Specification
METHOD FOR PREPARING ANODE ACTIVE MATERIAL
The present invention relates to a method for preparing an anode active
5 material and more particularly to a method for preparing an anode active material
comprising a core comprising a crystalline carbon-based material and a composite
coating layer comprising at least one material selected from the group consisting of
low crystalline carbon and amorphous carbon and a hydrophilic material comprising
an oxide capable of intercalating and deintercalating ions through a procedure
10 comprising mixing a precursor of a material for preparing the at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon
with the hydrophilic material comprising the oxide capable of intercalating and
deintercalating ions, followed by purification to prepare a mixture for coating, mixing
the mixture for coating with the crystalline carbon-based material to prepare a core-
15 shell precursor in which the mixture for coating is coated on the core comprising the
crystalline carbon-based material, and calcining the core-shell precursor to carbonize
the material for preparing the at least one material selected from the group consisting
of low crystalline carbon and amorphous carbon into the at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon.
-1-
Technological development and increased demand for mobile devices have led
to rapid increase in the demand for secondary batteries as energy sources. Among
such secondary batteries, lithium secondary batteries having high energy density, high
5 operating voltage, .long cycle span and low self-discharge rate are commercially
available and widely used.
In addition, increased interest in environmental issues has recently brought
about a great deal of research associated with electric vehicles (EV) and hybrid electric
vehicles (HEV) as alternatives to vehicles using fossil fuels such as gasoline vehicles
10 and diesel vehicles which are main causes of air pollution. Such electric vehicles
generally use nickel-metal hydride (Ni-MH) secondary batteries as power sources.
However, a great deal of study associated with use of lithium secondary batteries with
high energy density, discharge voltage and output stability is currently underway and
some are - commercially available.
A lithium secondary battery has a structure in which a non-aqueous electrolyte
containing a lithium salt is impregnated into an electrode assembly comprising a
cathode and an anode, each including an active material coated on a current conkctor,
with a porous separator interposed between the cathode and the anode.
Lithium cobalt-based oxide, lithium manganese-based oxide, lithium nickelbased
oxide, lithium composite oxide and the like are generally used as cathode active
materials of lithium secondary batteries. Carbon-based materials are generally used as
anode active materials. Use of silicon compounds, sulfur compounds and the like as
5 anode active materials is also under consideration.
However, lithium secondary batteries have various problems, some of which
are associated with fabrication and operating properties of an anode.
First, regarding anode fabrication, a carbon-based material used as an anode
active material is highly hydrophobic and thus has low miscibility with a hydrophilic
10 solvent, thereby reducing dispersion uniformity of solid components, in the process .of
preparing a slurry for electrode fabrication. In addition, hydrophobicity of the anode
active material complicates impregnation of highly polar electrolytes in the battery
fabrication process. Thus, electrolyte impregnation is a bottleneck in the battery
fabrication process, greatly decreasing productivity.
Addition of a surfactant as an additive to an anode, an electrolyte or the like
has been suggested as a possible solution to the problems. However, surfactants are
unsuitable due to side effects upon operating properties of batteries.
On the other hand, regarding the operating properties 'of an anode, the carbonbased
&ode active material induces an initial irreversible reaction since a solid
electrolyte interface (SEI) layer is formed on the surface of the carbon-based anode
active material during an initial chargeldischarge (activation) cycle. Removal
(breakage) and reformation of the SEI layer through repeated chargeldischarge cycles
also causes depletion of the electrolyte, thereby reducing battery capacity.
5 Various methods, such as formation of an SEI layer with much stronger
bonding to the anode active material and formation of an oxide layer or the like on the
surface of the anode active material, have been attempted to solve these problems.
However, these methods are unsuitable for commercialization due to problems such as
deterioration in electrical conductivity caused by the oxide layer and deterioration in
10 productivity caused by additional processes.
In addition, it is difficult to form an oxide layer with different properties on a
-.
highly non-polar anode active material and thus forming a uniform oxide layer
inherently increases process cost.
Thus, there is a great need for secondary batteries capable of fundamentally
15 solving these problems.
Therefore, the present invention has been made to solve the above and other
technical problems that have yet to be resolved.
