Island-covered Lithium Cobaltite Oxides
The present invention relates to a powderous lithium transition metal oxide, containing a
special type of Mn and Ni bearing LiCoO2. The cathode powder can be prepared at large
scale by a low-cost process. More specifically, the preparation is the sintering of a mixture
of a cobalt containing precursor, like LiCoO2, a Ni-Mn-Co containing precursor, like
mixed hydroxide MOOH, and Li2CO3. The sintering temperature is high enough to allow
for an exchange of cations between the LiCoO2 and Li-Ni-Mn-Co oxide phases being
formed, which results in a very specific morphology with a compositional gradient of the
different transition metals. The lithium transition metal oxide powder can be used as a
cathode active material in rechargeable lithium batteries.
Despite of some inherent limitations like poor safety and high cost LiCoO2 still is the most
applied cathode material for rechargeable lithium batteries. There is a strong demand
driven by customer expectation to increase the energy density of rechargeable lithium
batteries. One way to improve the energy density is to increase the charge voltage, which
requires more robust cathode materials which can be charged at higher voltage. Problems
which appear or become more severe if the charging voltage is increased are (a) low safety,
(b) poor storage properties during storage of charged batteries at elevated temperature and
(c) poor cycling stability. Numerous approaches have been disclosed to address these
problems. Partial improvements have been achieved but the basic problems have not been
fully resolved.
Beside the demand to increase the energy density, it is essential that rechargeable batteries
meet the power requirements. That means that the battery as a whole and particularly the
active cathode material itself has a sufficient high rate performance.
There exist general trends. Careful studying of published results on cathode materials
allows to better understand the limitations of LiCoO2 based rechargeable lithium batteries.
One basic limitation originates from the surface area dilemma. Increase rate performance
(i.e. high power) can be met by increasing the surface area because the solid-state lithium
diffusion length can be decreased; which results in an improved rate performance.
However, a high surface area increases the area where unwanted side reactions between
electrolyte and charged cathode take place. These side reactions are the course of poor
safety, poor cycling stability at elevated voltage and of poor storage properties of charged
cathode at elevated temperature. Furthermore, high surface area materials tends to have a
low packing density which reduces the volumetric energy density.
Another basic limitation originates from the cobalt stoichiometry. Lithium-nickel-
manganese-cobalt oxide based cathode materials (like LiMn1/3Ni 1/3Co1/3O2) have higher
stability against reactions between electrolyte and cathode than UCoO2, and the raw
material cost is lower, but these materials suffer from a lower volumetric energy density
and these materials typically have a lower lithium diffusion constant.
It can be concluded that there exist basic limitations in:
- Surface area: Low surface area cathode materials are desired to achieve high safety,
improved density and high stability during storage; however, the surface area cannot be
lowered too much because this will lower the rate performance.
- Composition: LiMO2 cathodes, where M dominantly is cobalt is desired to achieve high
lithium diffusion rate and high volumetric energy density; however a high content of
cobalt causes poor safety properties, increased cost and an inferior high voltage stability.
A solution to this dilemma would be to increase the diffusion constant. Increased D would
allow to lower the surface area without loosing rate performance.
LiMO2, where M=Ni-Mn-Co with Ni:Mn>l, has been previously disclosed. US 6,040,090
(Sanyo), for example, discloses a wide range of compositions LiMO2 (M=Mn, Ni, Co)
including LiMO2 with Ni:Mn>l. The patent application discloses that LiMO2 has a high
degree of crystallinity (small HWFM of peaks in the X-ray diffraction pattern). LiCoO2
doped with Ni and Mn has for example been disclosed in patent US7,078,128.
US7,078,128 discloses LiCoO2, doped by equal amounts of Ni and Mn is a preferred
implementation.
European patent application EP1716609 Al discloses a L1MO2 based active cathode
material where the composition of the particles depends on the size of me particles,
particularly, the cobalt content of particles decreases with decreasing size of the particles.
The decrease of cobalt content originates from a core-shell structured particles, where the
Mn-Ni containing shell has the same thickness, covering a LiCoO2 core. As a result, if the
particles are small, the LiCoO2 core is small and the cobalt content of the whole particle is
low.
European patent application EP1556915 Al discloses a LiMO2 with a gradient of
transition metal composition. The gradient originates from a mixed hydroxide shell,
covering the core which has significantly different metal composition. In a preferred
implementation the core is LiCoO2. After sintering a gradient of transition metal
composition with a radial change of stoichiometry is achieved, and a LiMO2 shell covers a
LiCoO2 based core. During sintering, cobalt diffuses from the LiCoO2 core to the LiMO2
shell. At the same time much less Ni diffuses from the LiMO2 shell into the LiCoO2 core.
Therefore the shell swells and the LiCoO2 core contracts. A swelling shell covering a
shrinking core typically causes the creation of voids between shell and core. These voids
are highly undesired.
It is an object of the present invention to define a cathode material having a high rate
performance, and showing high stability during extended cycling at high charge voltage.
The high temperature storage properties are also improved. This is achieved by a
powderous lithium transition metal oxide comprising Mn and Ni bearing LiCoO2 particles,
said particles having Mn and Ni enriched islands on their surface, said islands comprising
at least 5 mol%, and preferably at least 10 mol% of Mn.
The Mn and Ni enriched islands preferably have a thickness of at least 100 nm and cover
less than 70%, and preferably less than 50% of the surface of said Mn and Ni bearing
UC0O2 particles. Also, the Mn concentration in said islands is preferably at least 4 mol%,
and preferably at least 7 mol% higher than the Mn concentration in the bulk of said Mn
and Ni bearing LiCoO2 particles.
In a further embodiment the Ni concentration in said Mn and Ni enriched islands is at least
2 mol%, and preferably at least 6 mol% higher than the Ni concentration in the bulk of
said Mn and Ni bearing LiCoO2 particles.Preferably the Mn and Ni bearing LiCoO2
particles comprise at least 3 mol%, and more preferably at least 10 mol% of both Ni and
Mn. In one preferential embodiment the crystallographic lattice constants a and c of said
Mn and Ni bearing LiCoO2 particles are respectively 2.815 +/- 0.002 and 14.05 +/- 0.01.
Also, it is preferred that the Mn and Ni bearing LiCoO2 particles particles are monolithic
and free of inner porosities. Preferably also, the size distribution of said Mn and Ni
bearing LiCoO2 particles has a d50 larger than 10, preferably larger man 15, and most
preferably larger than 20 µm.
In a further preferred embodiment, the powderous lithium transition metal oxide
comprises between 30 wt.% and 95 wt.% of said Mn and Ni bearing LiCo02 particles.
The invention also covers a lithium transition metal oxide having a first phase consisting
of said Mn and Ni bearing LiCoO2 particles, and further comprising a second island-free
phase having a generalized formula of Li1+aM'1-aO2±b, with -0.03 < a < 0.05 and b < 0.02,
M' = NimMnCo1-m-a with m≥n, and 0.1 < m+n < 0.9. The powderous lithium transition
metal oxide then preferably has a total composition of LixMyO2±δ with 0.97 < x < 1.03,
0.97 < y < 1.03, x + y = 2 and δ< 0.05, and M = Co1-f-gNifMng, with 0.05 < f + g < 0.5 and
f ≥ g. It is also preferred that 0.98 < x/y < 1.00. In another preferred emboidment, said
oxide consists of only two phases, the first being said Mn and Ni bearing LiCoO2
particles, and the second being said island-free phase.
