U.S. patent application number 16/931513 was filed with the patent office on 2021-01-28 for powderous lithium cobalt-based oxide compound for rechargeable lithium ion batteries and a method for making thereof.
The applicant listed for this patent is Umicore, Umicore Korea Ltd.. Invention is credited to Maxime BLANGERO, KyeongSe SONG.
Application Number | 20210028455 16/931513 |
Document ID | / |
Family ID | 1000004977073 |
Filed Date | 2021-01-28 |
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United States Patent
Application |
20210028455 |
Kind Code |
A1 |
SONG; KyeongSe ; et
al. |
January 28, 2021 |
Powderous lithium cobalt-based oxide compound for rechargeable
lithium ion batteries and a method for making thereof
Abstract
A lithium cobalt-based oxide cathode active material powder
comprising particles having a median particle size D50 of superior
or equal to 20 .mu.m, preferably 25 .mu.m, and inferior or equal to
45 .mu.m, said particles having an averaged circularity of superior
or equal to 0.85 and inferior or equal to 1.00, said particles
having a general formula
Li.sub.1+aCo.sub.1-x-y-zAl.sub.xM'.sub.yMe.sub.zO.sub.2, wherein M'
and Me comprise at least one element of the group consisting of:
Ni, Mn, Nb, Ti, W, Zr, and Mg, with -0.01.ltoreq.a.ltoreq.0.01,
0.002.ltoreq.x.ltoreq.0.050, 0.ltoreq.y.ltoreq.0.020 and
0.ltoreq.z.ltoreq.0.050, the cathode active material powder having
a specific floating capacity of at most 80 mAh/g.
Inventors: |
SONG; KyeongSe;
(Chungcheongnam-do, KR) ; BLANGERO; Maxime;
(Chungcheongnam-do, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Umicore
Umicore Korea Ltd. |
Brussels
Chungcheongnam-do |
|
BE
KR |
|
|
Family ID: |
1000004977073 |
Appl. No.: |
16/931513 |
Filed: |
July 17, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62877364 |
Jul 23, 2019 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 4/364 20130101;
H01M 4/0471 20130101; H01M 10/0525 20130101; H01M 4/525 20130101;
H01M 2004/021 20130101; H01M 4/131 20130101; H01M 4/505
20130101 |
International
Class: |
H01M 4/525 20060101
H01M004/525; H01M 4/505 20060101 H01M004/505; H01M 4/36 20060101
H01M004/36; H01M 4/04 20060101 H01M004/04; H01M 4/131 20060101
H01M004/131; H01M 10/0525 20060101 H01M010/0525 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 23, 2019 |
IB |
PCT/IB2019/056282 |
Jul 23, 2019 |
IB |
PCT/IB2019/056284 |
Claims
1. A lithium cobalt-based oxide cathode active material powder,
which comprises particles having a median particle size D50 of
superior or equal to 20.00 .mu.m, preferably 25.00 .mu.m, and
inferior or equal to 45.00 .mu.m, said particles having an averaged
circularity of superior or equal to 0.85 and inferior or equal to
1.00, said particles having a general formula
Li.sub.1+aCo.sub.1-x-y-zAl.sub.xM'.sub.yMe.sub.zO.sub.2, wherein M'
and Me comprise at least one element of the group consisting of:
Ni, Mn, Nb, Ti, W, Zr, and Mg, with -0.01.ltoreq.a.ltoreq.0.01,
0.002.ltoreq.x.ltoreq.0.050, 0.ltoreq.y.ltoreq.0.020 and
0.ltoreq.z.ltoreq.0.050, said lithium cobalt-based oxide active
material powder being obtained by a process comprising the steps
of: a. preparing a first mixture comprising: a Li source, a first
Co-bearing precursor, optionally a M' source, and an Al source,
said first mixture having a Li to (Co+Al+M') molar ratio superior
or equal to 1.03 and inferior or equal to 1.10, b. sintering said
first mixture at a temperature of superior or equal to 950.degree.
C. and inferior or equal to 1100.degree. C. in an oxygen containing
atmosphere such as air, so as to obtain a first sintered
agglomerated powder, and c. milling and screening the first
sintered agglomerated powder so as to obtain an intermediate powder
having a general formula
Li.sub.1+a'Co.sub.1-x'-y'Al.sub.x'M'.sub.y'O.sub.2, M' being at
least one element of the group consisting of: Ni, Mn, Nb, Ti, W,
Zr, and Mg, with 0.03.ltoreq.a'.ltoreq.0.10,
0.002.ltoreq.x'.ltoreq.0.050, and 0.ltoreq.y'.ltoreq.0.02, and
comprising particles having a D50 of superior or equal to 20.00
.mu.m, preferably 25.00 .mu.m, and inferior or equal to 45.00 .mu.m
and an averaged circularity of superior or equal to 0.85 and
inferior or equal to 1.00, d. mixing the intermediate powder with a
second Co-bearing precursor and optionally, with a source of Me, to
prepare a second mixture, wherein the Li to (Co+Al+M') or the Li to
(Co+Al+M'+Me) molar ratio in said second mixture is superior or
equal to 0.99 and inferior or equal to 1.01, e. sintering said
second mixture at a temperature of superior or equal to 800.degree.