As a result of a variety of extensive and intensive studies and various
experiments to solve the above problems, the present inventors have developed, as
5 described below, an anode active material with a unique structure which can
simultaneously solve various problems associated with the anode fabrication process
and a lot of problems associated with operating properties of batteries, i.e., an anode
active material with a structure in which a specific composite coating layer is formed
on a crystalline carbon-based core, and have also developed a novel method for
10 effectively preparing such an anode active material through a simple process. The
present invention has been completed based on this work.
In accordance with the present invention, there is provided a method for
preparing an anode active material comprising a core comprising a crystalline carbon-
15 based material and a composite coating layer comprising at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon and a
hydrophilic material comprising an oxide capable of intercalating and deintercalating
ions, the method comprising (a) mixing a precursor of a material for preparing the at
least one material selected from the group consisting of low crystalline carbon and
amorphous carbon with the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions, followed by purification to prepare a mixture
for coating, (b) mixing the mixture for coating with the crystalline carbon-based
material to prepare a core-shell precursor in which the mixture for coating is coated on
5 the core comprising the crystalline carbon-based material, and (c) calcining the coreshell
precursor to carbonize the material for preparing the at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon
into the at least one material selected from the group consisting of low crystalline
carbon and amorphous carbon.
A crystalline carbon-based material as a core component and at least one
material selected from the group consisting of low crystalline carbon and, amorphous
carbon exhibit high hydrophobicity. Generally, a material which is to be converted
into at least one material selected from the group. consisting of low crystalline carbon
and amorphous carbon through calcination (i.e., a material for preparing at least one
15 material selected from the group consisting of low crystalline carbon and amorphous
carbon) also exhibits hydrophobicity. Therefore, if a material for preparing at least
one material selected from the group consisting of low crystalline carbon and
amorphous carbon and a hydrophilic material comprising an oxide capable of
intercalating and deintercalating ions, which exhibits relatively high hydrophilicity,
20 are directly mixed with a crystalline carbon-based material, the material for preparing
at least one material selected from the group consisting of low crystalline carbon and
amorphous carbon and the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions are difficult to homogenize, with the result that it
is difficult to obtain a desirable core-shell precursor having a structure in which a
5 uniform mixture of such materials is coated on a core comprising a crystalline carbonbased
material. Therefore, a domain whose main component is at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon
and a domain whose main component is a hydrophilic material comprising an oxide
capable of intercalating and deintercalating ions are formed on a composite coating
10 layer of an anode active material obtained through calcination, with the result that it is
difficult to achieve all of the desired effects of the present invention.
On the other hand, according to the present invention, a precursor of the
material for preparing at least one material selected from the group consisting of low
crystalline carbon and amorphous carbon is mixed with a hydrophilic material
15 comprising an oxide capable of intercalating and deintercalating ions, followed by
purification to prepare a mixture for coating, and the mixture for coating is then mixed
with a crystalline carbon-based material. Thus is obtained a core-shell precursor in
which a uniform mixture for coating, comprising a material for preparing at least one
material selected from the group consisting of low crystalline carbon and amorphous
20 carbon and a hydrophilic material comprising an oxide capable of intercalating and
deintercalating ions, is coated on a core comprising a crystalline carbon-based
material.
When the core-shell precursor obtained in this manner is calcined, it is
possible to obtain an anode active material having a unique structure in which a
5 composite coating layer, which comprises a matrix comprising one component
selected from at least one material selected from the group consisting of low
crystalline carbon and amorphous carbon and a hydrophilic material comprising an
oxide capable of intercalating and deintercalating ions and a filler comprising a
remaining component selected therefrom, the filler being incorporated in the matrix,
10 covers a core comprising a crystalline carbon-based material.
Generally, a carbon-based material is classified into graphite having a complete
layered crystal structure such as natural graphite, soft carbon having a low-crystalline
layered crystal structure (graphene structure in which hexagonal carbon units are
arrayed in a honeycomb shaped layer form), and hard carbon having a structure in
15 which such structures are mixed with non-crystalline parts.
In a preferred embodiment, the crystalline carbon-based material as a core
component of the present invention may be graphite or a mixture of graphite and low
crystalline carbon and one of the components of the composite coating layer may be
low-crystalline carbon, amorphous carbon, or a mixture thereof.