It is also preferred that the crystallographic lattice constants a' and c' of said island-free
phase have the following relationship with the lattice constants a" and c" of a
corresponding island-free phase of a reference lithium transition metal (Mref) oxide,
having the same composition LixMyO2±δ and consisiting of pure LiCoO2 particles and said
corresponding island-free phase:
0.980 < a'/a" < 0.998 and 0.9860 < c'/c" < 0.9985 ,
and preferably 0.990 < a/a" < 0.997 and 0.9920 < c'/c" < 0.9980.
If for example, the material of the actual invention, LiMO2 has been prepared from a Co
precursor and from a mixed metal hydroxide of composition M"=NimMnmCo1-m-n, then
the lattice constants a" and c" refer to a reference material with composition LiM"O2,
the different lattice constant a' and c' manifest that sufficient exchange of cations between
the LiCoO2 based first phase, and the island-free second phase has taken place.
The island-free phase preferably has secondary particles with a size distribution with a d50
between 2 and 10 micrometer, said secondary particles consisting of sintered agglomerates
of primary crystallites having a particle size distribution with a d50 between 0.5 and 2 urn.
In a further preferred embodiment both said Mn and Ni enriched islands and said island-
free phases further comprise Ti, whereby the Ti content is less than 10 mol% of M in the
oxide LixMyO2±δ
More preferred, the powderous lithium transition metal oxide further comprises less than 5
mol% of M of one or more dopants selected from the group consisting of Al and Mg, and
less than 1 mol% of M of one or more dopants selected from the group consisting of Be, B,
Ca, Zr, S, F, and P; in the oxide LixMyO2±δ
For the sake of simplicity, in the description, the Mn and Ni bearing LiCoO2 particles will
mostly be referred to as 'phase 1' or also as the 'modified LiCoO2 phase', and the island-
free phase having a generalized formula of Li1+aM'1-aO2±b will be referred to as the'
LiM'O2' (M'=Ni-Mn-Co) phase or 'phase 2' of the lithium transition metal oxide, which is
also referred to as the 'cathode material'.
The actual invention discloses that, surprisingly, the rate performance of mixtures of
LiCoO2 (phase 1) and LiM'O2 (M'=Ni-Mn-Co) with Ni:Mn ratio of > l (phase 2) is
dramatically improved if these mixtures have been heat treated with each other (co-
sintering) in a way which causes an exchange of cations between LiCoO2 and LiM'O2
during sintering, causing a distribution of composition of the particles of phase 1 and of
phase 2, At the same time a special morphology of the phase 1 particles (LiCoO2) is
obtained. The particles are partially covered by manganese containing LiM'O2 sheets. The
authors refer to this morphology as "island" morphology. At the same time, surprisingly,
the stability at high voltage is dramatically improved as well.
The modified LiCoO's morphology, has islands densely sintered to the bulk of the
modified LiCoO2, causing local gradients of transition metal stoichiometry. The islands
contain manganese in high concentration. Both the LiCoO2, as well as the LiM'O2
particles have a distribution of composition. Additionally, the LiM'O2 particles have a
morphology depending on the cobalt content. The size of primary crystallites increases
with cobalt content. Contrary to EP1556915 Al mentioned above, in the invention there is
no radial change of stoichiometry. It is rather a multi-center gradient with the LiM'O2
islands, located on the surface and acting as centers of the gradient Also, the only partial
coverage of the LiCoO2 by islands is a very important difference.
Another important aspect of the invention is that the islands not completely cover the
LiCoO2 particles. A complete coverage - with other words - a LiCoO2 core - LiM'O2
shell morphology can be achieved by precipitating mixed hydroxide onto the surface of
the LiCoO2. This approach has been described in above mentioned patent applications
EP1556915 Al and EP1716609 Al (Paulsen et al.). The case of the MOOH shell -
LiCoO2 core precursor has two major draw-backs, as described in Core-Shell Cathode
Material with Size-Dependent Composition, Jens M. Paulsen, Jong-Seok Jeong, and Ki-
Young Lee, Electrochem. Solid-State Lett., Volume 10, Issue 4, pp. Al01-A 105 (2007).
(1) the process is more expensive and (2) during sintering more cobalt diffuses from the
core into the shell. Thus the shell expands and the core shrinks at the same time. This
typically causes a partial separation of the shell from the core, causing large cavities.
These large cavities are very undesirable because (i) they increase the porosity of the
electrode - thus causing a lower energy density and (ii) they hinder the direct diffusion of
lithium across the cavity into or out of the core region of the LiCoO2 particle - thus
causing loss of rate performance.
The situation is different for the cathode materials of the actual invention. The manganese
containing islands cover only a fraction of the surface of the LiCoO2 particle. Therefore
the cobalt diffusion induced swelling of the islands and shrinking of the L1C0O2 core does
not cause the creation of large cavities. As a result a high volumetric density and a high
rate performance can be achieved.
The invention also covers an electrochemical cell comprising a cathode comprising as
active material the powderous lithium transition metal oxide described before.
A method for preparing the powderous lithium transition metal oxide described before
comprises the steps of:
- providing a mixture of LiCoO2 powder or a cobalt containing precursor compound
having a cobalt content of at least 90 mol%, and a Li-Ni-Mn-Co-oxide or a Ni-Mn-Co
precursor powder and optionally a Li-precursor compound, preferably lithium carbonate,
and
- sintering said mixture at a temperature T of at least 900°C, and preferably at least 950°C,
for a time t between 1 and 48 hrs,
so as to obtain Mn and Ni bearing LiCoO2 particles having Mn and Ni enriched islands on
their surface.
The cathode material is thus prepared by sintering a mixture of a LiCoO2 based powder
with a Li-Ni-Mn-Co-oxide or a Ni-Mn-Co containing powder and a source of lithium like
Li2CO3 at high temperature, exceeding 900°C. The temperature must be over 900°C, for
example 910°C or 920°C. During the sintering a partial exchange of cations between
LiCoO2 particles and the Ni-Mn containing particles takes place. It the sintering
temperature is low, then not enough cations are exchanged and the cathode does not show
high rate performance. If the sintering temperature is high, then the particles become too
dense, and the metal composition equilibrates too much, i.e. to too much exchange of
cations between LiCoO2 and Mn-Ni-Co takes place. In that case, there will be no Mn and
Ni enriched islands on the first phase particles.
Alternatively, a cobalt containing precursor powder (like cobalt oxide, cobalt hydroxide or
cobalt carbonate) can be mixed with a Ni-Mn-Co containing powder and a source of
lithium, followed by sintering at high temperature, preferably exceeding 950°C.
