[DESCRIPTION]
ANODE ACTIVE MATERIAL AND SECONDARY BATTERY COMPRISING
THE SAME
[TECHNICAL FIELD]
The present invention relates to an anode active material and a secondary
battery comprising the same. More specifically, the present invention relates to an
anode active material for secondary batteries, capable of intercalating and
deintercalating ions, comprising: a core comprising a crystalline carbon-based material;
and a composite coating layer comprising one or more materials selected from the group
10 consisting of low crystalline carbon and amorphous carbon, and a hydrophilic material,
wherein the composite coating layer comprises: a matrix comprising one component
selected from one or more materials selected from the group consisting of low
crystalline carbon and amorphous carbon, and a hydrophilic material; and a filler
comprising the other component, incorporated in the matrix.
15 [BACKGROUND ART]
Technological development and increased demand for mobile equipment have
led to a rapid increase in demand for secondary batteries as energy sources. Among
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these secondary batteries, lithium secondary batteries having high energy density and
voltage, long cycle span and low self-discharge are commercially available and widely
used.
In addition, increased interest in environmental issues has brought about a great
5 deal of research associated with electric vehicles, hybrid electric vehicles and plug-in
hybrid electric vehicles as alternatives to vehicles using fossil fuels such as gasoline
vehicles and diesel vehicles which are major causes of air pollution. These 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
10 batteries with high energy density, discharge voltage and power stability is currently
underway and some are commercially available.
A lithium secondary battery has a structure in which a non-aqueous electrolyte
comprising a lithium salt is impregnated into an electrode assembly comprising a
cathode and an anode, each comprising an active material coated on a current collector,
15 and a porous separator interposed therebetween.
Lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium
composite oxide and the like are generally used as cathode active materials of lithium
secondary batteries and carbon-based materials are generally used as anode active
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materials thereof. Use of silicon compounds, sulfur compounds and the like has also
been considered.
However, lithium secondary batteries have various problems, in particular,
problems associated with fabrication and driving properties of an anode.
5 First, regarding fabrication of an anode, a carbon-based material used as an
anode active material is highly hydrophobic and thus has problems of low miscibility
with a hydrophilic solvent in the process of preparing a slurry for electrode fabrication
and low dispersion uniformity of solid components. In addition, this hydrophobicity
of the anode active material complicates impregnation of highly polar electrolytes in the
10 battery fabrication process. The electrolyte impregnation process is a kind of
bottleneck in the battery fabrication process, thus greatly decreasing productivity.
In order to solve these problems, addition of a surfactant to an anode, an
electrolyte or the like is suggested. However, disadvantageous^, the surfactant may
have negative effects on driving properties of batteries.
15 Meanwhile, regarding driving properties of the anode, disadvantageous^, the
carbon-based anode active material induces 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 charge/discharge process (activation process), and
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battery capacity is reduced due to electrolyte depletion caused by removal (breakage)
and regeneration of the SEI layer during a continuous charge/discharge process.
In order to solve these problems, various methods such as formation of an SEI
layer through stronger bond, or formation of an oxide layer on the surface of the anode
5 active material have been attempted. These methods have properties unsuitable for
commercialization such as deterioration in electrical conductivity caused by the oxide
layer and deterioration in productivity caused by additional processes. Also, there still
exists a problem in that growth of lithium dendrites on the surface of the anode active
material may cause short-circuit.
10 Accordingly, there is an increasing need for secondary batteries capable of
solving these problems.
[DISCLOSURE]
[TECHNICAL PROBLEM]
Therefore, the present invention has been made to solve the above and other
15 technical problems that have yet to be resolved.
As a result of a variety of extensive and intensive studies and experiments to
solve the problems as described above, the present inventors discovered that, when an
anode active material is produced by forming a composite coating layer on a crystalline
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carbon-based core, various problems associated with anode fabrication and battery
driving properties can be solved. The present invention has been completed, based on
this discovery.
[TECHNICAL SOLUTION]
5 In accordance with one aspect of the present invention, provided is an anode
active material for secondary batteries, capable of intercalating and deintercalating ions,
comprising: a core comprising a crystalline carbon-based material; and a composite
coating layer comprising one or more materials selected from the group consisting of
low crystalline carbon and amorphous carbon, and a hydrophilic material, wherein the
10 composite coating layer comprises: a matrix comprising one component selected from
one or more materials selected from the group consisting of low crystalline carbon and
amorphous carbon, and a hydrophilic material; and a filler comprising the other
component, incorporated in the matrix.
