li1.2Ni0.2
and LiNi 0.5Mn0.6O
Mn cell
0.52 O cycled at C/10, The
2 components.
showing
typical featurestheofmechanism
the Li//Li(Niof thexactivation
Li(1/3-2x/3)ofMn Li(2/3-x/3)
2MnO3 and )O2 LiNi Mn0.5O
coin0.5cells 2 components.
cycled at C/10The typical
in the voltage
features of the Li//Li(Ni
0 + xLi(1/3-2x/3)Mn(2/3-x/3))O2 coin cells cycled at C/10 in the voltage range 2.0–4.8 V
range 2.0–4.8 V vs. Li /Li are shown in Figure 23. With an initial discharge capacity of 252.8 mAh¨ g´1 ,
vs. Li0/Li+ are shown in Figure 23. With an initial discharge capacity of 252.8 mAh·g−1, this electrode,
this electrode, Li1.2 Ni0.2 Mn0.6 O2 , appears to be the best among the studied materials. The capacity
Li1.2Ni0.2Mn0.6O2, appears to be the best among the studied ´ materials. The capacity decreased slightly
decreased slightly upon cycling at the rate−1 of 1.01 mAh¨ g 1 per cycle. These results are comparable
upon cycling at the rate of 1.01 mAh·g per cycle. These results are comparable to those in the
to those in the literature [52–54]. Liu et al. [53] reported a discharge capacity 253 mAh¨ g´1 for
literature [52–54]. Liu et al. [53] reported a discharge capacity 253 mAh·g−1 for MnO2-coated
MnOLi 2 -coated Li O2Ni
1.2Ni0.2Mn0.61.2 0.2 Mn
cycled at0.6 O2 cycled
C/10. Zhao et at C/10.
al. [54] Zhao
showed et the
that al. same
[54] showed that the doped
electrode materials same electrode
with
materials doped with Sn delivered a lower capacity
initial discharge ´ 1
Sn delivered a lower initial discharge of 212.6 capacity
mAh·g−1, of 212.6seems
which mAh¨tog be, whichdue to seems
the to
be due to the formation
formation of big secondary
of big secondary particles synthesized
particles synthesized via a carbonateviaco-precipitation
a carbonate co-precipitation
method. method.

Materials 2016, 9, 595 22 of 26

rangeFigure
Figure 122. >22.1 The
> xThe 2y;first
−first thecharge–discharge
charge–discharge profile
second step is profile
the ofaaprocess
of
redox Li//Li1.21.2
Li//Li NiNi
Co 3+Mn
0.2
→ 0.6O24+cell
0.2 Mn
Co 0.6in cycled
O2the
cell at C/10,
x <at1showing
cycled
range C/10, the
− 2y, asshowing
there is
the mechanism
practically
mechanism of
no overlap the activation of
between the
of the activation Li2MnO3 and LiNi0.5Mn0.5O2 components.
of Litwo redox reactions
LiNi0.5[38].
2 MnO 3 and Mn0.5 O2 components.

According to Figure 23, we find here that the Ni doping has improved the capacity but it had no
effect on the cycling stability, since the slope of the capacity as a function of the cycle number is the
same for the different compositions. This is in contrast with prior conclusions of Lu et al., who found
that the cycling stability was significantly enhanced in samples with x > 1/4 in
Li(NixLi1/3-2x/3Mn2/3-x/3)O2 [55–57]. Indeed, the stability of the Li-rich materials is the main problem that
still has to be solved before any application can be envisioned [58–62]. The characterization of a
0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 “composite” by the synchrotron X-ray powder diffraction has
shown complex reaction pathways that depend on the current density [63]. As the Li content relative
to Ni and Mn decreased, the LLL materials were observed to be either single-phase layered,
two-phase layered-rocksalt, or three-phase layered-rocksalt-spinel, depending on their location
within the Li-Mn-Ni-O phase diagram [64]. Gu et al. have shown that, upon 300 cycles of
charge/discharge, the structure of Li1.2Ni0.2Mn0.6O2 is transformed into a spinel structure [65].
Therefore, the evolution of the LLLs and their related degradation upon cycling is a complex
problem that is not entirely understood—in contrast with the NMC case, where the delithiation
proceeds in two well-identified steps in LixNiyMnyCo1−2yO2: the first step of the delithiation is
associated with the redox reaction involving the nickel ions: Ni2+ → Ni3+ → Ni4+ in the composition
Figure
Cyclic23. performance
Cyclic performance of Li//Li(Ni
of Li//Li(Ni xLi(1/3-2x/3)Mn(2/3-x/3))O2 electrodes at C/10.
Figure 23. x Li(1/3-2x/3) Mn(2/3-x/3) )O2 electrodes at C/10.

