DESCRIPTION
POSITIVE ELECTRODE ACTIVE MATERIAL AND PREPARATION METHOD
THEREOF
5
CROSS-REFERENCE TO RELATED APPLICATION(S)
[0001] This application claims the benefit of Korean Patent
Application Nos. 10-2014-0131747, filed on September 30, 2014,
and 10-2015-0135492, filed on September 24, 2015, the entire
10 contents of which are hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to a positive electrode
active material, a preparation method thereof, and a lithium
15 secondary battery which includes the positive electrode
active material.
BACKGROUND ART
[0003] Lithium secondary batteries are small, lightweight,
20 high capacity batteries which have been widely used as a
power source for mobile devices since 1991. Recently, with
rapid advancements in the electronics, communications, and
computer industries, camcorders, mobile phones, notebook PCs,
and the like, have appeared and continue to advance at an
25 incredible pace. The demand for lithium secondary batteries
2
as a power source for driving such mobile electronic
communication devices continues to increase.
[0004] Lithium secondary batteries are limited in that
lifetime rapidly decreases with repeated charging and
discharging. In particular, this limitation is more 5 severe
at high temperatures. This is because electrolyte breaks
down or active material degrades due to effects such as
moisture inside of the battery, etc., or because of phenomena
which occurs as the internal resistance of the battery
10 increases.
[0005] Examples of lithium secondary battery positive
electrode active materials which are being researched and
developed accordingly include lithium nickel oxide (LiNiO2),
lithium manganese oxide (LiMn2O4), lithium iron phosphate
15 (LiFePO4), and lithium nickel cobalt manganese oxide
(Li(NixCoyMnz)O2). However, in the case of LiNiO2, not only is
synthesis difficult, but there is a limitation in thermal
stability, and thus commercialization is difficult. In the
case of LiMn2O4, although there has been some
20 commercialization of low-priced products, lifetime properties
are poor due to structural distortion caused by Mn3+ (Jahn-
Teller distortion). In addition, although LiFePO4 has low
cost and good stability and is thus being extensively
researched for use in hybrid electric vehicles (HEV),
25 application in other areas is currently limited due to a low
3
conductivity.
[0006] Consequently, Li(NixCoyMnz)O2 has recently been the
most prominent among positive electrode active materials
which are being considered as a replacement for LiCoO2. Such
material is more inexpensive than LiCoO2 and has 5 advantages
of high-capacity and of being able to be used at high voltage,
but has disadvantages of poor rate capability and poor
lifetime properties at high temperature. Extensive research,
such as on a method for coating surfaces of electrode active
10 material with metal oxide coating layers, has been carried
out to overcome such limitations.
[0007] For example, Korean Patent No. 10-277796 discloses a
technique for coating metal oxide by coating metals such as
magnesium (Mg), aluminum (Al), cobalt (Co), potassium (K),
15 sodium (Na), calcium (Ca), etc., on the surface of positive
electrode active material and then performing heat treatment
in an oxidizing atmosphere.
[0008] However, there still remain difficulties in
overcoming the limitations of reaction between electrolyte
20 and positive electrode active material, and structural
transitions on the surface of positive electrode active
materials due to the existence of impurities on the surface
of positive electrode active materials. Consequently, there
is a demand for a positive electrode active material which is
25 capable of minimizing reduction in capacity or output and
4
improving lifetime properties in secondary batteries by
reducing addition reactions of electrolyte and active
material during charging and discharging, and reducing the
internal resistance of the battery.
[0009] 5 [Prior Art Document]
[0010] [Patent Document]
[0011] Korean Patent No. 10-277796
DISCLOSURE OF THE INVENTION
10 TECHNICAL PROBLEM
[0012] A first technical objective of the present invention
is to provide a positive electrode active material which has
excellent conductivity and whose interface reaction with
electrolyte solution is suppressed, and which may thereby
15 improve the output and cycle properties of a secondary
battery.
[0013] A second technical objective of the present invention
is to provide a method for economically and easily preparing
the positive electrode active material.
20 [0014] A third technical objective of the present invention
is to provide a positive electrode which includes the
positive electrode active material.
[0015] A fourth technical objective of the present invention
is to provide a lithium secondary battery which includes the
25 positive electrode.
5
TECHNICAL SOLUTION
[0016] To overcome such above limitations, the present
invention provides a positive electrode active material
including lithium transition metal oxide particles 5 and
conductive oxide particles, the conductive oxide particles
being any one selected from a group which consists of indium
tin oxide (ITO) and antimony tin oxide (ATO), or a mixture of
at least two thereof.
10 [0017] In addition, the present invention, according to an
embodiment, provides a method for preparing a positive
electrode active material which includes mixing and heat
treating lithium transition metal oxide particles and
conductive oxide particles, the conductive oxide particles
15 being any one selected from a group which consists of indium
tin oxide (ITO) and antimony tin oxide (ATO), or a mixture of
at least two thereof.
[0018] Moreover, the present invention provides a positive
electrode which includes the positive electrode active
20 material.
[0019] Furthermore, the present invention provides a lithium
secondary battery which includes the positive electrode.
ADVANTAGEOUS EFFECTS
25 [0020] A positive electrode active material according to an
6
embodiment of the present invention includes lithium
transition metal oxide particles and particular conductive
oxide particles which have a single phase, and thus the
positive electrode active material not only has superb
electronic conductivity, while having excellent ion 5 transfer
capability which allows transfer of metal ions such as
lithium ions to lithium transition metal oxide particles, but
may also minimize capacity reduction and output reduction in
a secondary battery.
10 [0021] Moreover, since there is a shock absorbing effect
when producing positive electrodes, in particular during a
pressing operation, due to structural properties of the
conductive oxide particles, fracturing of positive electrode
active material may be minimized. Consequently, when applied
15 to secondary batteries, lifetime properties may be further
improved.
[0022] In addition, according to a preparation method in
accordance with an embodiment of the present invention, a
positive electrode active material may be easily and
20 economically prepared by using pre-formed nano-sized oxide
particles, which are not in the form of precursors, in a
simple heat treatment of nano-sized oxide particles at the
exterior, interior, or exterior and interior of lithium
transition metal oxide.
25
7
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The following drawings accompanying the present
specification are examples of exemplary embodiments of the
present invention, and are provided to provide better
understanding of the descriptions and technical scope of 5 the
invention, and thus the present invention should not be
construed as limited to that which is set forth in the
drawings.
[0024] FIG. 1 illustrates predictive modeling of the pathway
10 of lithium in an yttria stabilized zirconia (YSZ) composite
particle which was optimized through Discrete Fourier
Transformation (DFT) structure optimization.
[0025] FIG. 2 is a graph analyzing ionic conductivity
according to oxygen vacancies in an yttria stabilized
15 zirconia (YSZ) composite particle which was optimized through
Discrete Fourier Transformation (DFT) structure optimization.
[0026] FIG. 3 is a scanning electron microscope (SEM) image
of Example 1 of the present invention.
[0027] FIG. 4 is a scanning electron microscope (SEM) image
20 of Example 2 of the present invention.
