Specification
METHOD FOR PREPARING ANODE ACTIVE MATERIAL
[TECHNICAL FIELD]
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 through a
procedure comprising mixing a precursor of a material for preparing the at least one
10 material selected from the group consisting of low crystalline carbon and amorphous
carbon with the hydrophilic material, followed by purification to prepare a mixture for
coating, 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 calcining the core-shell
15 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.
Technological development and increased demand for mobile devices have l d
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.
I In addition, increased interest in environmental issues has recently brought ~ about a great deal of research associated with electric vehicles (EV) and hybrid electric
1 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.
1 5 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 collector,
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 secqndary batteries. Carbon-based materials are generally used as
anode active materials. Use of silicon compounds, s u l k 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 sluny 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.
15 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 aq anode, the carbonbased
anode active material induces an initial irreversible reaction since a solid
-3 -
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.
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
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 fonning a uniform oxide layer
inherently increases process cost.
Thus, there is a great need for secondary batteries capable of fundamentally
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 effectively
10. 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
fiom the group consisting of low crystalline carbon and amorphous carbon and a
hydrophilic material, 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, 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 the at least one material
5 selected fiom the group consisting of low crystalline carbon andBmorphous 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
10 carbon exhibit high hydrophobicity. Generally, a material which is to be converted
into at least one material selected fiom the group consisting of low crystalline carbon
and amorphous carbon through calcination (i.e., a material for preparing at least one
material selected fiom the group consisting of low crystalline carbon and amorphous
carbon) also exhibits hydrophobicity. Therefore, if a material for preparing at least
15 one material selected fiom the group consisting of low crystalline carbon and
amorphous carbon and a hydrophilic material are directly mixed with a crystalline
carbon-based material, the material for preparing at least one material selected from the
gioup consisting of low crystalline carbon and amorphous carbon and the hydrophilie
material are difficult to homogenize, with the result that it is difficult to obtain a
20 desirable core-shell precursor having a structure in which a uniform mixture of such
materials is coated on a core comprising a crystalline carbon-based 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 are formed on a composite coating layer of an
5 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, followed
10 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 fiom the group consisting of low crystalline carbon and
amorphous carbon and a hydrophilic material, is coated on a core comprising a
15 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 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
20 amorphous carbon and a hydrophilic material and a filler comprising a remaining
-7-
component selected therefrom, the filler being incorporated in the matrix, 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
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 fiom 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 fiom a
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 highboiling
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, 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
5 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
cooling and grinding. The coating mixture may be obtained through these processes.
Especially, when the hydrophilic material is added in the pitch solution step,
uniform dispersion of the hydrophilic material can be advantageously maximized, as
10 compared to when the hydrophilic material 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
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.
15 The -type of the hydrophilic material as another component of the composite
coating layer in the present invention is not particularly limited so long as the
hydrophilic 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 an oxide, a nitride, a carbide, or the
like, that does not react with lithium. These materials may be used singly or as a
mixture of two or more thereof.
Preferred examples of the oxide include, but are not limited to, aluminum
oxide, magnesium oxide, zirconium oxide, or a mixture of two or more thereof.
Preferred examples of the nitride include, but are not limited to, silicon nitride.
. -
Preferred examples of the carbide include, but are not limited to, silicon
carbide, cobalt carbide, or a mixture thereof.
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 a hydrophilic material 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
15 selected from the group consisting of low crystalline carbon and amorphous carbon is
incorporated in a matrix comprising a hydrophilic material.
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
5 content of the hydrophilic material 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 may be mixed in a ratio
10 from 1 :9 to 9: 1 on a weight basis. Accordingly, in the step of carbonizing the material
for preparing carbon, 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 may be mixed in a ratio from 2:9
to 18: 1 on a weight basis in the coating mixture of step (b);
15 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
the composite coating layer may not be achieved. Conversely, when the amount of the
20 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
the composite coating layer. Preferably, calcination is performed under an inert
5 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 hydrophilic material is not
converted. In a preferred example, the material for preparing amorphous carbon may
have a carbonization yield of about 20 to 80% and the carbonization yield may have
10 various values according to the constitution of the material for preparing amorphous
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
15 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
crystalline carbon and amorphous carbon and a hydrophilic material is coated on a core
comprising a crystalline carbon-based material.