C. and inferior or equal to 1100.degree. C. in an oxygen containing
atmosphere, such as air, so as to obtain a second sintered
agglomerated powder, and f. milling and screening said second
sintered agglomerated powder so as to obtain the cathode active
material powder according to the invention, the cathode active
material powder having a specific floating capacity of at most 80
mAh/g obtained by the steps a. to f.
2. The lithium cobalt-based oxide cathode active material powder
according to claim 1, having a press density superior or equal to
3.95 g/cm.sup.3 and inferior or equal to 4.40 g/cm.sup.3.
3. The lithium cobalt-based oxide cathode active material powder
according to claim 1, having a volumetric capacity of at least 570
mAh/cm.sup.3, preferably of at most 700 mAh/cm.sup.3 .
4. The lithium cobalt-based oxide cathode active material powder
according to claim 1, wherein said particles have a R-3m crystal
structure.
5. The lithium cobalt-based oxide cathode active material powder
according to claim 1, comprising particles having an averaged
circularity of superior or equal to 0.90 and inferior or equal to
1.00, preferably of superior or equal to 0.85 and of inferior or
equal to 0.95.
6. The lithium cobalt-based oxide cathode active material powder
according to claim 1, wherein y and z=0.
7. A lithium-ion secondary battery suitable for electronic devices
comprising the lithium cobalt-based oxide cathode active material
powder according to claim 1.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application No. 62/877,364, filed Jul. 23, 2019; International
Application No. PCT/IB2019/056282, filed Jul. 23, 2019; and
International Application No. PCT/IB2019/056284, filed Jul. 23,
2019. The entire contents of each are incorporated by reference
herein.
TECHNICAL FIELD AND BACKGROUND
[0002] This invention relates to a lithium cobalt-based oxide (LCO)
cathode active material powder for lithium-ion secondary batteries
(LIBs) suitable for portable electronic device applications.
[0003] As the functionalities and performances of portable
electronic devices are constantly improving, LIBs having a higher
volumetric energy density are required.
[0004] The volumetric energy density of a cathode active material
powder is obtained according to a following equation:
Volumetric energy density (mAh/cm.sup.3)=volumetric capacity
(mAh/cm.sup.3).times.Charge cutoff voltage (V),
, wherein:
Volumetric capacity ( mAh / cm 3 ) = Specific discharge capacity (
mAh / g ) Density of a cathode active material ( g / cm 3 )
##EQU00001##
[0005] A higher charge cutoff voltage (such as superior or equal to
4.5V vs. Li.sup.+/Li reference potential) leads to a significant
increase of the volumetric energy density of a cathode material
powder.
[0006] It is therefore an object of the present invention to
provide a lithium cobalt-based oxide cathode active material powder
for lithium-ion secondary batteries, having an improved volumetric
capacity of at least 570 mAh/cm.sup.3 obtained by the analytical
methods of the present invention.
[0007] In addition to the improved volumetric capacity, the LCO
cathode active material compound according to the present invention
must have a sufficient structural stability at a voltage superior
or equal to 4.5V so far. Such a sufficient stability is indicated
by a specific floating capacity of at most 80 mAh/g (obtained by
the analytical methods of the present invention) during the use of
the cathode active material powder in a LIB.
SUMMARY OF THE INVENTION
[0008] This objective is achieved by providing a lithium
cobalt-based oxide cathode active material powder according to
claim 1.
[0009] It is indeed observed that an improved volumetric capacity
of higher than 570 mAh/cm.sup.3 and a specific floating capacity of
lower than 80 mAh/g, as illustrated in the results provided in
Table 2, are achieved with a battery using a LCO cathode material
powder according to EX1, having the following features: [0010] a
median particle size D50 of 38.00 .mu.m, [0011] an averaged
circularity of 0.87, and [0012] resulting from a double-sintering
process wherein the Li/(Co+Al)=1.04 when S1 (at a T.degree.
C.=1000.degree. C.) is applied and wherein the Li/(Co+Al)=1.00 when
S2 (at a T.degree. C.=980.degree. C.) is applied.
[0013] The cathode active material powder comprises particles
having an Al to (Co+Al+M'+Me) molar ratio (x) inferior or equal to
0.050 so as to minimize a capacity loss, and superior or equal to
0.002 so as to stabilize a crystal-structure of the LCO cathode
active material powder during cycling.
[0014] The cathode active material powder comprises particles
having a Li to (Co+Al+M'+Me) molar ratio (1+a) superior or equal to
0.99 and inferior or equal to 1.01, preferably superior or equal to
0.995 and inferior or equal to 1.005.