[0028] FIG. 5 is a scanning electron microscope (SEM) image
of Comparative Example 1.
[0029] FIG. 6 is a scanning electron microscope (SEM) image
of Comparative Example 2.
25 [0030] FIG. 7 is a scanning electron microscope (SEM) image
8
of Comparative Example 3.
[0031] FIG. 8 is a graph illustrating lifetime properties of
lithium secondary batteries which were manufactured in
Examples 1 and 2, and Comparative Examples 1 to 4.
[0032] FIG. 9 is a graph illustrating X-5 ray diffraction
(XRD) analysis results of indium tin oxide (ITO) transition
metal oxide particles which are included in a positive
electrode active material of the present invention.
[0033] FIG. 10 is a graph illustrating XRD analysis results
10 of antimony tin oxide (ATO) transition metal oxide particles
which are included in a positive electrode active material.
MODE FOR CARRYING OUT THE INVENTION
[0034] Hereinafter, the present invention is described in
15 greater detail in order to provide better understanding
thereof.
[0035] Terms used in the present specification and claims
should not be construed as limited to their typical or
dictionary definitions. Rather, based on the principle that
20 the concepts of terms may be appropriately defined by the
inventor in such a way which best describes the invention,
the terms should only be construed as definitions and
concepts which are in accordance with the technical scope of
the present invention.
25 [0036] A positive electrode active material according to an
9
embodiment of the present invention includes lithium
transition metal oxide particles and conductive oxide
particles, the conductive oxide particles being any one
selected from a group which consists of indium tin oxide
(hereinafter, ITO) and antimony tin oxide (5 hereinafter, ATO),
or a mixture of at least two thereof.
[0037] Moreover, the positive electrode active material
according to an embodiment of the present invention may
include the conductive oxide particles which have a single10
phase peak when measured by x-ray diffraction analysis.
[0038] The positive electrode active material according to
an embodiment of the present invention includes the lithium
transition metal oxide particles and specific conductive
oxide particles which have a single phase, and thus not only
15 has superb electronic conductivity while having excellent ion
transfer capability which allows transfer of metal ions such
as lithium ions to the lithium transition metal oxide
particles, but may also minimize capacity reduction and
output reduction in secondary batteries.
20 [0039] Moreover, since there is a shock absorbing effect
when producing positive electrodes, in particular during a
pressing operation, due to structural properties of the
conductive oxide particles, fracturing of the positive
electrode active material may be minimized so that, when
25 applied to the secondary batteries, the lifetime properties
10
may be further improved.
[0040] According to an embodiment of the present invention,
the conductive oxide particles may include any one, or a
mixed oxide of two or more kinds, selected from a group which
consists of ITO and ATO, and is desirably ATO alone, or 5 a
mixed conductive oxide which includes ATO.
[0041] When the mixed conductive oxide is used, the content
ratio of the ITO to the ATO may be a weight ratio of about
1:0.01 to about 1:1, and desirably a weight ratio of about
10 1:0.1 to about 1:0.5.
[0042] In the positive electrode active material according
to an embodiment of the present invention, the ATO may
include any one of compounds represented by the below Formula
1 or 2, or include a mixture thereof.
15
(SnO2)x(Sb2O3)y, x+y = 1, 0
(SnO2)x(Sb2O5)y, x+y = 1, 0
(InO2)a(Sb2O3)b, a+b = 1, 0
(InO2)a(Sb2O5)b, a+b = 1, 0
Li(1+a)Ni(1-b-c)Mn(b)Co(c) M'(s)M"(v)O2
20 [0088] In the above formula, M' includes any one from among
a group which consists of Sb, Sn, In, Y, Zr, La, Sr, Ga, Mg,
Mn, Ca, Sc, and Ni, or a mixed element of two or more kinds
selected from among the group, and desirably, any one from
among a group which consists of Y, Zr, and Ni, or a mixed
25 element of two or more kinds selected from among the group.
22
[0089] M'' is one or more element among Ca, Nb, W, Mg, Ti, B,
Mo, Sc, or Zr, and
[0090] 0≤a<0.2, 0≤b≤0.5, 0≤c≤0.5, 0≤s≤0.2, and 0≤v≤0.2.
[0091] According to an embodiment of the present invention,
in the above Formula 5, it is desirable that 0≤5 a<0.2 and
that M' include any one selected from among a group which
consists of Sb, Sn, In, Zr, Y, Zr, Ca, Sc, and Ni, or a mixed
element of two or more kinds among the group. The s and v
may have concentration gradients which decrease going from
10 the surface of the lithium transition metal oxide particle to
the interior.
[0092] Moreover, according to an embodiment of the present
invention, in the above Formula 1, 0≤a≤0.09 is desirable,
and 0≤a≤0.06 may be more desirable.
15 [0093] In the above Formula 1, when a is above 0.09,
especially when a is at least 0.2, the effect of coating the
conductive oxide particles and composite particles (for
example, YSZ) on the lithium transition metal oxide particle
may have a lifetime property effect difference which is
20 within about 10% when compared to the case of coating a
different oxide (for example ZrO2), and thus may not be
remarkable. On the other hand, when, in the above Formula 1,
a is 0.09 or less, especially when a is 0, the effect of
coating the composite particles on the lithium transition
25 metal oxide particle may display a remarkable difference of
23
about 30% to about 70% in the lifetime property effect when
compared to the case of coating a different oxide.
[0094] A Brunauer-Emmett-Teller (BET) specific surface area
of the positive electrode active material according to an
embodiment of the present invention of about 0.1 m2/5 /g to
about 10 m2/g is desirable. When the BET specific surface
area is outside of the above range, the output property of
the secondary battery may be degraded.
[0095] According to an embodiment of the present invention,
10 the specific surface area of the positive electrode active
material may be measured by using the BET method. For
example, the specific surface area may be measured through a
six-point BET method according to a nitrogen gas adsorption
flow method, by using a porosimetry analyzer (Bell Japan Inc,
15 Belsorp-II mini).
[0096] The present invention provides a preparation method
for the positive electrode active material.
[0097] The preparation method for the positive electrode
active material according to an embodiment of the present
20 invention includes mixing and heat treating the lithium
transition metal oxide particles and conductive oxide
particles. The conductive oxide particles include any one
selected from a group which consists of indium tin oxide
(ITO) and antimony tin oxide (ATO), or include a mixture of
25 two or more kinds from among the group. The positive
24
electrode active material may include the conductive oxide
particles which have a single-phase peak when measured by XRD
analysis.
[0098] In the preparation method for the positive electrode
active material according to an embodiment of 5 the present
invention, the composite particles may be further added
during the mixing.
[0099] The composite particle may include any one selected
from a group which consists of yttria stabilized zirconia
10 (YSZ), gadolinia-doped ceria (GDC), LaSrGaMg (LSGM), LSM(La(1-
x)SrxMnO3), CSZ, SSZ, and Ni-YSZ, or include a mixture of two
or more kinds from among the group.