A preferred example of the precursor of the material for preparing the at least
one material selected from the group consisting of low crystalline carbon and
amorphous carbon is a pitch solution. Generally, pitch is classified into petroleumbased
pitch and coal-based pitch. Therefore, the precursor may be derived from a
5 petroleum-based material, a coal-based material, or a mixture of petroleum and coalbased
materials. For example, petroleum-based pitch is obtained by purifying a
high-boiling residue remaining after crude oil is refined. Therefore, a highly uniform
coating mixture can be obtained by mixing the pitch solution with a hydrophilic
material comprising an oxide capable of intercalating and deintercalating ions,
10 followed by purification.
Specifically, the purification process of the pitch solution includes the
processes of adding some materials to the pitch solution and removing relatively low
boiling impurities such as hydrocarbons and sulfur therefrom through heat treatment
under an inert atmosphere at a temperature ranging from 350 to 700°C, followed by
15 cooling and grinding. The coating mixture may be obtained through these processes.
Especially, when the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions is added in the pitch solution step, uniform
- dispersion of the hydrophilic material comprising the oxide capable of intercalating and
deintercalating ions can be advantageously maximized, as compared to when the
hydrophilic material comprising the oxide capable of intercalating and deintercalating
ions is simply mixed with pitch.
A solution in various phases may be used as the pitch solution. For example,
not only a low-viscosity liquid-phase solution but also a high-viscosity and substantially
5 solid-phase solution may be used as the pitch solution. Of course, a solution partially
containing solid components may be used as the pitch solution as appropriate. -
The type of the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions as another component of the composite coating
layer in the present invention is not particularly limited so long as the hydrophilic
10 material does not have negative effects upon operating properties of batteries while
exhibiting high hydrophilicity and polarity relative to the at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon. The
hydrophilic material is preferably a metal oxide, a lithium metal composite oxide, or
the like, that is capable of intercalating and deintercalating ions. These materials
15 may be used singly or as a mixture of two or more thereof.
Preferred examples of the metal include, but are not limited to, titanium,
metalloids, or a mixture thereof, where titanium is most preferable.
Preferred examples of the oxide capable of intercalating and deintercalating
ions include, but are not limited to, Ti02, Li4Ti5012a,n d LiTi204.
The titanium oxide or lithium titanium oxide has a potential equal to and
greater than OV and less than 2V, relative to a lithium-metal reference electrode, and the
potential thereof is higher than graphite which has almost the same potential as lithium.
Due to such relatively high voltage of the titanium oxide or the lithium titanium oxide,
instantaneous application of power at a low temperature causes a reaction of
intercalation and deintercalation of ions into and from the titanium oxide or the lithium
titanium oxide. As a result, instantaneous output, which cannot be implemented using
carbon-based anode active materials, is possible.
Such a potential difference can also inhibit lithium dendrite growth in lithium
secondary batteries.
In the present invention, the structure of the composite coating layer may be
determined depending on components forming the matrix and the filler.
In a first exemplary structure, a filler comprising the hydrophilic material
comprising the oxide capable of intercalating and deintercalating ions is incorporated in
a matrix comprising at least one material selected from the group consisting of low
crystalline carbon and amorphous carbon.
In a second exemplary structure, a filler comprising at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon is
incorporated in a matrix comprising a hydrophilic material comprising an oxide capable
of intercalating and deintercalating ions.
In the composite coating layer, the content of the components of the matrix is
not necessarily greater than the content of the components of the filler since the
components of the matrix have continuous phases while the components of the filler
have independent phases.
In the composite coating layer, the content of the at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon and the
content of the hydrophilic material comprising the oxide capable of intercalating and
deintercalating ions are not particularly limited so long as the intended effects of the
present invention (as described above) are achieved. In a preferred embodiment, in the
composite coating layer that has been subjected to carbonization in step (c), the at
least one material selected from the group consisting of low crystalline carbon and
amorphous carbon and the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions may be mixed in a ratio from 1:9 to 9:l on a
weight basis. Accordingly, in the coating mixture of step (b), when the carbonization
yield is 50%, the material for preparing the at least one material selected from the
group consisting of low crystalline carbon and amorphous carbon and the hydrophilic
material comprising the oxide capable of intercalating and deintercalating ions may be
mixed in a ratio from 2:9 to 18: 1 on a weight basis.
