Lithium Cobalt Based Complex Oxide Having Good Lifespan Properties And Secondary Battery Anode Active Material Including Same
Abstract:
The present invention relates to a lithium cobalt-based complex oxide including lithium, cobalt, and manganese, which is represented by Chemical Formula 1, the lithium cobalt-based complex oxide being characterized by maintaining a O3 phase single-phase crystalline structure at a theoretical State of Charge (SOC) of 50% or greater. In the formula, LixCo1-y-zMnyAzO2 (1), 0.95≤x≤1.15, 0
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Notices, Deadlines & Correspondence
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
2. JEON Hye Lim
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
3. LEE Myung Ki
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
4. MIN Geun Gi
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
5. JUNG Wang Mo
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
Specification
LITHIUM-COBALT BASED COMPLEX OXIDE HAVING SUPERIOR
LIFESPAN CHARACTERISTICS AND CATHODE ACTIVE MATERIAL FOR
SECONDARY BATTERIES INCLUDING THE SAME
The present invention relates to a lithium-cobalt based complex oxide having
superior lifespan characteristics and a cathode active material for secondary batteries
including the same. More pal-titularly, the present invention relates to a lithium-cobalt
based complex oxide including lithium and cobalt maintaining a crystal structure of a
10 single 03 phase at a state of charge (SOC) of 50% or more.
As mobile device technology continues to develop and demand therefor
continues to increase, denland for secondary batteries as energy sources is rapidly
increasing. Among these secondary batteries, lithium secondary batteries, which have
15 high energy density and operating voltage, long cycle lifespan, and low self-discharge
rate, are commercially available and widely used.
In addition, recently, lithium ion batteries are commercially used as a power
supply in home electronics such as laptop computers, mobile phones and the like.
-1-
Furtherniore, as interest in environmental problcms is increasing, research into electric
vehicles (EVs), hybrid electric vehicles (I-IEVs), and the like that can replace vehicles
using fossil fuels, such as gasoline vehicles, diesel vehicles, and the like, which are one
of the main causes of air pollution, is underway.
5 As a cathode of conventionally used lithium ion batteries, lithium cobalt oxides
such as LiCo02 having a layered structure are used. As an anode, graphite based
materials are generally used.
Lithium cobalt oxides are currently widely used due to superior physical
properties such as superior cycle characteristics as compared to LiNiOz and LiMnz04.
10 To develop seconhy batteries having high energy density, cathode active materials
having large capacity are required. However, when operating voltage of lithium cobalt
oxides are fixed unlike thee component-based cathode active materials, it is
substantially impossible to enlarge capacities of materials.
Accordingly, lithium cobalt oxides must be used under high voltage to develop
15 secondary batteries having high energy density. However, approximately 50% or more
of lithium ions are eliminated under high voltage operation, structures of lithium cobalt
oxides collapse and, as such, lifespan characteristics are rapidly degraded.
To overcome this problem and to achieve high energy density, technologies
substituting some cobalt with Al, ,Mg, B or the like, or treating surfaces of lithium
cobalt oxides with a metal oxide such as A1203, MgzO, Ti02 or the like are !mown.
Howevel; when some cobalt is substituted with metals described above, there
5 is still a problem such as degradation of lifespan characteristics. When a surface of a
lithium cobalt oxide is coated with a metal oxide, specific capacity may be reduced due
to addition of a coating material that does not directly participate in charge and
discharge reaction, and a metal oxide with vely low electrical conductivity mainly
constitutes the coating material, which results in reduced conductivity. In addition, the
10 coating process reduces active reaction area, thereby increasing interfacial resistance
and deteriorating high-rate charge and discharge characteristics.
Therefore, there is an urgent need to develop technology for fundamentally
addressing these problems and enhancing high voltage lifespan characteristics of a
lithium cobalt oxide.
15 [DISCLOSURE]
The present invention aims to address the aforementioned problen~s of the
related art and to achieve technical goals that have long been sougl~t.
As a result of a variety of intensive studies and various experiments, the
inventors of the present invention confirmned that rate characteristics and lifespan
characteristics are inlproved when a lithium-cobalt based comnplex oxide maintains a
crystal structure of a single 03 phase at a state of charge (SOC) of 50% or more,
5 namely, under high voltage, thus colnpleting the present invention.