[00100] According to an embodiment of the present invention,
the conductive oxide particles desirably include ATO, or a
15 mixed particle of ATO and ITO, and the composite particle
desirably includes any one selected from the group which
consists of YSZ, CXZ, and SSZ, or a mixture of two or more
kinds from among the group.
[00101] According to an embodiment of the present invention,
20 the positive electrode active material more desirably
includes ATO as the lithium transition metal oxide particle
and conductive oxide particle, and YSZ as the composite
particle.
[00102] When ATO is used as the conductive oxide particle and
25 YSZ is used as the composite particle, the mixing (content)
25
ratio of the ATO to YSZ may be a weight ratio of about 1:0.01
to about 1:1.15, or desirably about 1:0.1 to about 1:1.
[00103] According to an embodiment of the present invention,
the heat treatment may be performed in a temperature range of
about 100℃ to about 1200℃ for about 4 hours to 5 o about 24
hours.
[00104] According to a preparation method for the positive
electrode active material in accordance with an embodiment of
the present invention, forming the coating layer which
10 includes the conductive oxide particles, or the conductive
oxide particles and composite particles on the surface of the
lithium transition metal oxide particle; including the
conductive oxide particles, or both the conductive oxide
particles and the composite particles in the interior of the
15 lithium transition metal oxide particle; or including the
conductive oxide particles, or the conductive oxide particles
and composite particles in both the interior and exterior of
the lithium transition metal oxide particle may have an
effect on the heat treatment temperature and time during heat
20 treatment.
[00105] According to an embodiment of the present invention,
when heat treatment is performed in a temperature range of
about 200℃ to about 800℃, desirably about 300℃ to about
600℃, the coating layer may be formed on the outer surface
25 of the lithium transition metal oxide particle through the
26
heat treatment.
[00106] Thus, even when heat treatment is performed in a
temperature range of about 200℃ to about 800℃, the coating
layer is formed on the lithium transition metal oxide
particle surface, and the positive electrode active 5 material
may be obtained in which the coating layer includes the
conductive oxide particles, or the conductive oxide particles
and composite particles, and in which the conductive oxide
particles and composite particles include a single-phase peak
10 when measured by XRD analysis.
[00107] According to an embodiment of the present invention,
some of the conductive oxide particles, or some of the
conductive oxide particles and composite particles may be
included in the interior of the lithium transition metal
15 oxide particle, even when heat treating in a temperature
range of about 200℃ to about 800℃. In such the case, the
conductive oxide particles, or the conductive oxide particles
and composite particles have concentration gradients which
decrease going from the surface of the lithium transition
20 metal oxide particle to the interior, and are included on the
surface of the lithium transition metal oxide particle or in
the interior of the lithium transition metal oxide particle,
such that the conductive oxide particles, or the conductive
oxide particles and composite particles may be composited
25 with the lithium transition metal oxide particle to thereby
27
form the composite material.
[00108] According to an embodiment of the present invention,
when forming an outer coating layer on the lithium transition
metal oxide particle, for example, when coating by using a
spraying method of spinning at a high 5 velocity,
nanodispersion is possible, and thus the coating layer may be
well formed as a single layer coating.
[00109] The thickness of the coating which is formed on the
lithium transition metal oxide particle may change according
10 to the amount of the conductive oxide particles.
Consequently, when the amount of the conductive oxide
particles exceeds the above range, the coating layer is in a
shape of conductive oxide particles formed not as a single
layer but instead as multiple layers, and thus undesirable
15 with respect to output and internal resistance.
[00110] According to an embodiment of the present invention,
when heat treatment is performed in a temperature range of,
for example about 600℃ to about 1200℃, the positive
electrode active material may be obtained which includes, in
20 the interior of the lithium transition metal oxide particle,
the conductive oxide particles, or the conductive oxide
particles and composite particles.
[00111] Here, the conductive oxide particles, or the
conductive oxide particles and composite particles have
25 concentration gradients which decrease going from the surface
28
of the lithium transition metal oxide particle to the
interior, and may form a composite material by being
composited with the lithium transition metal oxide particle.
In this case, the conductive oxide particles, or the
conductive oxide particles and composite particles 5 les may be
present from the surface of the lithium transition metal
oxide particle to about 500 nm or more into the interior.
[00112] According to an embodiment of the present invention,
even when heat treatment is performed in a temperature range
10 of about 600℃ to about 1200℃, the conductive oxide particles,
or the conductive oxide particles and the composite particles
may be present on the outer surface of the lithium transition
metal oxide particle.
[00113] According to the preparation method for the positive
15 electrode active material in accordance to an embodiment of
the present invention, the transition metal oxide particle
may include the lithium transition metal composite oxide
particle of the above Formula 1, and the below s and v may
have concentration gradients which decrease going from the
20 surface of the lithium transition metal oxide particle to the
interior.
[00114] According to the preparation method for the positive
electrode active material in accordance to an embodiment of
the present invention, the average particle diameter (D50) of
25 the conductive oxide particles, or the conductive oxide
29
particles and composite particles, which are used as surface
modifiers, is about 1 nm to about 100 nm, desirably about 5
nm to about 80 nm, and more desirably about 10 nm to about 60
nm.
[00115] In the present invention, the average 5 particle
diameter (D50) of the conductive oxide particles, or the
conductive oxide particles and composite particles may be
defined as the particle diameter at the 50% position of the
particle size distribution. The average particle diameter
10 (D50) of the particles according to an embodiment of the
present invention may be measured by using, for example, a
laser diffraction method. The laser diffraction method may
typically be used for measuring particles sizes from about
the submicron range to about several mm, and highly
15 reproducible and resolvable results may be obtained.
[00116] For example, in the method for measuring the average
particle diameter (D50) of the ATO, ATO is dispersed in
solution and introduced into a commercially available laser
diffraction type particle size measurement instrument (for
20 example, Microtrac MT 3000), and after emitting ultrasonic
waves of about 28 kHz at about 60 W output, the average
particle diameter (D50) at the 50% position of the particle
size distribution in the measurement instrument may be
calculated.
25 [00117] According to an embodiment of the present invention,
30
the surface modifier may be used in an amount of about 50 to
about 30000 ppm, desirably about 100 to about 20000 ppm, and
more desirably about 400 to about 10000 ppm.
[00118] According to the preparation method of the positive
5 electrode active material in accordance with an embodiment of
the present invention, a dry mixing method or a wet mixing
method (specifically, a nano-sol wet mixing method) may be
used for the mixing.
[00119] In the preparation method according to an embodiment
10 of the present invention, the dry mixing method may be
performed by mixing with a shaker, by a mortar grinder mixing
method, or by a mixing method which uses mechanical milling,
and desirably, mechanical milling may be desirable for
forming a uniform coating layer.
15 [00120] Describing in detail, the method of mixing with the
shaker may be performed through hand mixing by shaking the
lithium transition metal oxide particles and surface
modifiers several times and thereby mixing.
[00121] The mortar grinder mixing method is a mixing method
20 in which the mortar is used to uniformly mix the lithium
transition metal oxide particles and surface modifiers.