-12-
The amount of the composite coating layer (coated on the anode active
material) is preferably 0.5 to 20% by weight, based on the total amount of the anode
active material. When the amount of the composite coating layer is excessively low or
the thickness thereof is excessively small, disadvantageously, the effects of formation of
5 the composite coating layer may not be achieved. Conversely, when the amount of the
composite coating layer is excessively high or the thickness thereof is excessively great,
,. disadvantageously, a desired core-composite coating layer structure may not be formed,
thereby causing capacity reduction.
In the present invention, the core-shell precursor is calcined in step (c) to form
10 the composite coating layer. Preferably, calcination is performed under an inert
atmosphere or an oxygen deficient atmosphere at a temperature ranging from 600 to
2000°C. Through such calcination, the material for preparing amorphous carbon is
carbonized and converted into amorphous carbon while the oxide capable of
intercalating and deintercalating ions is not converted. In a preferred example, the
15 material for preparing amorphous carbon may have a carbonization yield of about 20 to
80% and the carbonization yield may have various values according to the constitution
of the material for preparing amorphous carbon.
The present invention also provides an anode active material prepared using
the method described above.
The anode active material prepared using the method described above can
simultaneously solve all problems associated with the related art since the anode active
material has a unique structure in which a composite coating layer with a matridfiller
structure comprising at least one material selected from the group consisting of low
5 crystalline carbon and amorphous carbon and a hydrophilic material comprising an
oxide capable of intercalating and deintercalating ions is coated on a core comprising a
crystalline carbon-based material.
First, the oxide capable of intercalating and deintercalating ions, which is
included as a matrix or filler component in the composite coating layer, exhibits a high
10 affinity for a hydrophilic solvent in a slurry for anode fabrication, thereby improving
dispersion of solid components in the slurry. Accordingly, when an anode is
fabricated by applying the slurry to a current collector, distribution uniformity between
components such as a binder and the anode active material can be improved and
superior electrode properties can thus be achieved.
Uniformity improvement through the hydrophilic material can minimize a
decrease in the bonding strength between the active material layer and a partial current
collector which occurs on a non-uniform electrode. Basically, the hydrophilic material
increases the affinity between the active material layer and the surface of the current
collector, improving the bonding strength between the active material layer and the
current collector, and thereby solves the problem of increase in internal resistance
. caused by separation of the active material layer from the current collector.
Similarly, the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions, the hydrophilic material being included in the
5 composite coating layer, imparts relatively high hydrophilicity to at least a part of the
anode active material. This greatly reduces impregnation time of the highly polar
electrolyte in the electrode fabrication process, thereby considerably improving battery
productivity.
Second, the hydrophilic material included in the composite coating layer
10 previously forms a layer that provides the same function as an SEI having a strong
chemical bond and forms an even stronger bond with the surface of the anode. This
reduces the amount of irreversible ions required to form the SEI layer and also
minimizes removal of the SEI layer during repeated charge and discharge, ultimately
improving battery lifespan.
Third, the oxide capable of intercalating and deintercalating ions included as a
matrix or filler component in the composite coating layer minimizes the problem of
deterioration in electrical conductivity which may be caused by the presence of the
material incapable of intercalating and deintercalating ions.
In addition, in the case of a lithium secondary battery, growth of lithium
dendrites may occur since the crystalline carbon-based material serving as a core has a
potential close to that of lithium. However, this growth can .be inhibited since the
surface of the crystalline carbon-based material is coated with the hydrophilic material
5 comprising the oxide capable of intercalating and deintercalating ions at a high
oxidation-reduction potential.
The present invention also provides an anode mix comprising the anode active
material.
The anode mix according to the present invention comprises 1 to 20% by
10 weight of a binder, and optionally comprises 0 to 20% by weight of a co-n ductive
material, based on the total weight of the anode mix.
Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene
fluoride (PVdF), cellulose, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch,
hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone,
15 tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymers
(EPDM), sulfonated EPDM, styrene butadiene rubbers, fluoro-rubbers, various
copolymers, and polymer-saponified polyvinyl alcohols.
Any conductive material may be used without particular limitation so long as
suitable conductivity is provided without causing chemical changes in the battery.