4. Concluding Remarks
In this work we have examined several cathode materials for Li-ion batteries, all of them
crystallizing in a layered network. The effect of the synthesis procedure on the cationic distribution
in NMC compounds with various configurations and the merit of the hierarchical
nano-/micro-structures was investigated. The local Ni2+ arrangement on the lithium layers has been
estimated as a function of the composition, the Li/metal ratio, and the metal/chelating agent used in
the sample preparation. It has been demonstrated that the high crystallinity is essential to obtain
Materials 2016, 9, 595 22 of 26

According to Figure 23, we find here that the Ni doping has improved the capacity but it
had no effect on the cycling stability, since the slope of the capacity as a function of the cycle
number is the same for the different compositions. This is in contrast with prior conclusions of
Lu et al., who found that the cycling stability was significantly enhanced in samples with x > 1/4 in
Li(Nix Li1/3-2x/3 Mn2/3-x/3 )O2 [55–57]. Indeed, the stability of the Li-rich materials is the main problem
that still has to be solved before any application can be envisioned [58–62]. The characterization of
a 0.5Li2 MnO3 ¨ 0.5LiMn0.42 Ni0.42 Co0.16 O2 “composite” by the synchrotron X-ray powder diffraction
has shown complex reaction pathways that depend on the current density [63]. As the Li content
relative to Ni and Mn decreased, the LLL materials were observed to be either single-phase layered,
two-phase layered-rocksalt, or three-phase layered-rocksalt-spinel, depending on their location within
the Li-Mn-Ni-O phase diagram [64]. Gu et al. have shown that, upon 300 cycles of charge/discharge,
the structure of Li1.2 Ni0.2 Mn0.6 O2 is transformed into a spinel structure [65]. Therefore, the evolution
of the LLLs and their related degradation upon cycling is a complex problem that is not entirely
understood—in contrast with the NMC case, where the delithiation proceeds in two well-identified
steps in Lix Niy Mny Co1´2y O2 : the first step of the delithiation is associated with the redox reaction
involving the nickel ions: Ni2+ Ñ Ni3+ Ñ Ni4+ in the composition range 1 > x > 1 ´ 2y; the second step
is the redox process Co3+ Ñ Co4+ in the range x < 1 ´ 2y, as there is practically no overlap between the
two redox reactions [38].

4. Concluding Remarks
In this work we have examined several cathode materials for Li-ion batteries, all of them
crystallizing in a layered network. The effect of the synthesis procedure on the cationic distribution in
NMC compounds with various configurations and the merit of the hierarchical nano-/micro-structures
was investigated. The local Ni2+ arrangement on the lithium layers has been estimated as a function of
the composition, the Li/metal ratio, and the metal/chelating agent used in the sample preparation.
It has been demonstrated that the high crystallinity is essential to obtain accurate electrochemical
performance and to maintain the structural integrity of the electrode lattice during cycling. Among
the mixed transition metal oxides, Li1/3 Ni1/3 Mn1/3 CoO2 appears to be an attractive material because
the combination of Ni, Mn, and Co can provide many advantages such as high specific capacity
compared with LiCoO2 . Its good structural integrity is due to the absence of Mn3+ Jahn–Teller ions.
Both Rietveld refinements and magnetic measurements have shown that the Li/Ni cation mixing on
the 3b Wyckoff site of the interslab space was very small (concentration of Ni2+ -3b ions lower than
2%) and consistent with the structural model (Li1-δ Niδ )3b (Liδ Nix-δ Mny Co1-x-y )3a O2 results obtained by
adjusting parameters of synthesis. Electrochemical tests carried out by galvanostatic charge–discharge
cycling reflected the high degree of sample optimization.
A significant increase in the specific capacity was obtained with Li2 MnO3 and LiNi0.5 Mn0.5 O2
composites (Li(Nix Li(1/3-2x/3) Mn(2/3-x/3) )O2 with 0.0 ď x ď 0.5), which are Li-rich compounds having
an intergrown structure (or integrated layered-layered). Their specific capacity reached 200 mAh¨ g´1
after 30 cycles or more. However, while the mechanism of the lithiation–delithiation process is well
understood in NMC materials, which in addition is reversible, that of the Li-rich compounds is still
under debate and the problem of degradation upon cycling is not yet solved. The rate capability is a
problem that seems more difficult to overcome. Li1.2 Ni0.2 Mn0.6 O2 core encapsulated by a nanospinel
(LiNix Mn2-x O4 ) layer with the thickness of about 10 nm combined the advantages of the highly
conductive spinel surface and high capacity layered core was able to deliver 274.6 mAh¨ g´1 at 1C
rate [61]. Song et al. used graphene oxide (GO) to wrap their Li(Li0.2 Mn0.54 Ni0.13 Co0.13 )O2 material [66].
In addition to the highly conductive cubic spinel transformed from the layered phase on the surface
during electrochemical cycling [67], the graphene oxide was also reduced. As a result, this composite
delivered 201 mAh¨ g´1 at a current density of 2500 mA¨ g´1 . However, even if coating the LLL
particles with different materials improves the capacity retention, none of them is currently able to
prevent the degradation upon many cycles. This is thus the main problem that remains to be solved,
Materials 2016, 9, 595 23 of 26

together with the voltage decay of LLLs over a long period of cycling, before these promising materials
can find an industrial development.

Acknowledgments: The authors are grateful to Xiaoyu Zhang, Ashraf Abdel-Ghany, and Nourredine Amdouni,
Julie Trottier, and René Veillette for their technical assistance in sample preparation, electrochemical measurements,
and HRTEM imaging.
Author Contributions: Writing of the manuscript was done by Christian Julien and Alain Mauger. Supervision
of the experimental works was performed by Karim Zaghib and Henri Groult.
Conflicts of Interest: The authors declare no conflict of interest.

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