[00122] The mechanical milling method may use, for example, a
roll-mill, a ball-mill, a high energy ball mill, a planetary
mill, a stirred ball mill, a vibrating mill, or a jet-mill to
25 perform mixing of the lithium transition metal oxide
31
particles and surface modifier through mechanical friction,
and compressive stress may be applied mechanically by
rotating at, for example, about 100 rpm to about 1000 rpm.
[00123] Moreover, to reduce the chance of the lithium
transition metal oxide particles being damaged by th5 e
solution, it is desirable to use the dry mixing method or,
considering the uniformity of the coating, the nano-sol wet
mixing method.
[00124] In the preparation method according to an embodiment
10 of the present invention, in the nano-sol wet mixing method,
after forming a colloidal inorganic nano-sol by, for example,
adding solvent and dispersing agent to a purified inorganic
precursor and then agitating, surface treatment may be
performed on the lithium oxide by adding the surface modifier
15 and lithium transition metal oxide particles to the nano-sol.
The nano-sol wet mixing method may advantageously improve the
uniformity of the coating.
[00125] The present invention provides a positive electrode
which includes the positive electrode active material.
20 [00126] The positive electrode may be manufactured by using a
typical method which is known in the field. For example, the
positive electrode may be manufactured by mixing and
agitating solvent and, as needed, binder, conductive agent,
or dispersant, with the positive electrode active material to
25 prepare slurry, coating and pressing the slurry on a metallic
32
current collector, and then drying.
[00127] According to an embodiment of the present invention,
with respect to toughness, the positive electrode active
material porous particles are strong, and thus especially
5 desirable to be included in a porous positive electrode.
[00128] The metallic current collector is a metal with high
conductivity, and any metallic current collector may be used
to which the slurry of the positive electrode active material
may be easily attached, and which is unreactive in the
10 voltage range of the battery. Non-limiting examples of the
positive electrode current collector include aluminum, nickel,
or foils which are produced from mixtures thereof.
[00129] The solvent for forming the positive electrode
includes organic solvents such as N-methyl pyrrolidone (NMP),
15 dimethyl formamide (DMF), acetone, dimethyl acetamide, etc.,
or water, and such solvents may be used alone or by mixing
two or more kinds. An amount of solvent is sufficient which
may dissolve and disperse the positive electrode active
material, binder, and conductive agent, taking into
20 consideration the coating thickness and production yield of
the slurry.
[00130] As the binder, various types of binder polymer may be
used, including poly(vinylidene fluoride-hexafluoropropylene)
copolymer (PVDF-co-HFP), polyvinylidene fluoride,
25 polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol,
33
carboxymethyl cellulose (CMC), starch, hydroxypropyl
cellulose, regenerated cellulose, polyvinylpyrrolidone,
tetrafluoroethylene, polyethylene, polypropylene, polyacrylic
acid, ethylene-propylene-diene monomer (EPMD), sulfonated
EPDM, styrene butadiene rubber (SBR), fluorocarbon 5 rubber,
polymers in which the hydrogen in such polymers was
substituted by Li, Na, Ca, etc., or various copolymers, etc.
[00131] The conductive agent is not particularly limited and
may be any which is conductive and does not cause a chemical
10 change to the battery, and, for example, graphite such as
natural graphite or synthetic graphite, carbon blacks such as
carbon black, acetylene black, ketjen black, channel black,
furnace black, lamp black, or thermal black, conductive
fibers such as carbon fiber or metal fiber, conductive tubes
15 such as carbon nanotube, metal powders such as fluorocarbon,
aluminum, or nickel powder, conductive whiskers such as zinc
oxide or potassium titanate, conductive oxides such as
titanium oxide, conductive materials such as polyphenylene
derivatives, etc., may be used as the conductive agent.
20 [00132] As the dispersant, an aqueous dispersant or an
organic dispersant such as N-methyl-2-pyrrolidone may be used.
[00133] The present invention may provide the secondary
battery which includes the positive electrode, a negative
electrode, and a separator which is disposed between the
25 positive electrode and negative electrode.
34
[00134] As a negative electrode active material which is used
in the negative electrode according to an embodiment of the
present invention, carbon material, lithium metal, silicon,
tin, etc., from which lithium ions may be occluded or
released, may typically be used. Desirably, 5 the carbon
material may be used, and both low-crystalline carbon or
high-crystalline carbon may be used as the carbon material.
Soft carbon and hard carbon are representative of the lowcrystalline
carbon, and high temperature fired carbon such as
10 natural graphite, kish graphite, pyrolytic graphite,
mesophase pitch based carbon fiber, meso-carbon microbeads,
mesophase pitches, petroleum or coal tar pitch derived cokes,
etc., are representative of the high-crystalline carbon.
[00135] The negative electrode current collector is typically
15 made to a thickness of about 3 μm to about 500 μm. Such the
negative electrode is not particularly limited and may be any
which is conductive and does not cause chemical change to the
battery, and, for example, copper, stainless steel, aluminum,
nickel, titanium, fired carbon, copper or stainless steel
20 whose surface is surface treated with carbon, nickel,
titanium, silver etc., or aluminum-cadmium alloy may be used
as the negative electrode. Moreover, as with the positive
electrode current collector, fine ridges and grooves may be
formed on the surface to strengthen the bonding strength of
25 the negative electrode active material, and the negative
35
electrode current collector may be used in various forms,
such as, film, sheet, foil, net, porous material, foam,
nonwoven fabric, etc.
[00136] As with the positive electrode, the binder and
5 conductive agent which are typically used in the field may be
used in the negative electrode. After preparing negative
electrode active material slurry by mixing and agitating the
negative electrode active material and the additives, the
negative electrode active material slurry may be coated and
10 pressed on the current collector to thereby manufacture the
negative electrode.
[00137] As the separator, typical porous polymer films which
are conventionally used as the separator, for example, porous
polymer films which are produced from polyolefin-based
15 polymers such as ethylene homopolymer, propylene homopolymer,
ethylene-butene copolymer, ethylene-hexene copolymer, or
ethylene-methacrylate copolymer may be used, alone or through
lamination thereof, or typical porous nonwoven fabric, for
example, nonwoven fabric made of high melting point glass
20 fiber or polyethylene terephthalate fiber may be used, but
the separator is not limited thereto.
[00138] As the lithium salt, which may be included as the
electrolyte which is used in the present invention, any which
are typically used in the electrolyte for use in the lithium
25 secondary battery may be used without limitation and, for
36
example, the negative ion of the lithium salt may be any one
selected from a group which consists of F-, Cl-, Br-, I-, NO3
-,
N(CN)2
-, BF4
-, ClO4
-, PF6
-, (CF3)2PF4
-, (CF3)3PF3
-, (CF3)4PF2
-,
(CF3)5PF-, (CF3)6P-, CF3SO3
-, CF3CF2SO3
-, (CF3SO2)2N-, (FSO2)2N-,
CF3CF2(CF3)2CO-, (CF3SO2)2CH-,(SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3
5 -,
CF3CO2
-, CH3CO2
-, SCN-, and (CF3CF2SO2)2N-.