[0015] If the ratio 1+a is less than 0.99 (a<-0.01), a Co
dissolution at a higher voltage such as 4.50V occurs since there is
no enough Li to hold the cobalt atoms in the structure of the
cathode active material particles and the capacity of the cathode
active material powder decreases. If the ratio 1+a is more than
1.01 (a>0.01), the cycle life of the cathode active material
powder deteriorates.
[0016] In the framework of the present invention, the D50 is the
volumetric median particle size and is superior or equal to 20.00
.mu.m, preferably 25.00 .mu.m, and inferior or equal to 45 .mu.m.
Preferably, the cathode active material powder according to the
present invention has a D50 superior or equal to 30.00 .mu.m and
inferior or equal to 40.00 .mu.m.
[0017] Due a larger D50 of the LCO cathode active material powder
according to the invention, in comparison with conventional D50
values (less than 20.00 .mu.m) for this type of cathode active
material, the claimed LCO cathode active material powder shows
packing density values which are much higher than the conventional
ones. The D50 should however be less than 45.00 .mu.m, because
surface scratching of the cathode during its preparation from the
LCO cathode active material powder is observed for D50 values
higher than this upper limit.
[0018] The present invention concerns the following
embodiments:
Embodiment 1
[0019] In a first aspect, the present invention concerns a lithium
cobalt-based oxide cathode active material powder, which comprises
particles having a median particle size D50 of superior or equal or
superior to 20.00 .mu.m+/-1.00 .mu.m, preferably 25.00 .mu.m+/-1.00
.mu.m, and inferior or equal to 45.00 .mu.m+/-1.00 .mu.m, said
particles having an averaged circularity of superior or equal to
0.85 and inferior or equal to 1.00, said particles having a general
formula Li.sub.1+aCo.sub.1-x-y-zAl.sub.xM'.sub.yMe.sub.zO.sub.2,
wherein M' and Me comprise at least one element of the group
consisting of: Ni, Mn, Nb, Ti, W, Zr, and Mg, with
-0.01.ltoreq.a.ltoreq.0.01, 0.002.ltoreq.x.ltoreq.0.050,
0.ltoreq.y.ltoreq.0.020 and 0.ltoreq.z.ltoreq.0.050, said lithium
cobalt-based oxide active material powder being obtained by a
process comprising the steps of: [0020] a. preparing a first
mixture comprising: a Li source, a first Co-bearing precursor,
optionally a M' source, and an Al source, said first mixture having
a Li to (Co+Al+M') molar ratio superior or equal to 1.03 and
inferior or equal to 1.10, [0021] b. sintering (step S1) said first
mixture at a temperature of superior or equal to 950.degree. C. and
inferior or equal to 1100.degree. C. in an oxygen containing
atmosphere such as air, so as to obtain a first sintered
agglomerated powder, and [0022] c. milling and screening the first
sintered agglomerated powder so as to obtain an intermediate powder
(LCO1) having a general formula
Li.sub.1+a'Co.sub.1-x'-yAl.sub.x'M'.sub.y'O.sub.2, M' being at
least one element of the group consisting of: Ni, Mn, Nb, Ti, W,
Zr, and Mg, with 0.03.ltoreq.a'.ltoreq.0.10,
0.002.ltoreq.x.ltoreq.0.050, and 0.ltoreq.y'.ltoreq.0.02, and
comprising particles having a D50 of superior or equal to 20.00
.mu.m, preferably 25.00 .mu.m, and inferior or equal to 45.00
.mu.m, and an averaged circularity of superior or equal to 0.85 and
inferior or equal to 1.00, [0023] d. mixing the intermediate powder
with a second Co-bearing precursor and optionally, with a source of
Me, to prepare a second mixture, wherein the Li to (Co+Al+M') or
the Li to (Co+Al+M'+Me) molar ratio in said second mixture is
superior or equal to 0.99 and inferior or equal to 1.01, [0024] e.
sintering (step S2) said second mixture at a temperature of
superior or equal to 800.degree. C. and inferior or equal to
1100.degree. C. in an oxygen containing atmosphere, such as air, so
as to obtain a second sintered agglomerated powder, and [0025] f.
milling and screening said first sintered agglomerated powder so as
to obtain the cathode active material powder according to the
invention (LCO2), said cathode active material powder having a
specific floating capacity of at most 80 mAh/g obtained by the
steps a. to f.
[0026] Preferably, y and z=0.
[0027] In the Embodiment 1 according to the invention, the D50
value and the averaged circularity value of the particles of the
intermediate powder (or the first sintered agglomerated powder
after milling and screening--step c.) are similar to the D50 value
and the averaged circularity values of the particles of the lithium
cobalt-based oxide cathode active material powder according to the
invention.