A method for preparing a powderous lithium transition metal oxide having the two phases
described above, comprises the steps of:
- providing a mixture of LiCoO2 powder or a cobalt containing precursor compound
having a cobalt content of at least 90 mol%, and a Li-Ni-Mn-Co-oxide or a Ni-Mn-Co
precursor powder and optionally a Li-precursor compound, preferably lithium carbonate,
and
- sintering said mixture at a temperature T of at least 900°C, and preferably at least 950°C,
for a time t between 1 and 48 hrs,
so as to obtain said Mn and Ni bearing LiCoO2 particles phase and said island-free phase
having crystallographic lattice constants a' and c', which have the following relationship
with the lattice constants a" and c" of said Li-Ni-Mn-Co-oxide or a reference lithium
transition metal (Mref) oxide obtained by sintering said Ni-Mn-Co precursor powder and
said Li-precursor compound at the same temperature T and for the same time t, said
relationship being
0.980 < a'/a" < 0.998 and 0.9860 < c'/c" < 0.9985 ,
and preferably 0.990 < a'/a" < 0.997 and 0.9920 < c'/c" < 0.9980.
In these methods, the Ni-Mn-Co precursor powder preferably is a transition metal
hydroxide, oxyhydroxide, carbonate, oxycarbonate, or lithium transition metal compound,
in which the transition metal composition M" is M" = NioMnpCo1-o-p, with o + p > 0.5 and
o > p. Also, the Ni-Mn-Co precursor powder preferably comprises between 5 and 70
mol% of the transition metal content of said powderous lithium transition metal oxide.
In one embodiment, the used LiCoO2 powder has a tap density of at least 2 g/cm3, and
consists of monolithic particles with a d50 of at least 10, preferably at least 15, and most
preferably at least 20 µm.
On the other hand, the cobalt containing precursor compound preferably is either one of
more of cobalt hydroxide, oxyhydroxide or carbonate.
In another embodiment, said LiC0O2 or cobalt containing precursor comprises at least
80% of the transition metal of said powderous lithium transition metal oxide, and the Ni-
Mn-Co comprising precursor powder consists of particles having a particle size
distribution with a d50 between 1 and 3 µm.
In yet another embodiment, said LiCoO2 or cobalt containing precursor comprises less
than 80% of the transition metal of said powderous lithium transition metal oxide, and the
Ni-Mn-Co comprising precursor consists of particles of the agglomerated type having a
particle size distribution with a d50 between 4 and 10 µm.
In both of these embodiments, the Ni-Mn-Co comprising precursor can furthermore
comprise Ti, preferably in the form of T1O2 particles with a d50 less than l00 nm.
Details of the invention are now further discussed below.
The cathode material of the actual invention is a powder, containing modified LiCoO2 and
mostly, but not exclusively, a second transition metal phase. Both phases are lithium-
transition-metal oxide phases with a layered crystal structure: ordered rocksalt type crystal
structure - space group r-3m. The cathodes can be stoichiometry Li1M1O2, with M being
cobalt, manganese and/or nickel, or slightly lithium deficient (Li1-xM1+xO2) or lithium rich
Li1+xM1-xO2, with x < 0.3. The existence of oxygen non-stoichiometry is generally doubted.
So the oxygen stoichiometry is aprox. 2.0, but it can not be excluded that the cathodes are
slightly oxygen deficient or rich in oxygen. Thus the total composition is LixMyO2±δ with
0.97
10-20 micrometer) which are dense and
monolithic. Suitable cobalt precursors are commercial LiCoO2, or high density (tap
density > 2 g/cm3) cobalt hydroxide, oxyhydroxide or carbonate. Suitable shape of the
precursors are spherical or irregularly potato shaped particles, for example.
The two typical implementation are not to be seen as alternatives, rather as two extreme
examples. It would, for example, be possible to use a Ni-Mn-Co precursor with bimodal
size distribution, containing small (below 0.5 - 1.5 micrometer) and larger (4-8
micrometer) agglomerated particles, where a large fraction of small particles are
consumed to form the islands and where a large fraction of the larger particles disconnects
during sintering. It is also possible to use smaller cobalt particles and submicrometer
MOOH, in this case an extreme high rate performance can be expected
The reaction - formation of a manganese containing island, accompanied by cation
exchange between cobalt and nickel - is the same in both implementations. The inventors
believe that an essential aspect which causes the formation of the island morphology is the
lower mobility of (4 valent) manganese compared to that of 3 valent nickel in LiCoO2 and
3 valent cobalt in LiM'O2. Also, the (4 valent) manganese does not take part in the
electrochemical insertion/extraction of lithium during charge/discharge of the batteries
some of the manganese can be replaced by other cations. A suitable cation is also titanium.
Similar as manganese it is electrochemically inert, has low mobility and it can be doped
into a Ni-Mn-Co precursor. For example, similar as manganese, titanium can be doped
into LiNiO2.
Another important aspect of the invention is that a high rate performance is achieved even
if the cathode material is slightly Lithium sub-stoichiometric. We observed that the
highest rate performance is achieved if the total lithium content per transition metal was
approx. 0.98, i.e. less than unity. This is very surprising, because in the case of lithium
transition metal oxides Li1+zM1-zO2 where M contains nickel it is widely accepted that a
lithium deficiency causes cation mixing (that are nickel atoms misplaced on
crystallographic lithium sites), and the increased cation mixing causes a poor rate
performance.
The Figures illustrating the invention are summarized as follows:
Fig. 1: SEM micrographs of the samples REF1 and REF2.
Fig. 2: SEM micrograph of the samples CX2 and CX3.
Fig. 3: SEM micrograph of the sample EX1 and EX3.
Fig. 4: SEM micrographs of the samples EX2 - phase 1 and 2.
Fig. 5: SEM micrographs of particles of EX 1 for EDS analysis.
Fig. 6: EDS mapping for a phase 1 particle of EX1.
Fig. 7: SEM micrographs of particles of EX1 for EDS analysis.
Fig. 8: SEM micrographs of phase 2 particles of EX1 for EDS analysis.
Fig. 9: Cycling behaviour of commercial LiCoO2 (REF1) and sample EX4.
Fig. 10: SEM micrograph of sample EX5E and CX6.
Fig. 11: Crystallographic map of REF1-2, CX2-3 and EX1-3.
Fig. 12: Crystallographic map of REF1-2, CX5 and EX4-5.
Fig. 13: X-ray diffraction pattern of CX2, CX4 & CX5, and EX1.
Fig. 14: X-ray diffraction pattern of CX6 and EX9E.
Fig. 15: The voltage profile of CX2, CX3 and EX1-EX3 during slow discharge.
Fig. 16: Cycling behaviour and rate performance of sample EX1.
Fig. 17: Rate performance of sample CX6 is compared with EX5E.
In the following examples some aspects of the actual invention will be further explained.
The following Tables give an overview of the test conditions and results.
Table 1 gives a summary of samples and preparation conditions.
Table 2 gives a summary of X-ray and BET surface are data.
Table 3 gives a summary of the electrochemical results obtained from coin cells.
Reference examples
The following reference samples were used:
- REFl-LiCoO2 is a commercial LiCoO2 and has a d50 of =20 µm and consists of
monolithic, dense particles.