[00139] The electrolyte which is used in the present
invention may be an organic liquid electrolyte, an inorganic
liquid electrolyte, a solid polymer electrolyte, a gel type
10 polymer electrolyte, a solid inorganic electrolyte, a molten
type inorganic electrolyte, etc., which may be used in
manufacturing the lithium secondary battery, but is not
limited thereto.
[00140] The outer appearance of the lithium secondary battery
15 of the present invention is not particularly limited, but may
be a cylindrical type which uses a can, a polygonal type, a
pouch type, a coin type, etc.
[00141] The lithium secondary battery according to the
present invention may not only be used in battery cells which
20 are used as a power source for small devices, but may also
desirably be used as a unit battery in a mid- to large-scale
battery module which includes multiple battery cells.
[00142] Exemplary embodiments of the mid- to large-scale
device may include electric vehicles, hybrid electric
25 vehicles, plug-in hybrid electric vehicles, power storage
37
systems, etc., but are not limited thereto.
[00143] Hereinafter, in order to describe the present
invention in more detail, detailed description will be
provided along with embodiments. However, the embodiments
may be modified in various forms, and the scope of 5 the
present invention should not be construed as being limited to
the embodiments given below. Embodiments of the present
invention are provided to better describe the present
invention to those with ordinary skill in the art.
10 [00144] Examples
[00145] Hereinafter, further description is given by using
examples and experimental examples, but the present invention
is not limited by the examples and experimental examples.
[00146] Performance Evaluation According to Material
15 Properties of Conductive Oxide Particles and Composite
Particles
[00147] Example 1 (Single Layer Coating)
[00148]
[00149] 100 g of LiNi0.78Mn0.11Co0.11O2 and 5 g of 40 nm
20 (SnO2)x(Sb2O3)y (ATO) nano-sol (methoxy propanol 90%, ATO 10%,
x= 0.9 y =0.05) were placed into a beaker and then ethanol
was added such that the total solids content was about 10%.
After placing the obtained mixed solution into MPO5 (Multi-
Purpose, Japan Coke Industry) and spray coating and drying
25 for about 10 minutes, drying was performed in an oven for 12
38
hours at about 130℃. After drying and then performing heat
treatment for about 10 hours at about 400℃, grinding and
sieving were performed to thereby obtain positive electrode
active material.
5
[00150]
[00151] 94 wt% of the positive electrode active material
which was obtained in the above Example 1, 3 wt% of carbon
black as conductive agent, and 3 wt% of polyvinylidene
10 fluoride (PVdF) as binder was added to a solvent, N-methyl-2-
pyrrolidone (NMP), to thereby prepare a positive electrode
mixture slurry. The positive electrode mixture slurry was
coated on an aluminum (Al) thin film, which is a positive
electrode current collector having thickness of about 20 μm,
15 and after drying to produce a positive electrode, roll
pressing was performed to thereby manufacture the positive
electrode.
[00152]
20 [00153] 96.3 wt% of carbon powder as the negative electrode
active material, 1.0 wt% of super-p as conductive agent, and
1.5 wt% and 1.2 wt% respectively of styrene butadiene rubber
(SBR) and carboxymethyl cellulose (CMC) were mixed and added
to a solvent, NMP, to thereby prepare a negative electrode
25 active material slurry. The negative electrode active
39
material was coated on a copper (Cu) thin film, which is a
negative electrode current collector having thickness of
about 10 μm, and after drying to produce a negative electrode,
roll pressing was performed to thereby manufacture the
5 negative electrode.
[00154]
[00155] Meanwhile, 1 M of LiPF6 non-aqueous electrolyte
solution was prepared as electrolyte by adding LiPF6 to non10
aqueous electrolyte solvent which was prepared by mixing
ethylene carbonate and dimethyl carbonate at a volumetric
ratio of about 30:70.
[00156]
15 [00157] After the positive electrode and negative electrode,
which were manufactured as such, and the mixed separator of
polyethylene and polypropylene, after intercalation thereof,
were manufactured into a polymer type battery through a
typical method, manufacture of the lithium secondary battery
20 was completed by injecting the prepared above non-aqueous
electrolyte solution.
[00158] Example 2
[00159] Other than using ATO instead of ITO in the above
25 Example 1, the positive electrode active material and lithium
40
secondary battery were obtained through performing the same
method as the above Example 1.
[00160] Example 3
[00161] Other than using ATO and ITO by mixing at a 5 1:1
weight ratio instead of ATO in the above Example 1, the
positive electrode active material and lithium secondary
battery were obtained through performing the same method as
the above Example 1.
10
[00162] Example 4
[00163] Other than using ATO and YSZ by mixing at a 1:1
weight ratio instead of ATO in the above Example 1, the
positive electrode active material and lithium secondary
15 battery were obtained through performing the same method as
the above Example 1.
[00164] Example 5
[00165] Other than using ITO and YSZ by mixing at a 1:1
20 weight ratio instead of ATO in the above Example 1, the
positive electrode active material and lithium secondary
battery were obtained through performing the same method as
the above Example 1.
25 [00166] Example 6
41
[00167] Other than using Li1.05Ni0.8Mn0.1Co0.1O2 (Li/M = 1.05)
instead of LiNi0.78Mn0.11Co0.11O2 in the above Example 1, the
positive electrode active material and lithium secondary
battery were obtained through performing the same method as
5 the above Example 3.
[00168] Example 7
[00169] Other than using ATO and YSZ by mixing at a 1:1
weight ratio instead of ATO in the above Example 1, the
10 positive electrode active material and lithium secondary
battery were obtained through performing the same method as
the above Example 6.
[00170] Example 8
15 [00171] Other than using ITO and YSZ by mixing at a 1:1
weight ratio instead of ATO in the above Example 1, the
positive electrode active material and lithium secondary
battery were obtained through performing the same method as
the above Example 6.
20
[00172] Example 9 (interior and exterior)
[00173] Other than performing the heat treatment at 900℃ for
6 hours, the positive electrode active material which
includes ATO in the interior and exterior of the
25 LiNi0.78Mn0.11Co0.11O2, and the lithium secondary battery were
42
obtained by performing the same method as the above Example 1.
[00174] Comparative Example 1 (multi-layered coating)
[00175] Other than using 50 g of 40 nm ATO ((SnO2)x(Sb2O3)y,
x=0.9, y=0.05) nano-sol (methoxy propanol 90%, ATO 10%) 5 in
the above Example 1, the positive electrode active material
which includes a multi-layered ATO coating layer, and the
lithium secondary battery were obtained by performing the
same method as the above Example 1.
10
[00176] Comparative Example 2
[00177] Other than using ITO instead of ATO in the above
Comparative Example 1, the positive electrode active material
and lithium secondary battery were obtained by performing the
15 same method as the above Comparative Example 1.
[00178] Comparative Example 3
[00179] Other than using TiO2 instead of ATO ((SnO2)x(Sb2O3)y,
x=0.9, y=0.05), the positive electrode active material and
20 lithium secondary battery were obtained by performing the
same method as the above Example 1.