Examples of the conductive material include graphite, carbon blacks such as acetylene
black, Ketjen black, channel black, hate black, lamp black and thermal black,
conductive fibers such as carbon fibers and metallic fibers, metallic powders such as
carbon fluoride powder, aluminum powder and nickel powder, conductive whiskers
5 such as zinc oxide and potassium titanate whiskers, conductive metal oxides such as
titanium oxide, and polyphenylene derivatives. Specific examples of commercially
available conductive materials include various acetylene black products (available from
Chevron Chemical company, Denka Singapore Private Limited and Gulf Oil company),
Ketjen Black EC series (available from Armak company), Vulcan XC-72 (available
10 from Cabot company) and Super P (available from Timcal company).
Where appropriate, a filler may be added as a component to inhibit expansion
of the anode. Any filler may be used without particular limitation so long as the filler
is a fibrous material that does not cause chemical changes in the battery. Examples of
the filler include olefin-based polymers such as polyethylene and polypropylene and
15 fibrous materials such as glass fibers and carbon fibers.
Optionally, other components such as viscosity controllers or adhesion
promoters may be further added singly or in combination of two or more thereof.
* -
The viscosity controller is a component that controls the viscosity of the
electrode mix to facilitate mixing of the electrode mix and application of the same to a
current collector, and may be added in an amount of up to 30% by weight, based on the
total weight of the anode mix. Examples of the viscosity controller include, but are not
limited to, carboxymethyl cellulose and polyvinylidene fluoride. In some cases, the
afore-mentioned solvent may also act as the viscosity controller.
5 The adhesion promoter is an auxiliary ingredient that is added to improve
adhesion of an active material to a current collector, and is present in an amount of not
more than 10% by weight, relative to the binder and examples thereof include oxalic
acid, adipic acid, formic acid, and acrylic acid derivatives and itaconic acid derivatives.
The present invention also provides an anode for secondary batteries in which
10 the anode mix is applied to a current collector.
The anode may be produced by adding an anode material containing an anode
active material, a binder or the like to a solvent such as NMP to prepare a slurry and
applying the slurry to an anode current collector, followed by drying and pressing.
The anode current collector is generally fabricated to a thickness of 3 to 500
15 pm. Any anode current collector may be used without particular limitation so long as
suitable conductivity is provided without causing chemical changes in the battery.
Examples of the anode current collector include copper, stainless steel, aluminum,
nickel, titanium, sintered carbon, copper or stainless steel surface-treated with carbon,
nickel, titanium or silver, and aluminum-cadmium alloys. The anode curreft collector
may include fine irregularities on the surface thereof so as to enhance adhesion of anode
active materials. In addition, the current collector may be used in various forms such as
a film, a sheet, a foil, a net, a porous structure, a foam and a nonwoven fabric.
The present invention also provides a secondary battery, preferably a lithium
5 secondary battery, comprising the anode.
The lithium secondary battery has a structure in which a non-aqueous
electrolyte containing a lithium salt is impregnated into an electrode assembly
comprising a cathode, an anode, and a separator interposed between the cathode and the
anode.
For example, the cathode may be prepared by applying a cathode active
material to a cathode current collector, followed by drying and pressing. Optionally,
the cathode may further include other components such as a binder or a conductive
material described above in association with the configuration of the anode.
The cathode current collector is generally manufactured to a thickness of 3 to
15 500 pm. Any cathode current collector may be used without particular limitation so
long as high conductivity is provided without causing chemical changes in the battery.
Examples of the cathode current collector include stainless steel, aluminum, nickel,
titanium, sintered carbon, or aluminum or stainless steel surface-treated with carbon,
nickel, titanium or silver. Similar to the anode current collector, the cathode current
-19-
collector may include fine irregularities on the surface thereof so as to enhance adhesion
to the cathode active material. In addition, the cathode current collector may be used
in various forms such as a film, a sheet, a foil, a net, a porous structure, a foam and a
nonwoven fabric.