In accordance with one aspect of the present invention, provided is a lithiumcobalt
based complex oxide including lithium, cobalt and manganese, represented by
Formula 1 below, wherein the lithium-cobalt based complex oxide maintains a crystal
10 structure of a single 03 phase at a state of charge (SOC) of 50% or nlore based on a
theoretical amount:
wherein 0.951x11.15,O
Lithium-cobalt based complex oxide samples manufactured according to
Examples 1 and 4, and Comparative Example 1 were prepared. An X-ray diffraction
10 (XRD) pattern of each sample was collected using a Siemens D500 diffiactometer
equipped with copper target X-ray tube and diffsacted beam monochromator. Since the
samples are thick and wide, the samples were manufactured in a flat and rectangular
powder-bed shape such that volume irradiated by X-ray beat11 is constant. Using GSAS
of a Rietveld refinement program disclosed in [A. C. Larson and R. B. Von Dreele,
15 "General Stmcture Analysis System (GSAS)", Los Alamos National Laboratory Report
LAUR 86-748 (2000)], a lattice constant of a unit cell was calculated. Results are
sutnmarized in Table 1 below.
Here, crystal structures of unit cells tnanufactnred according to Example 1 and
Comparative Example 1 were nleasured in a full voltage range. The lithium-cobalt
base& complex oxide sa~nple manufactured according to Example 4 maintained a
crystal structure of a single 03 phase in voltage of 4.4 V or more.A crystal structure
was not measured below the voltage range.
5 Referring to Table 1, the lithiutn-cobalt based oxides manufactured according
to Examples 1 and 4 maintained crystal structures of single 03 phases under full
charging voltage not exceeding 4.50 V. On the other hand, the lithium-cobalt based
complex oxide manufactured according to Comparative Example 1 showed another
phase, in addition to an 03 phase, over 4.35 V, resulting in two phases. Subsequently, at
10 4.50 V, all 03 phases transitioned to the another phase, resulting in formation of one
phase.
Using each of the lithium-cobalt based conlplex oxides manufactured
according to Exanlple 1 to 3 and Cotnparative Exanlple 1, the lithium-cobalt based
conlplex oxide:a conductive material (Denka b1ack):a binder (PVdF) in a weight ratio of
95:2.5:2.5 were added to NMP and then mixed to manufacture a cathode mixture. The
5 cathode mixture was coated to a thickriess of 200 Vrn on an aluminum foil and then
pressed and dried. As a result, a cathode was manufactured.
To manufacture a lithium secondary battery, Li metal was used as an anode and
a carbonate based electrolyte, namely, 1 ~nol LiPF6 dissolved in a mixture of ethyl
carbonate (EC) and ethyl methyl carbonate (EMC) mixed in a ratio of 1:l was used as
10 an electrolyte.
Measurement of initial charge and discharge capacities, and eficieticies
When the lnanufactured lithium secondary batteries were charged and
discharged at 0.1 C in a voltage range of 3.0 V to 4.4 V, initial capacities and
efficiencies wvere measured. Results are summarized in Table 2 below.
Measurement of lifespan characteristics
After charging and discharging the manufactured lithium secondary batteries
once at 0.1 C in chambers of 250 and in a voltage range of 3.0 V to 4.4 V, lifespan
characteristics wvere measured fifty times while charging at 0.5 C and discharging at 1
C. After charging and discharging once at 0.1 C in a 450 chamber and in a voltage
-21-
range of 3.0 V to 4.5 V, lifespan characteristics were measured fifty tillles while
charging at 0.5 C and discharging at 1 C. Results are su~nnlarizedi n Table 2 below and
illustrated in FIGS. 1 to 10.
Measurement of rate characteristics
5 Rate characteristics of the manufactured lithium secondary batteries were
tested in a voltage range of 3.0 V to 4.4 V and capacity at each C-rate with I-espect to
capacities at 0.1 C was calculated. Results are summarized in Table 2 below and
illustrated in FIG. 11.
[Table 21
Example 1
Example 2
Example 3
Comparative
Example 1
Initial capacity and efficiency
Lifespan
characteristics
Rate
characteristics
(YOa,t 50 cycles)
1.0 C
98.0
98.4
99.2
93.9
Charge
(mAh/g)
180.5
180.3
179.6
180.9
Discharge
(tnAldg)
177.4
177.1
176
176.8
Efficiency
(%)
98.2
98.3
98.0
97.8
Referring to Table 2 and FIGS. 1 to 10, initial capacities and efficiencies of
lithium secondary batteries using the lithium-cobalt based complex oxides
nlanufaetured according to Examples 1 to 3 were sliglitly higher but were not greatly
different, when compared to those of a lithiu~n secondary battery using the lithium-
5 cobalt based conlplex oxide manufactnred according to Comparative Example 1.