- REF2 - LiM'O2 has been prepared from mixed hydroxide MOOH and Li2CO3 at 950 °C
in air; the Li:M ratio was Li:M-1.01:l, and M'-Ni0.53Mn0.27Co0.2- REF2 has an
agglomerated morphology.
Both sample REF1 and REF2 were re-heated at 850 °C during 8 hrs before coin cell
assembly and BET measurement. X-ray diffraction pattern is measured and a Rietveld
refinement is performed. Figure 1 shows SEM micrographs of the samples REF1 and
REF2. The left figure shows REF1 in a 1000 x magnification. Particles are irregularly
shaped. No island morphology is present. The right figure shows REF2 in a 2500 x
magnification. Particles are agglomerated consisting of primary crystallites sintered into
larger irregularly shaped secondary particles.
Calculated example
For a hypothetical calculated sample CC1, being a mixture of 60% REFl-LiCoO2 and
40% REF2-LiM'O2 expected values for BET surface area, capacities and rate performance
are estimated by calculating the weighed average of the corresponding values of REF1 and
REF2.
Comparative examples
Example CX2: a cathode powder is prepared by mixing 60% of REF1-LiCoO2 with 40%
REF2-LiM'O2. Before mixing, both REFl-LiCoO2 and REF2-LiM'O2 were heat treated at
850 °C during 5 hrs in air. The total composition of the final CX2 cathode is LiM'O2 with
M'=Co0.68Ni0.21Mn0-11. Figure 2a shows a SEM micrograph (5000 x magnification) of the
mixed sample CX2. BET surface area of the mixed powder CX2 is measured. No island
morphology can be observed. Coin cells are prepared and the capacity, irreversible
capacity, cycling stability and rate performance is measured. X-ray diffraction pattern is
measured and a Rietveld refinement is performed. SEM micrographs are taken.
Tables 2 and 3 show that sample CX2 has properties which are roughly similar as the
weighed average of the precursors, in hypothetical sample CC1. The mixing does not
bring a significant benefit in rate performance or cycling stability. The SEM micrograph
confirms the absence of island morphology of LiCoO2 particles. The Rietveld refinement
confirms that the lattice constants obtained from the X-ray pattern of the mixture is the
same as the lattice constants obtained from the X-ray pattern of the LiCoO2 and LiM'O2,
respectively.
Example CX3: a cathode powder is prepared by mixing 60% of REFl-LiCoO2 with 40%
REF2-LiM'O2. The mixture is heat treated at 850°C during 5 hrs in air resulting in sample
CX3. The total composition of the cathode is LiM'O2 with M' = Co0.68Ni0.21Mn0.11, the
same as CX2. Figure 2b shows a SEM micrograph of the sample CX3. The magnification
is 2500 x. No island morphology is present.
Apparently, properties like cycling stability and rate performance of sample CX3 (being a
heat treated mixture) are slightly improved compared to CX2 (being a mixture of heat
treated samples). The Rietveld refinement confirms that the lattice constants of the
composing compounds LiM'O2 and LiCoO2 have not significantly changed during the heat
treatment. The constants of REF1 is the same as those of phase 1 in CX2 and CX3, and
the lattice constants of REF2 is the same as those of phase 2 in CX2 and CX3.
Example CX4: a cathode powder, being a heat treated mixture, is prepared identically to
the procedure described in comparative example CX3, with the exception that the heating
was made at 900 °C for 5 hrs instead of 850°C for 5 firs, resulting in sample CX4. Coin
cells are prepared. X-ray diffraction pattern is measured and a Rietveld refinement is
performed. SEM micrographs are taken.
Tables 2 and 3 show that sample CX4 has properties which are roughly similar to those of
CX3 which was prepared at lower temperature. The SEM micrograph show that an island
morphology is basically absent. X-ray diffraction shows a phase mixture of two phases,
the first having the lattice constants of REFl-LiCoO2 the second having the lattice
constants similar as sample REF2-LiM'O2- Obviously, no significant diffusion of Co from
phase 1 LiC0O2 into the second phase LiM'O2 has occurred. The rate performance is
similar as that of sample CX3. This comparative example showed that an increasing of
heat treatment temperature from 850 °C to 900 °C does not bring any significant
improvement of coin cell performance.
Examples of the invention
Example 1 (EX1): a cathode powder is prepared by mixing 60% of commercial LiCoO2
(Sample REF1) with 40% MOOH mixed transition metal hydroxide and Li2CO3. The
Li2CO3: MOOH ratio and the mixed hydroxide is the same as used for the preparation of
REF2-LiM'O2. The total composition of the cathode powder is LiM'O2 with
M-Co0.68Ni0.21Mn0.11, the same as the total composition of CX2 and CX3. The mixture is
heated at 970 °C during 8 hrs in air, resulting in sample EX1.
Coin cells are prepared. X-ray diffraction pattern is measured and a Rietveld refinement is
performed. SEM micrographs are taken. Figure 3a shows a SEM micrograph of the
sample EX1. The magnification is 5000 x. Two types of particles are present: (a) Phase 1:
dense, irregularly shaped LiCo02 based particles having the particularly island
morphology and (b) Phase 2: Agglomerated type LiM'O2 particles: the primary crystallite
size have a broadened distribution. Phase 1 is clearly illustrated in Fig. 3c. The EDS
analysis (see below) emphasizes the presence of Mn in the islands on the surface of the
modified LiCoO2 particles.
Properties such as cycling stability and rate performance are much better than for
hypothetical sample CC1 and significantly improved if compared with the samples CX2
and CX3.
The SEM micrograph confirms the presence of island morphology of LiCoO2 particles.
The Rietveld refinement confirms that the lattice constants of phase 1 (LiCoO2) has not
changed during the heat treatment but the lattice constant of phase 2 (LiM'O2) has changed
significantly. The change of lattice constant of LiM'O2 proves that a significant exchange
of cations between phase 1 and phase 2 has taken part.
Examples EX2 and EX3: cathode powders were prepared and investigated similarly to
EX1 of Example 1 with the exception that the sintering temperature was 960 and 950 °C
respectively (sintering time: 8 hrs). Figures 3b shows a SEM micrographs of the sample
EX3. Figure 4 shows a SEM micrographs of the two phases of sample EX2: the left
pictures shows predominantly phase 2 particles, the right picture predominantly phase 1
particles, where it can also be seen that the phase 1 particles are much larger than the
smaller phase 2 agglomerates.
Again, properties such as cycling stability and rate performance are much better than for
hypothetical sample CC1 and significantly improved if compared with the samples CX2
and CX3.
The SEM micrograph confirms the presence of island morphology of LiCoO2 particles.
The Rietveld refinement confirms that the lattice constants of L1C0O2 has not changed
during the heat treatment but the lattice constant of the LiM'Ch phase has changed
significantly. Comparing EX1,2 and 3, it can be concluded that the change is more
significant at higher temperature, indicating that (a) the amount of Co diffusing into
LiM'O2 increases with temperature but, at the same time (b) the improved properties do
not depend sensitively on the amount of Co in the LiM'O2 phase.