The cathode active material is a lithium transition metal oxide comprising two
or more transition metals as a substance that causes electrochemical reaction, and
examples thereof include, but are not limited to, layered compounds such as lithium
cobalt oxide (LiCo02) or lithium nickel oxide (LiNiO2) substituted by one or more
transition metals; lithium manganese oxide substituted by one or more transition metals;
10 lithium nickel-based oxides represented by the formula LiNil,M,02 (in which M=Co,
Mn, Al, Cu, Fe, Mg, B, Cr, Zn or Ga, the lithium nickel-based oxide including at least
one of the elements, and 0.011y10.7); lithium nickel cobalt manganese composite
oxides represented by the formula Li1+~NibM1lcCol-(b+~+d)M~0su(c2h- ~)as&
Lil+zNi~13C0113Mnl/3o0r2 Lil+zNi0.4Mn0.4Co~.(~in0 2w hich -0.51z10.5, 0.11b<0.8,
15 0.11c10.8, OId10.2, OIe10.2, b+c+d
An anode active material was produced and a coin-type half-cell was fabricated
c
in the same manner as in Example 1, except that the lithium titanate (Li4Ti5OI2w) as not
added during pitch production and thus only pitch was used as a coating material.
During pitch production, the lithium titanate was not added and the graphite,
10 pitch, and lithium titanate were simultaneously mixed in a weight ratio of 91 :8: 1. This
mixture was thermally treated under a nitrogen atmosphere in an electric furnace in the
same manner as in Example 1 to produce an anode active material and then to fabricate
a coin-type half-cell.
Electrolyte impregnation properties were evaluated using electrodes fabricated
in accordance with Examples 1 to 3 and Comparative Examples 1 and 2. The
electrode was roll-pressed to impart a porosity of about 23% and the time required for 1
microliter (pl) of an electrolyte of 1M LiPF6 dissolved in a carbonate solvent to
completely permeate into the surface of the electrode after being dropped on the surface
was measured. Results are shown in Table 1 below.
Table 1
As can be seen from Table 1, the electrodes using an anode active material
5 coated with a carbon/hydrophilic material composite as in Examples 1 to 3 of the
Impregnation
time (sec)
present invention exhibited considerably short electrolyte impregnation times, as
Ex. 2
86
Ex. 1
89
compared to an electrode using an anode active material coated with only carbon as in
Comparative Example 1. The reason for this is that the anode active material surface
Ex. 3
90
was coated with a hydrophilic material, enabling the highly polar electrolyte to rapidly
10 permeate between particles.
Comp. Ex. 1
142
Comp. Ex. 2
93
Chargeldischarge properties were evaluated using the coin-type half-cells
fabricated in accordance with Examples 1 to 3 and Comparative Examples 1 and 2.
Specifically, during charge, the cells were charged in a CC mode at a current density of
15 0.1 C to 5 mV and were then maintained in a CV mode at 5 mV and charging was
completed when current density reached 0.01 C. During discharge, the cells were
discharged in a CC mode at a current density of 0.1 C to 1.5V. As a result, the
chargeldischarge capacity and efficiency of a first cycle were obtained. Then,
chargeldischarge was repeated 50 times under the same conditions as above, except that
the current density was changed to 0.5 C. Results are shown in Table 2 below.
Table 2
5 As can be seen from Table 2, anode active materials coated with a
carbonlhydrophilic material composite as in Examples 1 to 3 of the present invention
Charge capacity
(mAWg)
Discharge
capacity
Efficiency (%)
Capacity
maintenance
(%) after 50
chargeldischarge
cycles
exhibited very high capacity maintenance after 50 chargeldischarge cycles, as compared
.. -
Ex. 2
378.3
349.2
92.3
94
Ex. 1
382.2
353.9
92.6
94
to an anode active material coated only with carbon as in Comparative Example 1.
The reason for this is that a hydrophilic material serving the same function as SEI
Ex. 3
382.8
354.1
92.5
92
10 formed a strong bond with a core material via carbon to inhibit removal of the SEI layer
during repeated chargeldischarge cycles and also that a material having high
Comp. Ex. 1
385.1
356.6
92.6
78
chargeldischarge voltage was coated to prevent precipitation of lithium and improve
Comp. Ex. 2
382.4
353.7
92.5
87
ionic conductivity.
It can also be seen that, when a simple mixture of graphite and a hydrophilic
material was used rather than adding the hydrophilic material during the pitch
preparation process as in Comparative Example 2, the hydrophilic material was not
homogeneously distributed, instead forming clusters. Thus, the fabricated electrode
5 was non-uniform, thereby decreasing the capacity maintenance ratio after 50
charge/discharge cycles, as compared to the examples.