However, rate characteristics and lifespan characteristics of the lithium secondary
batteries using the lithium-cobalt based complex oxides manufactured according to
Examples 1 to 3 were superior, when compared to those of a lithium secondary battery
using the lithium-cobalt based complex oxide manufactured according to Comparative
10 Example 1. In particular, rate characteristics at a high rate and lifespan characteristics at
high tenlperature werevastly*superior.
As described in Experimental Example 1, the lithium-cobalt based complex
oxide manufactured according to Example 1 maintained the crystal stn~cture of the
single 0 3 phase even under high voltage. On the other hand, the 0 3 phase of the
15 lithium-cobalt based complex oxide manufactured according to Conlparative Example 1
is partially or entirely changed into the P3 phase and thereby charge and discharge are
not maintained and irreversible capacity increases.
For reference, in FIGS. 1 and 2, graphs of Exatnple 2 overlap with graphs of
Example 3 and thereby the graphs are not easily distinguished.
Using each of the lithium-cobalt based complex oxides manufactured
according to Examples 1, 6 and 7, the lithium-cobalt based conlplex oxide:a conductive
material (Denka b1ack):a binder (PVdF) in a weight ratio of 95:2.5:2.5 were added to
5 NMP and then mixed to manufacture a cathode mixture. The cathode mixtme was
coated to a thickness of 200 pm on an aluminum foil and then pressed and dried. As a
result, a cathode was manufactured.
To manufacture a lithium secondary battery, Li metal was used as an anode and
a carbonate based electrolyte, namely, 1 mol LiPF6 dissolved in a mixture of ethyl
10 carbonate (EC) and ... ethyl methyl carbonate (EMC) mixed in a ratio of 1:l was used as
an electrolyte.
After charging and discharging the manufactured lithium secondary batteries
once at 0.1 C in a 450 chamber and in a voltage range of 3.0 V to 4.5 V, lifespan
characteristics were measured fifty times while charging at 0.5 C and discharging at 1
15 C. Results are illustrated in FIG. 12.
Referring to FIG. 12, the lithium-cobalt based complex oxides, which are
doped with Mg, manufactured according to Examples 6 and 7 sl~owede xcellent lifespan
characteristics, when compared with the lithium-cobalt based conlplex oxide
manufactured according to Exalnple 1.
Those skilled in the art will appreciate that various modifications, additions and
substitutions are possible, without departing from the scope and spirit of the invention
as disclosed it1 the accompanying claims.
5 As described above, a lithium-cobalt based complex oxide according to the
present invention maintains a c~ystals tructure of a single 03 phase at a state of charge
(SOC) of 50% or more, namely, under high voltage and thereby collapse of a sttvcture
of the lithium-cobalt based complex oxide is prevented, and, accordingly, rate
characteristics and lifespan characteristics are improved.
[claim 11 A lithium-cobalt based colnplex oxide represented by Forlnula 1
below comprising lithium, cobalt and manganese, wherein the lithium-cobalt based
colnplex oxide lnailitains a crystal structure of a single 03 phase at a state of charge
5 (SOC) of 50% or more based on theoretical capacity:
wherein 0.955~51.15,O
Documents
Application Documents
#
Name
Date
1
201617002101-Annexure [14-11-2024(online)].pdf
2024-11-14
1
Priority Document [20-01-2016(online)].pdf
2016-01-20
2
201617002101-Response to office action [14-11-2024(online)].pdf
2024-11-14
2
Form 5 [20-01-2016(online)].pdf
2016-01-20
3
Form 3 [20-01-2016(online)].pdf
2016-01-20
3
201617002101-IntimationOfGrant20-09-2023.pdf
2023-09-20
4
Form 18 [20-01-2016(online)].pdf
2016-01-20
4
201617002101-PatentCertificate20-09-2023.pdf
2023-09-20
5
Form 1 [20-01-2016(online)].pdf
2016-01-20
5
201617002101-FORM 3 [10-07-2023(online)].pdf
2023-07-10
6
Drawing [20-01-2016(online)].pdf
2016-01-20
6
201617002101-Information under section 8(2) [10-07-2023(online)].pdf
2023-07-10
7
Description(Complete) [20-01-2016(online)].pdf
2016-01-20
7
201617002101-PETITION UNDER RULE 137 [10-07-2023(online)].pdf
2023-07-10
8
201617002101.pdf
2016-01-24
8
201617002101-Written submissions and relevant documents [10-07-2023(online)].pdf
2023-07-10
9
201617002101-Correspondence to notify the Controller [23-06-2023(online)].pdf
2023-06-23
9
abstract.jpg
2016-06-27
10
201617002101-FORM-26 [23-06-2023(online)].pdf
2023-06-23
10
201617002101-PETITION UNDER RULE 137 [07-05-2018(online)].pdf