[00180] Comparative Example 4
[00181] Other than not adding ATO in the above Example 1, the
25 positive electrode active material and lithium secondary
43
battery were obtained by performing the same method as the
above Example 1.
[00182] Comparative Example 5
[00183] Other than using Li1.2Ni0.8Mn0.1Co0.1O2 (Li/M = 5 1.2)
instead of LiNi0.78Mn0.11Co0.11O2 (Li/M = 1), the positive
electrode active material and lithium secondary battery were
obtained by performing the same method as the above Example 1.
10 [00184] Comparative Example 6
[00185] Other than using Li1.2Ni0.8Mn0.1Co0.1O2 (Li/M = 1.2)
instead of LiNi0.78Mn0.11Co0.11O2 (Li/M = 1), the positive
electrode active material and lithium secondary battery were
obtained by performing the same method as the above Example 9.
15
[00186] Comparative Example 7
[00187] Other than using TiO2 instead of ATO ((SnO2)x(Sb2O3)y,
x=0.9 y =0.05), the positive electrode active material and
lithium secondary battery were obtained by performing the
20 same method as the above Example 9.
[00188] Compositions of the positive electrode active
material of the above Examples 1 to 9 and Comparative
Examples 1 to 7 may be organized such as in the following
25 Table 1:
44
[Table 1]
Exterior/Interior L/M Conductive
Oxide
Composite
Particle
(YSZ)
Example 1 Exterior
(single layer, 10nm)
L/M =1 ATO X
Example 2 Exterior
(single layer, 10nm)
L/M =1 ITO X
Example 3 Exterior
(single layer, 10nm)
L/M =1 ATO and
ITO
X
Example 4 Exterior
(single layer, 10nm)
L/M =1 ATO O
Example 5 Exterior
(single layer, 10nm)
L/M =1 ITO O
Example 6 Exterior
(single layer, 10nm)
L/M =1.05 ATO and
ITO
X
Example 7 Exterior
(single layer, 10nm)
L/M =1.05 ATO O
Example 8 Exterior
(single layer, 10nm)
L/M =1.05 ITO O
Example 9 Interior/Exterior
(single layer, 10nm))
L/M =1 ATO X
Comparative
Example 1
Exterior
(multi-layered, 40nm)
L/M =1 ATO X
Comparative
Example 2
Exterior
(multi-layered, 40nm)
L/M =1 ITO X
Comparative
Example 3
Exterior
(single layer, 10nm)
L/M =1 TiO2 X
Comparative
Example 4
Exterior
(single layer, 10nm)
L/M =1 X X
Comparative
Example 5
Exterior
(single layer, 10nm)
L/M =1 ATO X
Comparative
Example 6
Exterior
(single layer, 10nm)
L/M =1 ATO X
Comparative
Example 7
Exterior
(single layer, 10nm)
L/M =1 TiO2 X
[00189] Experimental Example 1: SEM Micrographs
[00190] SEM micrographs of each of the positive electrode
active materials which were prepared in the above Examples 1
and 2, and Comparative Examples 1 to 4 were observed, 5 served, and
results thereof are shown in Table 2 and FIGS. 3 to 7.
45
[Table 2]
Oxide Coating
Layer
Average Particle
Diameter of Oxide
(nm)
Coating Layer
Thickness (Single
Layer/Multi-layered
Example 1 ATO 10 nm 10 nm (Single layer)
Example 2 ITO 10 nm 10 nm (Single layer)
Comparative
Example 1
ATO 10 nm 40 nm (Multi-layered)
Comparative
Example 2
ITO 10 nm 40 nm (Multi-layered)
Comparative
Example 3
TiO2 10 nm 10 nm (Single layer)
Comparative
Example 4
None 0 0
[00191] As illustrated in Table 2 and FIGS. 3 to 7, when
including the conductive oxide coating layer on the lithium
transition metal oxide particle according to an embodiment of
5 the present invention, it may be known that a single layer is
formed which has a thickness of the coating layer of about 10
nm which is similar to the average particle diameter of the
conductive oxide particle.
[00192] Conversely, in the case of Comparative Examples 1 to
10 3, it may be known that a plurality of layers is formed which
has a thickness of the coating layer of about 40 nm which is
about 4 times the average particle diameter of the conductive
oxide particle.
15 [00193] Experimental Example 2: X-ray Diffraction Analysis
[00194] X-ray diffraction analysis was performed on the
positive electrode active material which was prepared in
Examples 1 and 2, and Comparative Examples 1 to 4. Results
46
thereof are shown in FIGS. 9 and 10.
[00195] In order to comparatively analyze XRD phases of ITO
and ATO which are included in the positive electrode active
material of the present invention, XRD diffraction
measurements were done on the positive electrode 5 rode active
material by using Cu (Kα radiation), and results thereof are
illustrated in FIG. 8.
[00196] - Target: Cu (Kα radiation) graphite monochromator
[00197] - Slit: divergence slit = 1 degree, receiving slit =
10 0.1 mm, scatter slit = 1 degree
[00198] - Measurement area and step angle/measurement time:
20.0 degrees<2θ<80 degrees, 4 degrees/1 minute (=0.2
degrees/3 seconds), here 2θ (theta) represents the
diffraction angle.
15 [00199] Observing FIGS. 9 and 10, it was verified that a
single phase ITO peak or ATO peak, the 2θ of which exists at
about 28 to about 35 degrees, appears in the positive
electrode active material.
20 [00200] Experimental Example 3: Cycle Property Evaluation 1
[00201] In order to find the relative efficiency of the
lithium secondary batteries, which were obtained in Examples
1 and 2, and Comparative Examples 1 to 4, according to number
of cycles, an electrochemical evaluation experiment was
25 performed as follows.
47
[00202] In detail, one cycle of charging was performed on the
lithium secondary batteries which were obtained in Examples 1
and 2, and Comparative Examples 1 to 4 by charging at 45℃
and constant current of 1 C until voltage of 4.2 V was
reached, and then charging with a constant voltage of 4.2 5 V
until charging current of 0.05 mAh was reached. Later, after
leaving as it is for 20 minutes, the lithium secondary
battery was discharged at constant current of 2 C until
voltage of 3.0 V was reached. Such was repeated for 1 to 5
10 cycles.
[00203] As may be seen in the above FIG. 8, as number of
cycles increases, Examples 1 and 2 of the present example are
found to have improved capacity retention rates compared to
those of Comparative Examples 1 to 4.
15 [00204] For example, when, as in Examples 1 and 2, the
conductive oxide coating layer was formed as a single layer
on the exterior of the lithium transition metal oxide
particles, capacity retention rate was improved by at least
10% for the 50th cycle when compared to Comparative Examples
20 1 and 2 in which the coating layer was formed as a plurality
of layers.
[00205] Even when the coating layer was formed as a single
layer on the lithium transition metal oxide particles, when
ATO or ITO was formed, an improvement of about 16% was found
25 when compared to Comparative Example 3 in which TiO2 was
48
formed.