EDS analysis of samples
Using energy-dispersive X-ray spectrometry (EDS) the composition of the LiC0O2 (phase
1) and LiM'O2 (phase 2) of the samples CX2 and CX3 (comparative examples) and of
example EX1 can be studied.
EDS analysis is a powerful tool to investigate the composition of particles near to the
surface. EDS is especially powerful to monitor changes and trends, but it is less powerful
to get accurate quantitative results. Table 4 discloses results of the EDS analysis of the
reference samples REF1 and REF2 which will be used as reference points for the EDS
analysis of the more complex samples CX2, CX3 and EX1.
Sample REF1 (LiCoO2) was investigated by EDS spectroscopy. A spectrum measured
from many particles was collected. The magnification was 1000 x, the region which was
scanned is the one shown in Figure 1. Similar the EDS spectrum of sample REF2 was
collected at 1000 x magnification.
Table 4: ICP and EDS measurement of transition metal contents of REF 1 and 2.
Comparing the results obtained from ICP chemical analysis and EDS analysis shows that
EDS
(1) estimates the transition metal ratios approximately correctly
(2) exaggerates the sulfur content (sulfur impurity possibly located at the surface)
The cathode sample EX1 was investigated by applying EDS analysis to single particles.
The EDS spectrum of 6 different particles of phase 1 was obtained. All particles showed
the island morphology. The SEM micrographs of the 6 particles are shown in Figure 5.
EDS analysis clearly shows that particles of phase 1 (LiCoO2), contain large amounts (>
15%) of nickel and manganese, (see Table 5 below) This is very surprising because the
Rietveld refinement of the X-ray diffraction pattern showed that phase 1 (containing Ni
and Mn) has the same lattice constants as LiCoO2. Furthermore, 5 of the 6 particles have a
Ni:Mn ratio above 3.0. This shows mat more nickel than manganese has diffused into the
1st phase. During sintering an exchange of cations has taken place where dominantly
nickel but also manganese has entered from the LiM'O2 particles into the LiCoO2 particles.
The EDS analysis also confirms that particles of the 1st phase (LiCoO2) have a distribution
of composition with a varying transition metal composition.
Table 5: EDS measurement of transition metal contents of particles of EX 1
2 particles (Particle #1 and particle #2) of the 6 particles of Table 5 were investigated by
EDS mapping. The EDS mapping of particle #1 in Figure 6 shows that "islands" have a
higher content of manganese whereas the areas in-between the island, the "oceans" (or
bulk) have a low content of manganese. Particles #4 and #6 were further investigated by
spot EDS analysis (see Table 6). Figure 7 shows the locations of the spots. Spot spectra
were collected.
Table 6: EDS measurement of transition metal contents of different regions of particles of
EX1
All "island" spots (X2, X4, X6, X7) have a clearly lower Ni:Mn ratio than that of the
whole particle (Table 5). All "ocean" spots (X5, X8, X9) have a much lower manganese
content than that of the whole particle. The example confirms that particles with island
morphology have high Mn content in most islands and low manganese content in-between
islands. Obviously there exists a manganese gradient with islands being the center of the
gradient.
The EDS spectrum of 3 single particles of the second phase (LiM'O2) of sample EX1 was
collected. These particles originate from the MOOH which has the same metal
composition as sample REF2, with Ni:Mn ratio of approx. 2.0 and a cobalt content of
approx. 20%. Figure 8 shows the SEM micrographs. These three particles obviously have
different sized crystallites. Particle 1 (left) has crystallites of approx. 0.5-1.5 µm; Particle
2 (middle) has crystallites of approx. 1-2 µm and Particle 3 (right) has crystallites of
approx. 1.5-3 µm. Similar, the EDS spectra of single LiM'O2 particles (phase 2) of sample
CX2 and CX3 was collected. All results are reported in Table 7.
The cobalt content of the second phase LiM'O2 particles of sample EX1 has increased
significantly during sintering. This is in sharp contrast to the results of LiM'O2 particles of
the samples CX2 and CX3 which have roughly the same EDS spectrum as sample REF2.
This observation displays that during sintering of EX1 an exchange of cations has taken
place where cobalt from the LiCoO2 (phase 1) has entered into the LiM'O2 (phase 2)
particles. Furthermore, comparing the SEM micrographs in Figure 8 and the data of the
table shows that the size of primary crystallites and the cobalt content of phase 2 particles
of sample EX1 correlate. Obviously, as cobalt diffuses into the LiM'O2 , the sinterability
of the LiM'O2 is enhanced causing a faster crystallite growth.
Example 4: Jet-milling of precursors
A submicrometer sized mixed hydroxide was prepared by jet-milling mixed hydroxide
MOOH. The MOOH is the same as used for the preparation of the REF2-LiM'O2. The
particle size distribution was measured by laser diffraction. After 3 times jet-milling 80%
of the volume consist of particles with size below 1 micrometer.
90% by weight of commercial LiCoO2 (Sample REFl, with 20 micrometer particles) and
10% of the 3 times jet-milled MOOH were mixed with Li2CO3. For 1 mol jet-milled
MOOH 1/2 mol Li2CO3 was added. ( The Li.M ratio is the same as used for the preparation
of the REF2-LiM'O2.) After mixing the sample was sintered at 970°C for 8 hrs.
The final sample EX4 was investigated by SEM, BET surface analysis and X-ray
diffraction. Coin cells were prepared. Rate performance and cycle stability was measured.
Figure 9 compares the rate performance (cell voltage V vs. capacity in mAh/g) of the
commercial LiCoO2 (REFl) on the left (A), with the rate performance of sample EX4 on
the right (B). The Figures show the discharge voltage profile during C/10, C/5, C/2,1C.
1.5C, 2C, 3C, 5C and 10C rate where 1C (corresponding to a discharge in one hour) is
defined as 160 mA/g. The temperature was kept constant at 24°C, and the voltage range
was 4.3-3.0V. Obviously, the rate performance has been dramatically increased. The SEM
micrograph (not shown) clearly shows that an island morphology is present.
Study of co-sintering conditions
A sample CX5 was prepared identically to the samples EX1, EX2, EX3, with the
exception that the sintering temperature was lowered to 900 °C (sintering time: 8 hrs).
The sample was clearly different from EX1, EX2, EX3. The BET surface area was much
larger: 0.35 m2/g. X-ray diffraction shows a phase mixture of two phases, the first having
the lattice constants of REFl-LiCoO2, the second having the lattice constants similar as
sample REF2-LiM'O2. Obviously, no significant diffusion of Co from the phase 1 LiCoO2
into the second phase LiM'O2 has occurred. Similar, the volume fraction of the 2nd phase
is clearly less, this being consistent with less Co having diffused into phase 2 (LiM'O2).
The electrochemical properties are inferior (Table 3). A poor cycling stability is observed
(the fading rate at 4.5V is about 2-3 times faster than that of samples EX1-EX3). The rate
performance is significantly lower (87.5% at 3C rate, compared with 90-91% for samples
EX1, EX2, EX3. The rate performance is similar as mat of sample CX3. The SEM
micrographs (not shown) shows some small LiM'O2 particles attached on the surface of
the larger LiCoO2, but an island morphology is basically absent.