As such, the anode active material having a structure in which the core
15 comprising a crystalline carbon-based material is coated with the composite coating
layer having a matrix/filler structure comprising one or more materials selected from the
group consisting of low crystalline carbon and amorphous carbon, and a hydrophilic
material can solve the problems in the related art, based on specific active material
structure and components.
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First, the surface of the hydrophilic material comprised as a matrix or filler
component in the composite coating layer exhibits high miscibility with a hydrophilic
solvent in a slurry for fabrication of an anode according to the type of materials used,
thus improving dispersibility in solid components in the slurry. Accordingly, when an
5 anode is fabricated by applying this 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 obtained.
The improvement in uniformity caused by the hydrophilic material can
minimize a decrease in bonding strength between the slurry and the partial current
10 collector which occurs on the non-uniform electrode. The hydrophilic material
improves affinity between the active material layer and the surface of the current
collector, and bonding strength between the active material layer and the current
collector and thereby solves a problem of increase in internal resistance caused by
separation of the active material layer from the current collector.
15 Similarly, the hydrophilic material comprised in the composite coating layer
imparts relatively high hydrophilicity to at least a part of the anode active material,
thereby greatly reducing impregnation time of the highly polar electrolyte in the
electrode fabrication process and considerably improving battery productivity.
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Second, the hydrophilic material comprised in the composite coating layer
forms a layer that has the same function as SEI having a strong chemical bond and
forms a stronger bond with the surface of the anode, thereby reducing an amount of
irreversible ions required for formation of the SEI layer, minimizing collapse of the SEI
5 layer during repeated charge and discharge and ultimately improving battery lifespan.
Third, one or more materials selected from the group consisting of low
crystalline carbon and amorphous carbon comprised as a matrix or filler in the
composite coating layer minimize deterioration in electrical conductivity which may be
induced by presence of the hydrophilic material. Also, in the case of a lithium
10 secondary battery, growth of lithium dendrites may occur, since the crystalline carbonbased
material serving as a core has a similar electric potential to lithium, but this
growth can be inhibited by coating one or more materials selected from the group
consisting of low crystalline carbon and amorphous carbon on the surface of the
crystalline carbon-based material at a high oxidation-reduction potential.
15 [BEST MODE]
Hereinafter, the present invention will be described in detail.
As described above, the anode active material according to the present
invention comprises: a core comprising a crystalline carbon-based material; and a
composite coating layer comprising: a matrix comprising one component (for example,
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amorphous carbon) selected from one or more materials selected from the group
consisting of low crystalline carbon and amorphous carbon, and a hydrophilic material;
and a filler comprising the other component (for example, hydrophilic material),
incorporated in the matrix.
5 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 honeycomb shaped
planes of carbon are arrayed in the form of a layer), and hard carbon having a structure
in which the low-crystalline structures are mixed with non-crystalline parts.
10 In a preferred embodiment, the core component of the present invention, the
crystalline carbon-based material may be graphite, or a mixture of graphite and low
crystalline carbon, and one of the composite coating layer components may be lowcrystalline
carbon, amorphous carbon or a mixture thereof.
Meanwhile, there is no limitation as to the hydrophilic material which is
15 another component constituting the composite coating layer in the present invention so
long as it exhibits relatively high hydrophilicity and polarity to one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon and
does not have a negative effect on driving characteristics of batteries. Preferably, the
hydrophilic material is an oxide that does not react with lithium, a nitride that does not
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react with lithium or a carbide that does not react with lithium. The hydrophilic
material may be used alone or in combination of two or more thereof.
Preferably, examples of the oxide include, but are not limited to, aluminum
oxide, magnesium oxide, zirconium oxide or a mixture thereof.
5 Preferably, the nitride is silicon nitride, but is not limited thereto.
Preferably, the carbide is silicon carbide, cobalt carbide or a mixture thereof,
but is not limited thereto.
In the present invention, the structure of the composite coating layer may be
determined, depending on matrix and filler components.