[00206] In the case of Comparative Example 4, in which the
coating layer of conductive oxide was not formed on the
lithium transition metal oxide, a remarkable decrease of
about 23% was observed when compared to Examples 1 and 5 2 of
the present invention.
[00207] Performance Evaluation According to Mixing Ratio of
Conductive Oxide Particles and Composite Particles
10 [00208] Example 10
[00209] Other than mixing ATO and YSZ at a weight ratio of
about 1:0.01 instead of about 1:1 in the above Example 4, the
positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
15 above Example 4.
[00210] Example 11
[00211] Other than mixing ATO and YSZ at a weight ratio of
about 1:0.1 instead of about 1:1 in the above Example 4, the
20 positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
above Example 4.
[00212] Example 12
25 [00213] Other than mixing ATO and YSZ at a weight ratio of
49
about 1:0.5 instead of about 1:1 in the above Example 4, the
positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
above Example 4.
5
[00214] Example 13
[00215] Other than mixing ATO and YSZ at a weight ratio of
about 1:1.5 instead of about 1:1 in the above Example 4, the
positive electrode active material and lithium secondary
10 battery were obtained by performing the same method as the
above Example 4.
[00216] Comparative Example 8
[00217] Other than mixing ATO and YSZ at a weight ratio of
15 about 1:0.005 instead of about 1:1 in the above Example 4,
the positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
above Example 4.
20 [00218] Comparative Example 9
[00219] Other than mixing ATO and YSZ at a weight ratio of
about 1:2 instead of about 1:1 in the above Example 4, the
positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
25 above Example 4.
50
[00220] Experimental Example 4: Cycle Property Evaluation 2
[00221] In order to find the relative efficiency of the
lithium secondary batteries, which were obtained in Examples
4 and 10 to 13, and Comparative Examples 8 and 5 9, according
to number of cycles, an electrochemical evaluation experiment
was performed as follows, and results thereof are shown in
the following Table 3.
[Table 3]
ATO:YSZ Initial
Capacity
(Relative)
Capacity
After 30
Cycles (%)
Capacity
After 50
Cycles (%)
Example 4 1:1 100 93.5 89.2
Example 10 1:0.01 100 90.1 86.3
Example 11 1:0.1 100 92.5 88.3
Example 12 1:0.5 100 93.3 89.8
Example 13 1:1.5 100 93.2 89.1
Example 8 1:0.005 100 89.5 85.1
Example 9 1:2 97 93.3 89.1
10 [00222] Referring to the above Table 3, in the case of
Examples 4 and 10 to 13, in which the conductive oxide
particles (ATO) and composite particles (YSZ) were added at a
1:0.1 to 1:1.15 ratio, initial capacity was excellent and
capacity retention rate after tens of cycles was also
15 excellent, and thus superb cycle properties were observed,
but in the case of Comparative Examples 8 and 9 which deviate
from the above range of ratios, it was observed that cycle
properties were degraded or initial capacity was low. In
particular, initial capacity was found to be degraded due to
51
effects such as a coating layer becoming excessively thick
when the ratio of the composite particles was high.
[00223] Therethrough, it was observed that in order to
satisfy both initial capacity properties and cycle properties,
it is advantageous to mix the conductive oxide particles 5 and
composite particles at a ratio of about 1:0.01 to about 1.15,
and furthermore, in order to obtain an even better effect,
advantageous to mix at a ratio of about 1:0.1 to about 1:1.
10 [00224] Evaluation According to Mixing Ratio of Mixed
Conductive Oxide Particles
[00225] Example 14
[00226] Other than mixing ATO and ITO at a weight ratio of
15 about 1:0.01 instead of about 1:1 in the above Example 3, the
positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
above Example 3.
20 [00227] Example 15
[00228] Other than mixing ATO and ITO at a weight ratio of
about 1:0.1 instead of about 1:1 in the above Example 3, the
positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
25 above Example 3.
52
[00229] Example 16
[00230] Other than mixing ATO and ITO at a weight ratio of
about 1:0.5 instead of about 1:1 in the above Example 3, the
positive electrode active material and lithium 5 secondary
battery were obtained by performing the same method as the
above Example 4.
[00231] Comparative Example 10
10 [00232] Other than mixing ATO and YSZ at a weight ratio of
about 1:0.005 instead of about 1:1 in the above Example 3,
the positive electrode active material and lithium secondary
battery were obtained by performing the same method as the
above Example 4.
15
[00233] Comparative Example 11
[00234] Other than mixing ATO and YSZ at a weight ratio of
about 1:2 instead of about 1:1 in the above Example 3, the
positive electrode active material and lithium secondary
20 battery were obtained by performing the same method as the
above Example 4.
[00235] Experimental Example 4: Cycle Property Evaluation 2
[00236] In order to find the relative efficiency of the
25 lithium secondary batteries, which were obtained in Examples
53
3 and 14 to 16, and Comparative Examples 10 and 11, according
to number of cycles, an electrochemical evaluation experiment
was performed as follows, and results thereof are shown in
the following Table 4.
5 [Table 4]
ITO:ATO Initial
Capacity
(Relative)
Capacity After
30 Cycles (%)
Capacity After
50 Cycles (%)
Example 3 1:1 100 91.4 87.6
Example 14 1:0.01 100 90.2 86.1
Example 15 1:0.1 100 90.5 86.2
Example 16 1:0.5 100 91.0 87.1
Comparative
Example 10
1:0.005 100 90.1 86.0
Comparative
Example 11
1:2 98 91.1 87.5
[00237] Referring to the above Table 4, in the case of
Examples 3 and 14 to 16, in which the conductive oxide
particles (ATO and ITO) are added at a ratio of about 1:0.1
to 1:1, initial capacity was excellent and capacity retention,
10 even after tens of cycles, was excellent, and thus superb
cycle properties were observed, but in the case of
Comparative Examples 10 and 11 which deviate from the above
range of ratios, it was observed that cycle properties were
degraded or initial capacity was low. In particular, when
15 ratio of ITO was high, initial capacity was found to be
degraded due to effects such as the coating layer becoming
excessively thick or mixing becoming non-uniform.
[00238] Therethrough, it was observed that in order to
satisfy both initial capacity properties and cycle properties,
54
it is advantageous to mix the conductive oxide particles and
composite particles at a ratio of about 1:0.01 to about 1:1,
and furthermore, in order to obtain an even better effect, it
is advantageous to mix at a ratio of about 1:0.1 to about 1:1.
[00239] While this invention has been particularly shown 5 and
described with reference to preferred embodiments thereof and
drawings, it will be understood by those skilled in the art
that various changes in form and details may be made therein
without departing from the spirit and scope of the invention
10 as defined by the appended claims.
55
CLAIMS
1. A positive electrode active material, comprising:
lithium transition metal oxide particles;
conductive oxide particles; 5 ; and
composite particles,
wherein the conductive oxide particles include antimony
tin oxide (ATO) or a mixture of indium tin oxide (ITO) and
ATO, and
10 the conductive oxide particles and the composite
particles include a single-phase peak when measured by X-ray
diffraction (XRD) analysis.