A cathode powder CX6 is prepared and analyzed identically to the cathode powder of
Example 4. However, a different precursor for the second phase LiM'O2 was used. In this
example 90% REFl LiCoO2 are mixed with 10% of a jetmilled precursor and 0.05 mol%
Li2CO3. The precursor is lithium deficient Li1-xM1+xO2 . The precursor was prepared
similar as the REF2-LiM'O2 with the exception that the Li:M ratio was 0.9 and the
temperature was 900°C. After preparation, the precursor was jetmilled twice, resulting in a
sub-micrometer particle product. Particle size distribution was measured by laser
diffraction in water. The particle size distribution is bi-modal, with about 50% of the
volume having a size between 0.05-1 µm (maximum at approx. 0.3 urn) and the remaining
50% of the volume have a size between 1-6 µm (maximum at approx. 2 µm). The mixture
was heated at 970°C for 8h in air. X-ray diffraction pattern is measured and a Rietveld
refinement is performed. SEM micrographs are taken. Coin cells are prepared.
The ray diffraction pattern shows basically one phase with lattice constants similar to
LiCoO2. A second LiM'O2 cannot be clearly distinguished. (This is different to the sample
of Example 4 which clearly showed the presence of a second Phase). Figure 10b shows a
SEM micrograph. Very few LiM'O2 particles (=phase 2) of agglomerated type are present.
Almost all particles are LiCoO2 based (=phase l). These particles generally have a very
smooth surface. Clearly, island morphology is absent Consistent with this observation is
the observed very low BET surface area of only 0.14 m2/g
Apparently, the sample CX6 has been sintered more efficiently than the sample EX4.
Possibly too much cobalt has diffused from the phase 1 LiCoO2 into the phase 2 LiM'O2.
At the same time, the small LiM'CO2 particles have been consumed by the larger LiCoO2
particles, and possibly, the manganese cations in the LiCoO2 have been diluted, and as a
result, island morphology is absent. The compositions of phase 2 and phase 1 effectively
have approached each other. The second phase, even comprising a larger fraction of the
cathode than in the case of less sintered samples, now is very similar to phase 1 and the
phases cannot be clearly distinguished anymore, for example by X-ray.
Electrochemical testing shows that:
(a) The slope of voltage profile at the end of discharge disappeared - this is consistent
with phase 2
LiM'O2 basically being absent,
(b) The rate performance is significantly lower than that of sample EX4,
(c) the cycling stability is inferior
It can be concluded that the island morphology and the presence of a second phase is
essential to obtain a high rate performance. Furthermore, there exists a quite narrow
window to achieve high rate cathodes. If the sintering is too strong (Sample CX6), the
islands disappear because of high transition metal diffusion, if the sintering is not enough
(Sample CX3 and CX4) then islands don't form because of unsufficient transition metal
diffusion. Table 2 and 3 summarize the obtained data. In order to perform the process of
the invention correctly, it is necessary to establish a temperature vs. sintering time matrix
where the SEM micrographs of the obtained product clearly shows the island
configuration of EX 1-4. If co-sintering has not occurred phase 2 is clearly distinguished
and pure LiCoO2, without island morphology, is observed. If the co-sintering has taken
place too intensively, phase 2 has nearly disappeared, and the resulting Li-Co-Ni-Mn-
oxide has a smooth surface with rounded edges.
If the two phases LiCoO2 and LiM'O2 are present it is also possible to measure the lattice
constants of the obtained samples, and compare them with a reference sample which is a
sintered compound obtained only with the precursors needed to obtain phase 2 (absence of
LiCoO2 or a corresponding cobalt precursor). The relationship between the obtained
lattice constants should be within the limits cited before.
Influence of sub-stoichiometry
The following examples (EX5A to F) will show that the electrochemical properties can be
further improved if the samples have a slight substoicheometry of lithium. Samples were
prepared identically as sample EX4, with the exception that less Li2CO3 was added, and in
some cases the sintering temperature was slightly raised.
In all cases 90% of 20 urn LiCoO2 (=REF1) was mixed with 10% of jetmilled MOOH and
Li2CO3. The molar ratio of Li (in Li2CO3) to MOOH is given in Table 8 below. Table 8
also displays the sintering temperature and gives results of BET surface area measurement.
The column Li:M gives the results for the lithium to transition metal ratio obtained from
chemical analysis of the final samples. The chemical analysis results are very similar to
the expected values, if keeping in mind that the sample REF1 has a Li:Co of approx. 1.02,
and, depending on temperature, always a small amount of lithium evaporates during
sample preparation. Obviously, the samples EX5D, EX5E and EX5F are increasingly
lithium sub-stoichioemtric. SEM analysis was made and confirms that all 6 samples show
island morphology. The SEM micrograph of sample EX5E is displayed in Figure 10a. X-
ray analysis in all cases showed a mixture of two phases (see below).
Table 8: Analysis of sub-stoicheometric samples (sintering time: 8 hrs)
Coin cells were prepared and tested in similar conditions as described before. The results
are summarized in Table 9 below.
Electrochemical data were obtained from two sets of two coin cells. The first set of two
cells was tested using a cycling stability schedule. The other set was tested using a rate
performance schedule. The cycling stability schedule gives the following numbers: Qrev,
Qirr, fade rate (C/10) and fade rate (C1), listed in Tables 3 and 9. The electrochemical
data are the average of each set of two cells. Qrev and Qirr are the reversible capacity
(mAh/g) and irreversible capacity (%, Qirr=[QCh-QDC]/QCh) of the first cycle, measured
at C/10 rate. The numbers of the fade rate at C/10 is obtained by comparing the discharge
capacity at the slow (C/10) 3rd and 41st cycle, the fade rate at 1C is obtained by comparing
the discharge capacity at the faster (1C) 4th and 42nd cycle. From cycle 5 to 40 the cells
were cycled at C/5 charge and C/2 discharge rate at 4.5-3.0V. The fade rate is extrapolated
to 100 cycles.
The rate performance schedule gives the numbers 1C/0.1C, 2C/0.1C and 3C/0.1C for the
rate performance, listed in Table 3 and 9. The schedule is as follows. After 1 slow cycle
(C/10) the cells are charged at C/5 rate and discharged at increasing rate (C/5, C/2,1C,
1.5C, 2C, 3C, 5C and 10C). The voltage range is 4.3-3.0V.
In-order to measure the capacities and rate performance with high reliability, the electrode
loading (g/cm2) of cells was different. Cells tested for the stability schedule had approx.
12 mg/cm2 electrode loading. Cells tested with the rate schedule had approx. 5-6 mg/cm2
loading.
Table 9: Electrochemical data of sub-stoichiometric samples
The data in the tables show that the rate performance increases if the Li:M ratio is lowered.
The highest rate is obtained for the sample which is approx. 1.5% lithium sub-
stoichiometric. At the same time, the 1.5% lithium sub-stoichiometric sample EX5E
shows also the highest cycling stability at 4.5V. However, if the lithium sub-
stoichiometry is too large, then properties deteriorate. So sample EX5F, which is approx.
3% lithium sub-stoichiometric, has inferior capacity and very poor rate performance.