10 In a first exemplary structure, a filler comprising a hydrophilic material is
incorporated in a matrix comprising one or more materials selected from the group
consisting of low crystalline carbon and amorphous carbon.
In a second exemplary structure, a filler comprising one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon is
15 incorporated in a matrix comprising a hydrophilic material.
In the composite coating layer, since the matrix has a structure, components of
which have a continuous phase and the filler has a structure, components of which have
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independent phases, the content of the matrix component is not necessarily greater than
the content of the filler component.
In the composite coating layer, the content of one or more materials 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 (described above) are obtained. In a preferred
embodiment, the content of one or more materials selected from the group consisting of
low crystalline carbon and amorphous carbon may be 10 to 95% by weight, based on
the total amount of the composite coating layer and the content of the hydrophilic
10 material may be 5 to 90% by weight, based on the total amount of the composite coating
layer.
The amount (coating amount) of the composite coating layer 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
15 excessively small, effects caused by formation of the composite coating layer may not
be obtained and, on the other hand, when the amount of the composite coating layer is
excessively high or the thickness thereof is excessively great, disadvantageously, the
desired core-composite coating layer structure may not be formed and capacity may be
deteriorated.
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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
5 material, based on the total weight of the anode mix.
Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene
fluoride (PVdF), cellulose, polyvinyl alcohol, carboxymethylcellulose (CMC), starch,
hydroxypropylcellulose, regenerated cellulose, polyvinyl pyrollidone,
tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymers
10 (EPDM), sulfonated EPDM, styrene butadiene rubbers, fluoro-rubbers, various
copolymers, and polymer-saponified polyvinyl alcohol.
Any conductive material may be used without particular limitation so long as
it has suitable conductivity without causing chemical changes in the fabricated battery.
Examples of conductive materials include graphite; carbon blacks such as carbon black,
15 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 carbon fluoride powder, aluminum powder and nickel powder; conductive whiskers
such as zinc oxide and potassium titanate; conductive metal oxides such as titanium
oxide; and polyphenylene derivatives. Specific examples of commercially available
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conductive materials may 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 I
(available from Cabot Company) and Super P (Timcal Co.).
5 If desired, a filler is optionally added to inhibit expansion of the anode. Any
filler may be used without particular limitation so long as it does not cause adverse I
chemical changes in the manufactured battery and is a fibrous material. Examples of
the filler include olefin polymers such as polyethylene and polypropylene; and fibrous
materials such as glass fibers and carbon fibers.
10 Other components such as viscosity controllers or adhesion promoters may be
added alone or in combination.
The viscosity controller is a component to control the viscosity of the electrode
mix and thereby facilitate mixing of the electrode mix and application of the same to a
current collector, and is present in an amount of 30% by weight or less, based on the
15 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.
The adhesion promoter is an auxiliary ingredient to improve adhesion of an
active material to a current collector and is present in an amount of 10% by weight,
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based on the binder and examples thereof include oxalic acid, adipic acid, formic acid,
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.
5 For example, the anode is 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 have a thickness of 3 to
500 nm. Any anode current collector may be used without particular limitation so long
10 as it has suitable conductivity without causing adverse chemical changes in the
fabricated battery. Examples of the anode current collector include copper, stainless
steel, aluminum, nickel, titanium, sintered carbon, and copper or stainless steel
surface-treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys.
The anode current collector includes fine irregularities on the surface thereof so as to
15 enhance adhesion of anode active materials. In addition, the current collectors may be
used in various forms including films, sheets, foils, nets, porous structures, foams and
non-woven fabrics.
The present invention also provides a secondary battery comprising the anode
and the battery is preferably a lithium secondary battery.
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The lithium secondary battery has a structure in which a lithium salt-containing
non-aqueous electrolyte is impregnated in an electrode assembly comprising a separator
interposed between the cathode and the anode.
For example, the cathode is prepared by applying a cathode active material to a
5 cathode current collector, followed by drying and pressing, and further optionally
comprises other components such as binders or conductive materials as described above
in association with the configuration of the anode.