[0028] The D50 is a volumetric-based value (see section 1.1 below)
expressed in .mu.m+/-0.01 .mu.m.
[0029] The averaged circularity is a number-based value (see
section 1.7 below).
Embodiment 2
[0030] Preferably, the cathode active material powder of the
Embodiment 1 has a press density superior or equal to 3.95
g/cm.sup.3 and inferior or equal to 4.40 g/cm.sup.3.
Embodiment 3
[0031] More preferably, the cathode active material powder
according to the Embodiment 1 or 2 has a volumetric capacity of at
least 570 mAh/cm.sup.3, preferably of at most 700 mAh/cm.sup.3.
Embodiment 4
[0032] In a fourth Embodiment, the cathode active material powder
according to any of the preceding Embodiments, wherein said
particles have an averaged circularity of superior or equal to 0.90
and inferior or equal to 1.00, preferably of superior or equal to
0.95 and inferior or equal to 1.00, more preferably of superior or
equal to 0.85 and inferior or equal to 0.95, most preferably of
superior or equal to 0.90 and inferior or equal to 0.95.
[0033] In said fourth Embodiment, the intermediate powder has
particles having an averaged circularity of superior or equal to
0.90 and inferior or equal to 1.00, preferably of superior or equal
to 0.95 and inferior or equal to 1.00, more preferably of superior
or equal to 0.85 and inferior or equal to 0.95, most preferably of
superior or equal to 0.90 and inferior or equal to 0.95.
Embodiment 5
[0034] Preferably, in a fifth Embodiment according to any of the
preceding Embodiments, the first Co-bearing precursor has a D50
superior or equal to 20.00 .mu.m+/-1.00 .mu.m, preferably 25.00
.mu.m+/-1.00 .mu.m, and inferior or equal to 45 .mu.m+/-1.00
.mu.m.
[0035] More preferably, the first Co-bearing precursor has a D50
superior or equal to 35.00 .mu.m+/-1.00 .mu.m, and inferior or
equal to 45.00 .mu.m+/-1.00 .mu.m, so that the lithium cobalt-based
oxide cathode active material powder comprises particles having a
median particle size D50 of superior or equal to 35.00 .mu.m+/-1.00
.mu.m, and inferior or equal to 45.00 .mu.m+/-1.00 .mu.m.
[0036] If the D50 of the first Co-bearing precursor is inferior to
20.00 .mu.m+/-1.00 .mu.m, it is required to increase the Li to
(Co+Al+M') molar ratio of the second mixture or to sinter said
second mixture at a temperature superior to 1100.degree. C.
[0037] Optionally, the first Co-bearing precursor contains Al and
M'.
[0038] Preferably, the second Co-bearing precursor has a D50
inferior to 10.00 .mu.m, more preferably inferior to 5.00 .mu.m to
maximize the volumetric density of the second cathode active
material according to the Embodiment 1.
[0039] Li sources can be either one or more of Li.sub.2O, LiOH,
LiOH.H.sub.2O, Li.sub.2CO.sub.3, and LiNO.sub.3.
[0040] Co-bearing precursors can be either one or more of
CoO.sub.z, CoCO.sub.3, CoO(OH), and Co(OH).sub.2.
Embodiment 6
[0041] Preferably, in a sixth Embodiment according to any of the
preceding Embodiments, the first sintering step is performed during
a period of at least 3 hours and at most 20 hours.
Embodiment 7
[0042] Preferably, in a seventh Embodiment according to any of the
preceding
[0043] Embodiments, the second sintering step is performed during a
period of at least 1 hour and at most 20 hours.
BRIEF DESCRIPTION OF THE FIGURES
[0044] FIG. 1: Morphology of EX1.
DETAILED DESCRIPTION
[0045] The invention is further illustrated in the following
examples:
1. DESCRIPTION OF ANALYSIS METHODS
[0046] 1.1. Particle Size distribution
[0047] The D50 is an indicator of a powder particle size
distribution (hereafter referred to as psd) and is obtained by a
laser psd measurement method. In this invention, the laser psd is
measured by using a Malvern Mastersizer 2000 with Hydro 2000MU wet
dispersion accessory, e.g. after having dispersed the powder in an
aqueous medium. In order to improve the dispersion of the powder in
the aqueous medium, sufficient ultrasonic irradiation and stirring
are applied and an appropriate surfactant is introduced in the
aqueous medium.
[0048] If the powder according to the invention has a multimodal
psd profile, then said multimodal profile is deconvoluted, then if
one or several deconvoluted modes having a D50 comprised in the
20.00 .mu.m, preferably 25.00 .mu.m, and 45.00 .mu.m range are
identified, said powder has a D50 according to claim1.
[0049] If the powder according to the present invention has a
monomodal psd profile with a single mode having a D50 comprised in
the in the 20.00 .mu.m, preferably 25.00 .mu.m, and 45.00 .mu.m
range, said powder has therefore a D50 according to claim1.