2. The positive electrode active material of claim 1,
15 wherein the mixing ratio by weight of the conductive oxide
particles to the composite particles is 1:0.01 to 1:1.5.
3. The positive electrode active material of claim 1,
wherein a coating layer which includes the conductive oxide
20 particles and composite particles is formed on an outer
surface of the lithium transition metal oxide particle.
4. The positive electrode active material of claim 1,
wherein the conductive oxide particles and composite
25 particles are included in the interior of the lithium
56
transition metal oxide particle, and thus have
concentration gradients in which the concentrations of
the conductive oxide particles and composite particles
decrease going from the surface of the lithium transition
metal particle to the interior, and the conductive 5 ctive oxide
particles and composite particles are composited with the
lithium transition metal particle to form a composite
material.
10 5. The positive electrode active material of claim 4,
wherein:
the concentrations of the conductive oxide particles
and composite particles are at least about 20% higher in an
exterior bulk of the lithium transition metal particle than
15 in an interior bulk; and
the interior bulk is the center and adjacent regions of
the lithium transition metal oxide particle, and includes
about 50% of the total number of transition metal atoms which
are in the particle.
20
6. The positive electrode active material of claim 4,
wherein the conductive oxide particles and composite
particles are included, in a direction going from the surface
of the particle to the interior, within a thickness range of
25 about 0.0001 to about 80% of the particle radius.
57
7. The positive electrode active material of claim 1,
wherein:
a coating layer which includes the conductive oxide
particles and composite particles is formed on 5 n an outer
surface of the lithium transition metal oxide particle; and
the conductive oxide particles and composite particles
are included in the interior of the lithium transition metal
oxide particle, and thus have concentration gradients which
10 decrease going from the surface to the interior, and are
composited with the lithium transition metal particle to form
a composite material.
8. The positive electrode active material of claim 1,
15 wherein the conductive oxide particles are included in an
amount of 50 to 30000 ppm with respect to the entirety of the
positive electrode active material.
9. The positive electrode active material of claim 3 or 7,
20 wherein the coating layer further comprises an oxide which
includes one or more of calcium (Ca), niobium (Nb), tungsten
(W), magnesium (Mg), titanium (Ti), boron (B), molybdenum
(Mo), scandium (Sc), or zirconium (Zr).
25 10. The positive electrode active material of claim 3 or 7,
58
wherein the conductive oxide particles include those which
have an average particle diameter of 1 nm to 100 nm.
11. The positive electrode active material of claim 1,
5 wherein the composite particle includes any one selected from
a group which consists of yttria stabilized zirconia (YSZ),
gadolinia-doped ceria (GDC), lanthanum strontium gallate
magnesite (LSGM), lanthanum strontium manganite (LSM), Ca
doped zirconia or calcia stabilized zirconia (CSZ), Sc doped
10 zirconia (SSZ), and Ni-YSZ, or a mixture of at least two
thereof.
12. The positive electrode active material of claim 11,
wherein oxygen vacancies are present in proportion to the
15 amount of the element yttrium (Y).
13. The positive electrode active material of claim 11,
wherein the YSZ is Zr(1-x)YxO2-x/2 (0.01≤x≤0.30).
20 14. The positive electrode active material of claim 11,
wherein the conductive oxide particles include ATO and the
composite particles include YSZ.
15. The positive electrode active material of claim 1,
25 wherein the conductive oxide is a mixed oxide of indium tin
59
oxide and antimony tin oxide which are included at a weight
ratio of 1:0.01 to 1:1.
16. The positive electrode active material of claim 1,
wherein the antimony tin oxide includes any one 5 of compounds
represented by the below Formula 1 or 2, or a mixture
thereof:
(SnO2)x(Sb2O3)y
10 where, x and y satisfy x+y = 1, 0
(SnO2)x(Sb2O5)y
where, x and y satisfy x+y = 1, 0
(InO2)a(Sb2O3)b
where, a and b satisfy a+b = 1, 0
60
(InO2)a(Sb2O5)b
where, a and b satisfy a+b = 1, 0
Li(1+a)Ni(1-b-c)Mn(b)Co(c)M'(s)M"(v)O2
10 where,
M' includes any one selected from among the group which
consists of antimony (Sb), tin (Sn), indium (In), yttrium(Y),
zirconium (Zr), lanthanum (La), strontium (Sr), gallium (Ga),
magnesium (Mg), manganese (Mn), calcium (Ca), scandium (Sc),
15 and nickel (Ni), or includes a mixed element of at least two
thereof, or an oxide thereof;
M" includes one or more element among calcium (Ca),
niobium (Nb), tungsten (W), magnesium (Mg), titanium (Ti),
boron (B), molybdenum (Mo), scandium (Sc), or zirconium (Zr),
20 or oxides thereof; and
a, b, c, s, and v satisfy 0≤a<0.2, 0≤b≤0.5, 0≤c≤0.5,
0≤s≤0.2, and 0≤v≤0.2, respectively.
19. The positive electrode active material of claim 18,
25 wherein, in Formula 5, s and v have concentration gradients
61
which decrease going from the surface of the lithium
transition metal oxide particle to the interior.
20. The positive electrode active material of claim 1,
5 wherein the average particle diameter is 3 μm to 30 μm.
21. The positive electrode active material of claim 1,
wherein the compressive strength is 10 to 500 MPa under
pressure of 0.5 to 10 mN.
10
22. A method for preparing positive electrode active
material, the method comprising:
mixing lithium transition metal oxide particles,
conductive oxide particles, and composite particles; and
15 heat treating the mixed particles,
wherein the conductive oxide particles include antimony
tin oxide (ATO) or a mixture of indium tin oxide (ITO) and
ATO, and
the conductive oxide particles and the composite
20 particles include a single-phase peak when measured by XRD
analysis.
23. The method of claim 22, wherein:
the mixing is dry mixing or wet mixing; and
25 the conductive oxide particles and composite particles
62
are coated on the surface of the lithium transition metal
oxide particle.
24. The method of claim 23, wherein the coating layer is
5 formed through a spraying method.
25. The method of claim 22, wherein the heat treatment is
performed in a temperature range of 100℃ to 1200℃.
10 26. The method of claim 22, wherein the heat treatment is
performed in a temperature range of 200℃ to 800℃.
27. The method of claim 26, wherein, through the heat
treatment, the conductive oxide particles and composite
15 particles form a coating layer which is a single layer on the
surface of the lithium transition metal oxide particle.
28. The method of claim 22, wherein the heat treatment is
performed in a temperature range of 600℃ to 1200℃.
20
29. The method of claim 28, wherein:
through the heat treatment, the conductive oxide
particles and composite particles are included in the
interior of the lithium transition metal oxide particle, and
25 thus have concentration gradients in which the concentrations
of the conductive oxide particles and composite particles
decrease going from the surface of the lithium transition
metal particle to the interior, and the conductive oxide
particles and composite particles are composited with the
5 lithium transition metal particle.
30. A positive electrode, comprising the positive electrode
active material of claim 1.
10 31. A lithium secondary battery, comprising the positive
electrode of claim 30.