As is apparent from the above description, advantageously, the method
according to the present invention can effectively produce an anode active material with
10 a unique structure in that a composite coating layer comprising at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon and
a hydrophilic material comprising an oxide capable of intercalating and deintercalating
ions is formed on the outer surface of a core comprising a crystalline carbon-based
material with high uniformity.
15 It will be apparent to those skilled in the art that various applications and
modifications can be made based on the above description without departing from the
scope of the invention.
[claim 11 A method for preparing an anode active material comprising a core
comprising a crystalline carbon-based material and a composite coating layer
comprising at least one material selected from the group consisting of low crystalline
carbon and amorphous carbon and a hydrophilic material comprising an oxide capable
of intercalating and deintercalating ions, the method comprising:
(a) mixing a precursor of a material for preparing the at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon
with the hydrophilic material comprising the oxide capable of intercalating and
deintercalating ions, followed by purification to prepare a mixture for coating;
(b) mixing the mixture for coating with the crystalline carbon-based material
to prepare a core-shell precursor in which the mixture for coating is coated on the core
comprising the crystalline carbon-based material; and
(c) calcining the core-shell precursor to carbonize the material for preparing
15 the at least one material selected from the group consisting of low crystalline carbon
and amorphous carbon into the at least one material selected from the group consisting
of low crystalline carbon and amorphous carbon.
[claim 21 The method according to claim 1, wherein the composite coating
layer has a structure in which a filler is incorporated. in a matrix comprising one
-30-
component selected from the at least one material selected from the group consisting
of low crystalline carbon and amorphous carbon and the hydrophilic material
comprising the oxide capable of intercalating and deintercalating ions, the filler
comprising a remaining component selected therefrom.
5 [claim 31 The method according to claim 1, wherein the crystalline carbonbased
material comprises at least one of graphite and low- crystalline carbon.
[claim 41 The method according to claim 1, wherein the precursor of the
material for preparing the at least one material selected from the group consisting of
low crystalline carbon and amorphous carbon is a pitch solution.
10 [claim 51 The method according to claim 1, wherein the precursor is derived
from a coal-based material, or a petroleum-based material, or a mixture of petroleum
and coal-based materials.
[claim 61 The method according to claim 1, wherein the hydrophilic material
comprising the oxide capable of intercalating and deintercalating ions comprises at
15 least one selected from the group consisting of a metal oxide and a lithium metal
composite oxide.
[claim 71 The method according to claim 6, wherein the metal is titanium.
[claim 81 The method according to claim 6, wherein the oxide comprises at
least one selected from the group consisting of Ti02, Li4Ti5012 and LiTi204.
[Claim 91 The method according to claim 1, wherein the calcination is
performed under an inert atmosphere or an oxygen deficient atmosphere at a
temperature ranging from 600 to 2000°C.
5 [claim 101 The method according to claim 1, wherein the composite coating
layer has a structure in which a filler comprising the hydrophilic material comprising
the oxide capable of intercalating and deintercalating ions is incorporated in a matrix
comprising the at least one material selected from the group consisting of low
crystalline carbon and amorphous carbon.
10 [claim 11 1 The method according to claim 1, wherein the composite coating
layer has a structure in which a filler comprising the at least one material selected from
the group consisting of low crystalline carbon and amorphous carbon is incorporated in
a matrix comprising the hydrophilic material comprising the oxide capable of
intercalating and deintercalating ions.
15 [claim 121 The method according to claim 1, wherein, in the composite coating
layer that has been subjected to carbonization in the step (c), the at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon
and the hydrophilic material comprising the oxide capable of intercalating and
deintercalating ions are mixed in a ratio from 1 :9 to 9: 1 on a weight basis.
[claim 13 1 The method according to claim 1, wherein the amount of the
composite coating layer is 0.5 to 20% by weight, based on the total weight of the anode
active material.
' [claim 141 An anode active material prepared using the method according to
5 any one of claims 1 to 1 3.
[ l a m 15 1 An anode for secondary batteries in which an anode mix comprising
the anode active material according to claim 14 is applied to a current collector.
[claim 161 - A secondary battery comprising the anode for secondary batteries
according to claim 15.
10 [claim 17 1 " The secondary battery according to claim 16, wherein the battery is a
lithium secondary battery.
[claim 18] A middle or large-sized battery pack comprising the secondary
battery according to claim 17 as a unit cell.