[0050] 1.2. Pressed Density
[0051] The pressed density (PD) is measured according to the
following procedure: 3 grams of a LCO cathode active material
powder is filled into a pellet die with a diameter "d" of 1.3 cm. A
pressure of 207 MPa is applied for 30 seconds. After relaxing the
load, the thickness "t" of the pressed LCO cathode active material
powder is measured. The pressed density PD is 3 g divided by the
volume of the pressed powder (.pi..times.(d/2).sup.2.times.t).
[0052] 1.3. Inductively Coupled Plasma
[0053] The inductively coupled plasma (ICP) method is used to
measure the content of elements such as Li, Co, and Al by using an
Agillent ICP 720-ES device.
[0054] 2 g of a powder sample is dissolved in 10 mL high purity
hydrochloric acid in an Erlenmeyer flask. The flask is covered by a
glass and heated on a hot plate until complete dissolution of the
precursor is achieved. After being cooled to the room temperature,
the solution is moved to a 100 mL volumetric flask. After having
filled the flask with the solution, the volumetric flask is filled
with deionized water up to the 100 mL mark. 5 mL of the resulting
solution is transferred into a 50 mL volumetric flask for a
2.sup.nd dilution, where the volumetric flask is filled with 10%
hydrochloric acid up to the 50 mL mark and then homogenized.
Finally, this 50 mL solution is used in the ICP measurement.
[0055] 1.4. High Angular Resolution Synchrotron X-Ray
Diffraction
[0056] High angular resolution synchrotron powder x-ray diffraction
(SXRD) is carried out on the BL04-MSPD beamline of the ALBA
synchrotron (Cerdanyola del Valles, Spain). All powders were packed
in 0.5 mm diameter capillaries. The typical 20 angular range was
from 0.degree. to 70.degree. with 0.006.degree. angular step and 3
minutes accumulation time. The patterns were recorded in a
Debye-Scherrer geometry with a wavelength of
.lamda.=0.825.ANG.+/-0.010.ANG..
[0057] 1.5. Crystallographic Characterization
[0058] Inorganic Crystal Structure Database (ICSD, provided by FIZ
Karlsruhe and the U.S. Secretary of Commerce) contains information
on all inorganic crystal-structures published since 1913. peak
positions in the obtained diffraction pattern and the elements in a
powder sample (e.g. Li, Co, O, Al) are searched in the ICSD so as
to determine a crystal-structure of a power sample.
[0059] 1.6. Electrochemical Analysis: Capacity and a Floating Test
Analysis
[0060] 1.6.1. Coin Cells Preparation
[0061] Coin cells that are used in a discharge capacity and
floating test analysis are assembled according to the following
steps:
[0062] Step 1) Preparation of a Cathode:
[0063] A slurry that contains the solids: a LCO cathode active
material powder, a conductor (Super P, Timcal) and a binder (KF
#9305, Kureha) in a weight ratio 90:5:5, and a solvent (NMP,
Sigma-Aldrich) are mixed in a high speed homogenizer so as to
obtain a homogenized slurry. The homogenized slurry is spread on
one side of an aluminum foil using a doctor blade coater with a 230
.mu.m gap. the slurry-coated aluminum foil is dried in an oven at
120.degree. C., then pressed using a calendaring tool, and dried
again in a vacuum oven to remove the solvent completely.
[0064] Step 2) Coin Cell Assembly:
[0065] A coin cell is assembled in a glovebox which is filled with
an inert gas (argon). For the discharge capacity analysis, a
separator (Celgard) is located between the cathode and a piece of
lithium foil used as an anode. For the floating test, two pieces of
separator are located between the cathode and an anode, which
consists of graphite. 1M LiPF.sub.6 in EC:DMC (1:2 in volume) is
used as electrolyte and dropped between separator and electrodes.
Then, the coin cell is completely sealed to prevent leakage of
electrolyte.
[0066] 1.6.2. Discharge Capacity Analysis
[0067] The first charge and discharge capacity (CQ1 and DQ1) are
measured by constant current mode with 0.1C rate, where 1C is
defined as 160 mAh/g and charge cutoff voltage is 4.30V and
discharge cutoff voltage is 3.0V. The volumetric discharge capacity
DQ1V (mAh/cm.sup.3) is obtained according to multiplying DQ1 by
PD.
[0068] 1.6.3. Floating Test Analysis
[0069] The floating test analyses the crystal-stability of LCO
compounds at a high voltage at an elevated temperature.
[0070] The prepared coin cell is tested according to the following
charge protocol: the coin cell is first charged to 4.5V at constant
current mode with C/20 rate (1C=160 mAh/g) in a 50.degree. C.
chamber. The coin cell is then kept at constant voltage (4.5V) for
5 days (120 hours), which is a very severe condition.