Crvstallographic maps
The X-ray diffraction pattern of the reference samples REF1, REF2, the comparative
samples CX2-CX3, and of the samples EX1-3 was obtained. Samples CX2, CX3, EX1-
EX3 are composed of two phases, a first phase, based on LiCoO2 and a second phase,
based on LiM'O2. The lattice constants of these phases were obtained by a two phase
Rietveld refinement and can be compared to the lattice constants of samples REF1
(LiCoO2) and REF2 (LiM'O2), which were obtained by a one-phase refinement.
Table 2 lists the results. Figure 11 shows the results in a suitable manner form which the
authors call a crystallographic map, plotting the hexagonal c-axis vs. the hexagonal a-axis.
The figure gives the crystallographic map of the samples REF1, REF2, CX2, CX3, EX1,
EX2 and EX3. The inlets show enlarged re-plots of small regions marked by a rectangle.
Table 2 and Figure 11 very clearly show that the lattice constant of phase 2 (LiM'O2) of
the samples EX1, EX2 and EX3 have significantly changed, away from the value of REF2,
whereas the lattice constants of phase 2 in CX2, CX3 is identical to those of REF2. The
change is more pronounced with increasing sintering temperature. Increasing the sintering
temperature causes the map location to move towards LiCoO2, away from the expected
REF2 position. This change of position on the map is typical for a solid state solution
between LiCoO2 and LiM'O2. Obviously cobalt has diffused from the phase 1 (LiCoO2)
into the particles of phase 2 (LiM'O2).
Surprisingly, the lattice constants of phase 1 (LiCoO2) did not change during the sintering.
All samples CX2, CX3 and EX1, EX2 and EX3 have lattice constants identically to those
of REFl.
The Rietveld refinement also yields the fraction of phase 2 (LiM'O2), which are listed in
Table 2. The data show that the fraction of phase 2 increases during sintering. The
fraction of LiM'O2 of sample CX2 should be 40%. Obviously the Rietveld gives larger
values for the LiM'O2 phase. This mistake is possibly caused by a re-arrangement of small
(phase 2, LiM'O2) and large (phase 1, LiCoO2) particles during X-ray sample preparation
which might cause an enrichment of phase 1 near to the surface. The effect might be
enhanced by preferred orientation of the particles of phase 1. However, neglecting this
mistake we observe a clear trend. The fraction of LiM'O2 increases with sintering
temperature. It is indicated that during sintering more Co diffuses from phase 1 (LiCoO2)
into phase 2 than Ni (and Mn) diffuses from phase 2 into phase 1.
Figure 12 shows a crystallographic map with datapoints of the samples EX4, EX5A-EX5F
and CX5, together with samples REF1, REF2. The datapoints were obtained by a two-
phase Rietveld refinement. The graph nicely displays that the lattice constants of phase 2
(LiM'O2) of EX4, EX5A-EX5F are in-between those of LiCoO2 - REFl and REF2-
LiM'O2. This is consistent with discussed diffusion of Co into the 2nd phase. At the same
time the lattice constants of phase 1 have not changed at all and are identical to those of
REFl-LiCoO2.
Figure 12 also compares sample CX5 with the samples EX4, EX5A-F based on their
location on a crystallographic map. It can be concluded that the lattice constants of phase
2 of CX5 are identical to REF2. This is consistent with the lower sintering temperature -
causing an in-sufficient cation exchange between phase 1 and phase 2.
X-rav diffraction patterns
The samples REF1 and REF2 have high crystallinity, hence they show an X-ray
diffraction pattern with sharp diffraction peaks. Figure 13 shows the X-ray diffractogram
(basis: scattering angle (deg)) of CX2, CX4, CX5 and EX1. All these samples have the
same overall composition. The inlet of figure 13 shows an enlarged re-plot of the region
marked by a rectangle. Sample CX2, being the mixture of (heat treated) REF1 and REF2
shows, as expected, a X-ray diffraction pattern which is the super position of the patterns
of REF1 and REF2. Even if the mixture is heat treated at 900°C (Sample CX4) or a
mixture of LiCoO2, mixed hydroxide and Li2CO3 (CX5), the X-ray diffraction pattern
remains basically the same. This tells us that the 1st phase LiC0O2 and the 2nd phase
LiM'O2 have not changed.
The situation, however, is very different for samples which are typical for the present
invention. Figure 13 shows that peak positions and the shape of peaks of sample EX1 has
changed. The peaks of phase 1 (LiCoO2 based) remain quite sharp sample and the position
is identical, however peaks of phase 2 (LiM'O2 based) have broadened significantly and
their position has clearly moved. The main reason of this broadening is the distribution of
Co and Ni stoichiometry. During sintering, Ni diffused away from the 2nd phase, and
cobalt diffuses into the 2nd phase. As a result, different particles and/or crystallites have a
different stoichiometry, each stoichiometry has its own peak position, so as a result a
broader diffraction peak is observed. In a Rietveld refinement it is difficult to simulate a
distribution of lattice constants. However, quite fortunately, a small crystal size causes a to
some degree similar peak broadening. So a Rietveld refinement of a cathode typical of the
present invention will show a large crystallite size for the first phase (LiC0O2 based) and a
much smaller crystallite size for the second phase (LiM'O2). At the same time, the peak
position of the diffraction peaks of the 2nd phase have moved significantly towards the
position of the 1st LiC0O2 phase.
Figure 14 shows the X-ray diffractogram of samples CX6 and EX9E. These samples have
the same overall composition. Sample CX6 is different from the samples described above.
The sample has been sintered too strongly. Hence the diffusion has progressed too much.
As a result the 2nd phase became similar to the 1st phase and cannot be distinguished
anymore by their X-ray pattern. All what remains is a tiny shoulder of phase 1 peaks
towards low angle. Contrary to this, sample EX9E shows a small but clear peak at lower
angle. A few of these peaks in Fig 14 are marked by arrows.
Contrary to this, sample EX9E shows a small but clear peak at lower angle. Our
understanding is that if Co goes into the second phase, its quantity increases, and its lattice
constants 'move' towards LiCoO2's lattice constants (see above), hence the X-ray peaks
move nearer, overlap and finally coincide. Therefore phase 2 in the oversintered phase
possibly does not disappear, but becomes too similar to be distinguished from LiCoO2.
It can be concluded that a cathode according the present invention shows an X-ray pattern
which can be approximated as a LiCoO2 pattern with high crystallinity, and a LiM'O2
pattern with lower crystallinity. Crystallinity is still quite good for both phases. Some
commercial cathode materials are less crystalline than phase 2. Also, the lattice constant of
the 2nd phase is lower than expected (the peaks are more near to the LiC0O2 peaks); the
expected value being the typical value of a LiM'O2 phase which has been prepared from
the same MOOH precursor.
Table 2 summarizes the results of the Rietveld refinement.