First, the hydrophilic material, which is included as a matrix or filler
component in the composite coating layer, exhibits a high affinity for a hydrophilic
solvent in a sluny for anode fabrication, thereby improving dispersion of solid
components in the slurry. Accordingly, when an anode is fabricated by applying the
5 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 hydrophlic 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 included in the composite coating layer
imparts hydrophilicity to at least a part of the anode active material. ihis 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
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
5 minimizes removal of the SEI layer during repeated charge and discharge, ultimately
improving battery lifespan.
Third, the at least one material selected fiom the group consisting of low
crystalline carbon and amorphous carbon included as a matrix or filler component in the
composite coating layer minimizes the problem of deterioration in electrical
10 conductivity which is caused by the presence of the hydrophilic material. 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 at least one material selected fiom the group
15 consisting of low crystalline carbon and amorphous carbon.
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
weight of a, binder, and optionally comprises 0 to 20% by weight of a conductive
material, based on the total weight of the anode mix.
Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene
5 fluoride (PVdF), cellulose, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch,
hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone,
tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymers
(EPDM), sulfonated EPDM, styrene butadiene rubbers, fluoro-rubbers, various
copolymers, and polymer-saponified polyvinyl alcohols.
10 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, furnace black, lamp black and thermal black,
conductive fibers such as carbon fibers and metallic fibers, metallic powders such as
15 carbon fluoride powder, aluminum powder and nickel powder, conductive whiskers
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
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
5 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
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.
10 '. 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
15 afore-mentioned solvent may also act as the viscosity controller.
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
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
5 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
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,
10 nickel, titanium, sintered carbon, copper or stainless steel surface-treated with carbon,
nickel, .titanium or silver, and aluminum-cadmium alloys. The anode current 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.
15 The present invention also provides a secondary battery, preferably a lithium
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
I
5
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 ,
I
material to a cathode current collector, followed by drying and pressing. ,Optionally,
5 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
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.
10 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
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 (LiNi02) substituted by one or more
transition metals; lithium manganese oxide substituted by one or more transition metals;
lithium nickel-based oxides represented by the formula LiNil,MYQ2 (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 Lil+zNib~C~1-(b+c+dlMd0(2-seu)c-hA ea s
Lil+zNil13C0113Mnl13o0r2 Lil+ZNio4~.4Co0.2(i0n 2w hich -0.51z10.5, 0.11b10.8,
0.11c10.8, O1dI0.2, OIe10.2, b+c+d
An anode active material was produced and a coin-type half-cell was fabricated
in the same manner as in Example 1, except that aluminum oxide was not added during
pitch production and thus only pitch was used as a coating material.
5 An anode active material was produced and a coin-type half-cell was fabricated
in the same manner as in Example 1, except that the weight ratio of pitch to aluminum
oxide was 1 :9.
Since the carbonization yield of the pitch is 50%, the content of the aluminum
oxide is greater than 90% based on the total amount of the carbon and aluminum oxide.
10
During pitch production, the aluminum oxide was not added and the graphite,
pitch, and aluminum oxide were simultaneously mixed in a weight ratio of 90:8:2.
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 a coin-
15 type half-cell was fabricated therefrom.
Electrolyte impregnation properties were evaluated using electrodes fabricated
in accordance with Examples 1 to 3 and Comparative Examples 1 to 3. The electrode
-25-
II,
was roll-pressed to impart a porosity of about 23% and the time required for 1 microliter
(~1)o f 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.
5 Table 1
. As can be seen from Table 1, the electrodes using an anode active material
coated with a carbon/hydrophilic material composite as in Examples 1 to 3 of the
present invention exhibited considerably short electrolyte impregnation times, as
compared to an electrode using an anode active material coated with only carbon as in
10 Comparative Example 1. The reason for this is that the anode active material surface
was coated with a hydrophilic material, enabling the highly polar electrolyte to rapidly
permeate between particles.
Impregnation
time (sec)
I
Ex. 2
90
Ex. 1
8 8
Chargeldischarge properties were evaluated using the coin-type half-cells
15 fabricated in accordance with Examples 1 to 3 and Comparative Examples 1 to 3.
Specifically, during charge, the cells were charged in a CC mode at a current density of
0.1 C to 5 mV and were then maintained in a CV mode at 5 mV and charging was
Ex. 3
8 6
Comp. Ex.