[0071] Once side reactions or metal dissolution happen, there will
be a voltage drop. The electrochemical instrument will
automatically compensate the (loss of) current to keep the voltage
constant. Therefore, the recorded current is a measure of the
ongoing side reactions during cycling.
[0072] The specific floating capacity (QF) is the total amount
capacity (mAh/g) during the floating test. After the floating test,
the coin cell is disassembled. The anode and the separator
(localized close to the anode) are analyzed by ICP for a metal
dissolution analysis. The measured cobalt content is normalized by
the total amount of active material in the electrode so that a
specific cobalt dissolution value (Co.sub.Dis) is obtained.
[0073] 1.7. Morphology Analysis
[0074] The morphology of a powder sample is analyzed with a
Scanning Electron Microscopy (SEM) technique. The measurement is
performed with a JEOL JSM-6000. An image of the powder sample is
recorded with a magnification of 500 times to demonstrate the
averaged circularity of the powder sample particles. In the SEM
image, ten particles are selected and the circularity of these
particles is calculated as follows:
Circularity = 4 .pi. A P 2 ##EQU00002##
, wherein A is an area of a particle, P is a perimeter of a
particle, these parameters being obtained using an ImageJ software
(reference is made to the Sections 30.2 to 30.7--"Set measurement"
of the Image J User Guide version IJ 1.46r).
[0075] The averaged circularity according to the invention may be
expressed as follows:
Averaged circularity = ( i = 1 n 4 .pi. A i P i 2 ) n ,
##EQU00003##
wherein n is the number of particles i analyzed according to the
below-provided protocol. The averaged circularity is then a
number-based average value.
[0076] A sufficient number of particles is at least 10 for a SEM
image recorded with a magnification of 500 times. The at least 10
particles have a size of at least 20.00 .mu.m.
[0077] As mentioned above, the calculation of the circularity
implies the measurement of: [0078] i) The perimeter which is
effected by: a) determining an outside boundary of the SEM image of
a particle, by b) decomposing the outside boundary into individual
segment-based selections, each of these selections having an
individual perimeter, and by c) adding the values of the lengths of
the individual perimeters so as to obtain the value of the
perimeter of a particle; and [0079] ii) The area which is done by:
adding a plurality of pixel areas included in a surface defined by
the outside boundary.
[0080] An averaged circularity of 1.00 means that the particles
representative of a sample have a spherical shape.
[0081] An averaged circularity inferior to 1.00 means that the
particles representative of a sample have a non-spherical
shape.
[0082] An averaged circularity superior to 0 and inferior to 1
refers to an ellipsoidal shape.
[0083] The invention is further illustrated in the following
examples:
2. EXAMPLES AND COMPARATIVE EXAMPLES
Example 1
[0084] A CoCO.sub.3 powder having a D50 of 38.00 .mu.m and an
Al.sub.2O.sub.3 powder are mixed so as to obtain a mixture having
an Al to (Co+Al) molar ratio of 0.04 and the mixture is heated at
600.degree. C. for 3 hours under a flow of air to prepare an Al
coated Co oxide "CAO1". The CAO1 powder and Li.sub.2CO.sub.3 are
mixed so as to obtain a mixture having a Li to (Co+Al) molar ratio
of 1.04 and the mixture is heated at 1000.degree. C. for 10 hours
under a flow of air. The sintered powder is grinded and named
LCO1A-EX1 having a general formula of
Li.sub.1.04Co.sub.0.96Al.sub.0.04O.sub.2 and a D50 of 37.00
.mu.m.
[0085] LCO1B-EX1, which is prepared by a same procedure as
LCO1A-EX1 except that the Li to (Co+Al) molar ratio is 1.06, has a
general formula of Li.sub.1.06Co.sub.0.96Al.sub.0.04O.sub.2 and a
D50 of 39.00 .mu.m.
[0086] A Co.sub.3O.sub.4 powder having a D50 of 3.00 .mu.m and
Al.sub.2O.sub.3 powder are mixed so as to obtain a mixture having
an Al to (Co+Al) molar ratio of 0.04, and the mixture is heated at
1000.degree. C. for 10 hours under a flow of air to prepare an Al
coated Co oxide "CAO2".
[0087] LCO1A-EX1 and CAO2 are mixed to prepare EX1A having a
general formula Li.sub.1.00Co.sub.0.96Al.sub.0.04O.sub.2. The
mixture is heated at 980.degree. C. for an hour under a flow of
air. The sintered powder is grinded and named EX1A.
[0088] EX1B is prepared by a same procedure as EX1A except that
LCO1B-EX1 is used instead of LCO1A-EX1.
[0089] EX1A and EX1B are according to the present invention.
Comparative Example 1
[0090] CAO2 and Li.sub.2CO.sub.3 are mixed so as to obtain a
mixture having an Al to (Co+Al) molar ratio of 1.00, and the
mixture is heated at 1000.degree. C. for 10 hours under a flow of
air. The sintered powder is grinded and named LCO1A-CEX1 which has
a general formula Li.sub.1.00Co.sub.0.96Al.sub.0.04O.sub.2 and a
D50 of 4 .mu.m.