Voltage Profiles
Coin cells were prepared from all reference samples REF1, REF2, from all comparative
samples CX2, CX3 and from EX1, EX2 and EX3. The voltage profile of CX2, CX3 and
EX1-EX3 during slow discharge is shown in Figure 15. The samples CX2 and CX3 show
a clear plateau at 3.88V. This plateau is typical for LiCoO2. The presence of this plateau
indicates that phase 1 is pure LiCoO2. However, for sample EXl, EX2 and EX3 this
plateau progressively disappears with increasing sintering temperature. Obviously, the
phase 1 is not LiCoO2 anymore. This is consistent with the fact that particles of phase 1
contain Ni and Mn, as the EDS analysis clearly showed. However, very surprisingly,
phase 1 has exactly the X-ray diffraction pattern of UC0O2, with lattice constants very
different from the values which are expected for Ni-Mn doped LiCoO2.
Rate performance and cycling stability
Table 3 lists the results obtained from coin cell testing of the references REF1 and REF2
as well as of the samples CX2, CX3, EXl, EX2 and EX3 and a calculated value for the
hypothetical sample CC1. All samples have the same overall composition. The table gives
averaged data for 2 coin cells of each sample.
We observe that the sample CX2 (mixture of heated LiCoO2 and LiM'O2) has properties
which are very similar to those of the hypothetical sample. Clearly — mixing of LiCoO2
and LiM'O2 does not give any benefit. Sample CX3 and CX4 (heated mixture of LiCoO2
and LiM'O2) has slightly better rate performance and slightly improved cycling stability
but generally the properties are not very different from sample CX2 or CC1.
However, samples EXl, EX2 and EX3 show a significantly improved rate performance.
At 1C, 2C, 3C approx. 95,93 and 91% of the capacity is obtained, compared to 91-93,86-
88 and 83-86% of the hypothetical sample CC1 or the mixture CX2, or compared to 94,
91 and 89% of the sample CX3.
We note that the improved rate performance is not related to a different morphology. All
samples CX2, CX3, EX1-3 have almost identical BET surface area, and all samples are -
in a general picture - a mixture of large dense irregularly shaped particles (phase 1) and
agglomerated smaller particles (phase 2). Furthermore, the particle size distribution is
roughly the same. Achieving an increase of rate without increasing the BET area is a very
important aspect of the invention. In principle it will be possible to lower the BET surface
area to meet safety and density requirements and still achieving a sufficient rate
performance.
At the same time the cycling stability of EXl, EX2 and EX3 is dramatically improved.
Figure 16 displays the obtained data for sample EXl. Fig. 16a shows the calculation of the
fade rate per 100 cycles (capacity vs. cycle number #), being 6.4%. The small dots
represent the capacity on charging, the large dots on discharging. Fig. 16b shows the
cycling stability of EX1. Fig. 16c shows the rate performance of EX1.
In Figure 17 the cycling behavior of sample CX6 (left: A) is compared with EX5E (right:
B).
283-Amended sel of claims - PCT n° PCT/EP2008/000313
1. A powdcrous lithium transition metal oxide comprising Mn and Ni bearing LiCoO2
particles, said particles having Mn and Ni enriched islands on their surface, said islands
having a Mn and Ni concentration that is higher than in the bulk of said particles, "said
islands comprising at least 5 mol%, and preferably at least 10 mor% of Mn-
2. The powdcrous lithium transition metal-oxide according to claim 1, characterised in that
said Mn and is'i enriched islands have a thickness of at least 100 run and cover less -than
70%, and preferably less than 50% of the surface of said Mn and Ni bearing LiCO2
particles.
3. The powderous lithium transition metal oxide according to claims 1 or 2, wherein the
Mn concentration in said islands is at least 4 mol %, and preferably at least 7 mol% higher
than the Mn concentration in the bulk of said Mn and Ni bearing LiCoO2 particles.
4. The powderous lithium transition metal oxide according to any one of claims 1 to 3,
and wherein the Ni concentration in said Mn and Ni enriched islands is at least 2 mol%,
and preferably at least 6 mol% higher than the Ni concentration in the bulk of said Mn and
Ni bearing LiCoO2 particles.
5. The powderous lithium transition metal oxide according to any one of claims 1 to 4,
having Mn and Ni bearing LiCoO2 particles comprising at least 3 mol%, and preferably at
least 10 mol% of both Ni and Mn.
6. Tbe powderous htmum transition metal oxide according to any -one of claims 1 to 5,
characterised in that the crystallographic lattice constants a and c of said Mn and Ni
bearing LiCoO2 particles are respectively 2.815 +/- 0.002 and 14.05 +/- 0.01.
7. The powdcrous lithium transition metal oxide according to any one pf claims 1 to 6,
characterised in that the Mn and Ni bearing LiCoO2 particles particles are monolithic and
free of inner porosities.
8. The powderous lithium transition metal oxide according to any one of claims 1 to 7,
characterised in that the size distribution of said Mn and Ni bearing LiCoO2 particles has a
d50 larger than 10, preferably larger than 15, and most preferably larger than 20 µm.
9. Tbe powderous lithium transition metal oxide according to any one of claims 1 to 8,
comprising between 30 wt.% and 95 wt% of said Mn and Ni bearing LiCoC2 particles.
10. The powderous lithium transition metal oxide according to any one of claims 1 to 9,
comprising a first phase consisting of said Mn and Ni bearing LiCoO2 particles, and former
comprising a second island-free phase having a generalized formula of Li1+aM'1-aO2±b, with
-0.03 0.5 and o > p.
20. The method according to any one of claims 18 to 19, wherein the Ni-Mn-Co precursor
powder comprises between 5 and 70 mol% of the transition metal content of-said
powderous lithium transition metal oxide.
21. The method according to any one of claims 18 to 20, wherein the LiCoO2 powder has a
tap density of at least 2 g/cm3, and consists of monolithic particles with a d50 of at least 10,
preferably at least 15, and most preferably at least 20 µm.
22. The method according to any one of claims 18 to 20, wherein the cobalt containing
precursor compound is either one of more of cobalt hydroxide, oxyhydroxide or
carbonate.
23. The method according to any one of claims 18 to 22, wherein said LiCoO2 or cobalt
containing precursor comprises at least 80% of the transition metal of said powderous
lithium transition metal oxide, and the Ni-Mn-Co comprising precursor powder consists of
particles having a particle size distribution with a d50 between 1 and 3 put.
24. The method according to any one of claims 18 to 22, wherein said LiCoO2 or cobalt
containing precursor comprises less than 80% of the transition metal of said powderous
lithium transition metal oxide, and the Ni-Mn-Co comprising precursor consists of
particles of the agglomerated type having a particle size distribution with a d50 between 4
and 10 µm.
25. The method according to any one of claims 18 to 24, wherein the Ni-Mn-Co
comprising precursor further comprises Ti, preferably in the form of TiO2 particles with a
d50 less than l00 nm.
Disclosed is a cathode active material and a method to produce the same at low cost. The cathode powder comprises modified LiC0O2, and possibly a second phase which is LiMO2 where M' is Mn, Ni, Co with a stoichiometric ratio Ni: Mn ≥1. The modified LiCoO2 is Ni and Mn bearing and has regions of low and high manganese content, where regions with high manganese content are located in islands on the surface. The cathode material has high cycling stability, a very high rate performance and good high temperature storage properties.