1
142
Comp. Ex.
2
95
Comp. Ex.
3
92
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 arid 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
As can be seen from Table 2, anode active materials coated with a
carbon/hydrophilic material composite as in Examples 1 to 3 of the present invention
exhibited very high capacity maintenance after 50 chargeldischarge cycles, as compared
Charge capacity
(mAh/g)
Discharge
capacity
(mrng)
Efficiency (%)
Capacity
maintenance
(%) after 50 -
chargeldischarge
cycles
10 to an anode active material coated only with carbon as in Comparative Example 1.
Ex. 3
383.1
354.1
92.6
90
The reason for this is that a hydrophilic material serving the same function as SEI
Ex. 1
382.5
354.1
92.6
92
formed a strong bond with a core material via carbon to inhibit removal of the SEI layer
Comp. Ex.
1
385.1
356.6
92.6
7 8
Ex. 2
383.9
355.1
92.5
90
during repeated chargeldischarge cycles and also that a material having high
Comp. Ex.
2
357.9
325.3
90.9
62
Comp. Ex.
3
3 82.6
353.5
92.4
8 6
chargeldischarge voltage was coated to prevent precipitation of lithium and improve
ionic conductivity.
In addition, it can be seen that anode active materials containing a very high
content of a hydrophilic material that did not react with lithium as in Comparative
Example 2 exhibited very low discharge capacity and the surfaces thereof exhibited
high electrical resistance, thus reducing capacity maintenance after 50 chargeldischarge
cycles.
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 3, the hydrophilic material was not
homogeneously distributed, instead forming clusters. Thus, the fabricated electrode
was non-uniform, thereby decreasing the capacity maintenance ratio after 50
chargeldischarge 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
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 b d
9
a hydrophilic material is formed on the outer surface of a core comprising a crystalline
I carbon-based material with high uniformity.
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
[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
5 carbon and amorphous carbon and a hydrophilic material, 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, followed by purification to prepare a mixture for
coating;
10 (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
1 comprising the crystalline carbon-based material; and
(c) 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
15 and amorphous carbon into amorphous carbon.
i ~ l a i m21 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
component selected from the at least one material selected from the group consisting
I
of low crystalline carbon and amorphous carbon and the hydrophilic material, the
filler comprising a remaining component selected therefrom.
I~laim31 The method according to claim 1, wherein the crystalline carbonbased
material comprises at least one of graphite and low crystalline carbon.
5 [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.
[claim $1 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
10 and coal-based materials.
[claim 6) The method according to claim 1, wherein the hydrophilic material
comprises at least one selected fiom the group consisting of an oxide, a nitride, and a
carbide that exhibit high hydrophilicity relative to the at least one material selected fiom
the group consisting of low crystalline carbon and amorphous carbon and that do not
15 react with lithium.
[claim 71 The method according to claim 6, wherein the oxide comprises at
least one selected from the group consisting of aluminum oxide, magnesium oxide, and
zirconium oxide.
[claim 81 The method according to claim 6, wherein the nitride is silicon
nitride.
[claim 91 The method according to claim 6, wherein the carbide comprises at
least one selected from the group consisting of silicon carbide and cobalt carbide.
5 [Claim 101 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.
[Claim 111 The method according to claim 1, wherein the composite coating
layer has a structure in which a filler comprising the hydrophilic material is
10 incorporated in a matrix comprising the at least one material selected from the group
consisting of low crystalline carbon and amorphous carbon.
[claim 121 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
15 a matrix comprising the hydrophilic material.
[claim 131 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 are mixed in a ratio from 1 :9 to 9: 1 on a weight basis.
[claim 141 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 151 An anode active material prepared using the method according to
5 any one of claims 1 to 14.
[claim 161 An anode for secondary batteries in which an &ode mix comprising
the anode active material according to claim 15 is applied to a current .collector.
. [claim 17'1 , A secondary' battery comprising -the anode for .' secondary batteries '
according to claim 16.
10 [claim 18 1 The secondary battery according to claim 17, wherein the battery is a
lithium secondary battery.
I(~laim.191 A middle or large-sized battery pack comprising the secondary -
battery according to claim I8 as a unit cell.
Dated this 02.07.2013
ATTORNEY FOR THE.@?PLICANT[S]'