[0091] LCO1B-CEX1, LCO1C-CEX1, and LCO1D-CEX1 are prepared by a
same procedure as LCO1A-CEX1 except that the Li to (Co+Al) molar
ratios in the mixture are 1.02, 1.04, and 1.06, respectively. The
general formulas of LCO1B-CEX1, LCO1C-CEX1, and LCO1D-CEX1 are
Li.sub.1.02Co.sub.0.96Al.sub.0.04O.sub.2,
Li.sub.1.04Co.sub.0.96Al.sub.0.04O.sub.2, and
Li.sub.1.06Co.sub.0.96Al.sub.0.04O.sub.2, respectively. The D50 of
LCO1B-CEX1, LCO1C-CEX1, and LCO1D-CEX1 are 8 .mu.m, 15 .mu.m, 20
.mu.m, respectively.
[0092] LCO1A-CEX1 is heated at 980.degree. C. for an hour under a
flow of air. The sintered powder is grinded and named CEX1A which
has a general formula Li.sub.1.00Co.sub.0.96Al.sub.0.04O.sub.2.
[0093] LCO1B-CEX1 and CAO2 are mixed so as to obtain a mixture
having Li to (Co+Al) molar ratio of 1.00. The mixture is heated at
980.degree. C. for an hour under a flow of air. The sintered powder
is grinded and named CEX1B having a general formula
Li.sub.1.00Co.sub.0.96Al.sub.0.04O.sub.2.
[0094] CEX1C and CEX1D are prepared by a same procedure as CEX1B
except that LCO1C-CEX1 and LCO1D-CEX1 are used instead of
LCO1B-CEX1.
[0095] CEX1A, CEX1B, CEX1C, and CEX1D are not according to the
present invention.
3. DISCUSSION
[0096] Table 1 shows the key preparation conditions of the LCO
cathode active material powders according to Example 1 and
Comparative example 1. EX1A and EX1B are prepared by the two
sintering steps according to the method claimed in the present
invention. The methods to prepare CEX1A and CEX1B are not according
to the present invention because neither the D50 of Co precursor of
LCO1 is superior to 20 .mu.m nor the ratio 1+a' is superior or
equal to 1.03. The methods to prepare CEX1C and CEX1D are also not
according to the present invention because the D50 of LCO1 is not
superior to 20 .mu.m.
[0097] Table 2 shows analytical results, obtained according to the
analysis method described in the section 1.2. Pellet density,
1.6.2. discharge capacity analysis, 1.6.3. floating test analysis,
and 1.4. cross-SEM Al EDX mapping analysis, of LCO compounds in
Example 1, Comparative example 1, and Comparative example 2.
[0098] DQ1V corresponds the volumetric capacity of batteries. The
parameters QF and Co.sub.Dis are obtained by the floating test
(cfr. section 1.6.3) and are indicators of the crystal-structural
stability at a high voltage such as 4.50V or higher. QF and
Co.sub.Dis should be as low as possible.
[0099] EX1A and EX1B have lower QF and Co.sub.Dis as well as higher
DQ1V.
TABLE-US-00001 TABLE 1 Formula of LCO1 and D50 of Co precursor or
LCO1 D50 of Co precursor of Crystal Averaged Example ID LCO1 ID
Formula of LCO1 LCO1 (.mu.m) structure* circularity EX1A LCO1A-EX1
Li.sub.1.04Co.sub.0.96Al.sub.0.04O.sub.2 38 R-3 m 0.87 EX1B
LCO1B-EX1 Li.sub.1.06Co.sub.0.96Al.sub.0.04O.sub.2 38 R-3 m 0.91
CEX1A LCO1A-CEX1 Li.sub.1.00Co.sub.0.96Al.sub.0.04O.sub.2 3 R-3 m
0.68 CEX1B LCO1B-CEX1 Li.sub.1.02Co.sub.0.96Al.sub.0.04O.sub.2 3
R-3 m 0.77 CEX1C LCO1C-CEX1
Li.sub.1.04Co.sub.0.96Al.sub.0.04O.sub.2 3 R-3 m 0.83 CEX1D
LCO1D-CEX1 Li.sub.1.06Co.sub.0.96Al.sub.0.04O.sub.2 3 R-3 m 0.81
*acquired by SXRD (cfr. sections 1.4 and 1.5)
TABLE-US-00002 TABLE 2 Analytical results Related Psd Li/(Co +
Sintering temperature Electrochemical property Example to the D50
Al) (.degree. C.) PD DQ1V QF CO.sub.Dis IDs invention (.mu.m) S1 S2
S1 S2 (g/cm.sup.3) (mAh/cm.sup.3) (mAh/g) (mg/g) EX1A Yes 38 1.04
1.00 1000 980 4.0 584.0 76 9 EX1B Yes 40 1.06 1.00 1000 980 4.1
583.2 73 10 CEX1A No 5 1.00 1.00 1000 980 3.3 508.2 169 28 CEX1B No
9 1.02 1.00 1000 980 3.4 518.8 99 14 CEX1C No 16 1.04 1.00 1000 980
3.6 542.7 70 9 CEX1D No 21 1.06 1.00 1000 980 3.7 552.0 69 8
[0100] The present invention is covered by the following
clauses:
[0101] 1. A lithium cobalt-based oxide cathode active material
powder, which comprises particles having a median particle size D50
of superior or equal to 20.00 .mu.m+/-1.00 .mu.m, preferably 25.00
.mu.m+/-1.00 .mu.m, and inferior or equal to 45.00 .mu.m+/-1.00
.mu.m, said particles having an averaged circularity of superior or
equal to 0.85 and inferior or equal to 1.00, said particles having
a general formula
Li.sub.1+aCo.sub.1-x-y-zAl.sub.xM'.sub.yMe.sub.zO.sub.2, wherein M'
and Me comprise at least one element of the group consisting of:
Ni, Mn, Nb, Ti, W, Zr, and Mg, with -0.01.ltoreq.a.ltoreq.0.01,
0.002.ltoreq.x.ltoreq.0.050, 0.ltoreq.y.ltoreq.0.020 and
0.ltoreq.z.ltoreq.0.050, said lithium cobalt-based oxide active
material powder being obtained by a process comprising the steps
of: [0102] a. preparing a first mixture comprising: a Li source, a
first Co-bearing precursor, optionally a M' source, and an Al
source, said first mixture having a Li to (Co+Al+M') molar ratio
superior or equal to 1.03 and inferior or equal to 1.10, [0103] b.
sintering said first mixture at a temperature of superior or equal
to 950.degree. C. and inferior or equal to 1100.degree. C. in an
oxygen containing atmosphere such as air, so as to obtain a first
sintered agglomerated powder, and [0104] c. milling and screening
the first sintered agglomerated powder so as to obtain an
intermediate powder having a general formula
Li.sub.1+aCo.sub.1-x'-y'Al.sub.x'M'.sub.y'O.sub.2, M' being at
least one element of the group consisting of: Ni, Mn, Nb, Ti, W,
Zr, and Mg, with 0.03.ltoreq.a'.ltoreq.0.10,
0.002.ltoreq.x'.ltoreq.0.050, and 0.ltoreq.y'.ltoreq.0.02, and
comprising particles having a D50 of superior or equal to 20.00
.mu.m, preferably superior or equal to 25.00 .mu.m, more preferably
superior or equal to 35.00 .mu.m, and inferior or equal to 45.00
.mu.m, preferably inferior or equal to 40.00 .mu.m, and an averaged
circularity of superior or equal to 0.85 and inferior or equal to
1.00, preferably inferior or equal to 0.95, [0105] d. mixing the
intermediate powder with a second Co-bearing precursor and
optionally, with a source of Me, to prepare a second mixture,
wherein the Li to (Co+Al+M') or the Li to (Co+Al+M'+Me) molar ratio
in said second mixture is superior or equal to 0.99 and inferior or
equal to 1.01, [0106] e. sintering said second mixture at a
temperature of superior or equal to 800.degree. C. and inferior or
equal to 1100.degree. C. in an oxygen containing atmosphere, such
as air, so as to obtain a second sintered agglomerated powder, and
[0107] f. milling and screening said first sintered agglomerated
powder so as to obtain the cathode active material powder according
to the invention, the cathode active material powder having a
specific floating capacity of at most 80 mAh/g obtained by the
steps a. to f.
[0108] 2. The lithium cobalt-based oxide cathode active material
powder according to clause 1, having a press density superior or
equal to 3.95 g/cm.sup.3 and inferior or equal to 4.40
g/cm.sup.3.
[0109] 3. The lithium cobalt-based oxide cathode active material
powder according to clause 1 or 2, having a volumetric capacity of
at least 570 mAh/cm.sup.3, preferably of at most 700
mAh/cm.sup.3.
[0110] 4. The lithium cobalt-based oxide cathode active material
powder according to according to any of the preceding clauses,
wherein said particles have a R-3m crystal structure.
[0111] 5. The lithium cobalt-based oxide cathode active material
powder according to any of the preceding clauses, comprising
particles having an averaged circularity of superior or equal to
0.90 and inferior or equal to 1.00, preferably inferior or equal to
0.95.
[0112] 6. The lithium cobalt-based oxide cathode active material
powder according to any of the preceding clauses, wherein y and
z=0.
[0113] 7. A lithium-ion secondary batteries comprising the lithium
cobalt-based oxide cathode active material powder according to any
of the preceding clauses.
* * * * *