The cathode current collector is generally manufactured to have a thickness of
3 to 500 |M1. Any cathode current collector may be used without particular limitation
10 so long as it has suitable conductivity without causing adverse chemical changes in the
fabricated battery. Examples of the cathode current collector include stainless steel,
aluminum, nickel, titanium, sintered carbon, and aluminum or stainless steel surfacetreated
with carbon, nickel, titanium or silver. Similar to the anode current collector,
the cathode current collectors include fine irregularities on the surface thereof so as to
15 enhance adhesion to the cathode active material. In addition, the cathode current
collector may be used in various forms including films, sheets, foils, nets, porous
structures, foams and non-woven fabrics.
The cathode active material is a lithium transition metal oxide comprising two
or more transition metals as a substance that causes electrochemical reaction, and
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examples thereof include, but are not limited to, layered compounds such as lithium
cobalt oxide (LiCoC^) or lithium nickel oxide (LiNiC^) substituted by one or more
transition metals; lithium manganese oxide substituted by one or more transition metals;
lithium nickel oxide represented by the formula of LiNii.yMy02 (in which M = Co, Mn,
5 Al, Cu, Fe, Mg, B, Cr, Zn or Ga, the lithium nickel oxide including one or more
elements among the elements, 0.01
Graphite having a mean particle diameter of about 20 fim as a core material
10 (A), pitch having a carbonization yield of 50% as a material for low crystalline carbon
(B), and aluminum oxide (AI2O3) having a mean particle diameter of about 100 nm as a
hydrophilic material (C) were homogeneously mixed in a weight ratio of A : B : C =
90 : 8 : 2. This mixture was thermally-treated under a nitrogen atmosphere at 1,200D
for 2 hours in an electric furnace. During thermal treatment, the pitch was softened
15 and carbonized to form a composite with aluminum oxide (AI2O3) and the composite
was coated on a graphite surface to produce an anode active material coated with a
carbon/aluminum oxide composite.
The anode active material, SBR and CMC were mixed in a weight ratio of
active material : SBR : CMC = 97.0 : 1.5 : 1.5 to prepare a slurry and the slurry was
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applied to a Cu-foil to prepare an electrode. The electrode was roll-pressed to have a
porosity of about 23% and punched to fabricate a coin-type half cell. Li-metal was
used as a counter electrode of the cell and a coin-shaped battery was obtained using a
1M LiPF6 electrolyte solution in a carbonate solvent.
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 magnesium oxide (MgO) having a
mean particle diameter of about 100 nm was used, instead of aluminum oxide (AI2O3).
10 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 hydrophilic material (C) was not
used.
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An anode active material was produced and a coin-type half cell was fabricated
15 in the same manner as in Example 1, except that graphite, pitch and aluminum oxide
were mixed at a weight ratio of 90:1:9.
<
Because the carbonation ratio of the pitch was 50%, a content of aluminum
oxide was higher than 90%, based on the total weight of carbon and aluminum oxide.
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Experimental Example 1>
Electrolyte impregnation properties of the electrodes fabricated in accordance
with Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated. The
electrode was roll-pressed to have a porosity of about 23% and a time taken for 1
5 microliter (|i£) of a 1M LiPF6 electrolyte solution in a carbonate solvent dropped on the
surface of the electrode to completely permeate into the surface was measured.
Results are shown in Table 1 below.
Ex. 1 Ex. 2 Comp. Ex. 1 Comp. Ex. 2
ImFp reg^n ation 92 90 142 95
time (sec)
As can be seen from Table 1, the electrodes using an anode active material
10 coated with a carbon/hydrophilic material composite according to Examples 1 and 2 of
the present invention exhibited considerably short electrolyte impregnation times, as
compared to an electrode using an anode active material coated with carbon alone
according to Comparative Example 1. The reason for this is that the surface of the
anode active material was coated with a hydrophilic material, thus enabling a highly
15 polar electrolyte to be rapidly permeated into particles.
Experimental Example 2>
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Charge/discharge properties were evaluated using the coin-type half cells
fabricated in accordance with Examples 1 and 2 and Comparative Examples 1 and 2.
Specifically, during charge, the cells were charged in a CC mode at a current density of
0.1C to 5 mV and then maintained in a CV mode at 5 mV, charging was completed
5 when current density reached 0.01C. During discharge, the cells were discharged in a
CC mode at a current density of 0.1 C to 1.5V. As a result, charge/discharge capacity
and efficiency of a first cycle were obtained. Then, charge/discharge was repeated 50
times under the same conditions as above, except that the current density was changed
to 0.5C. Results are shown in Table 2 below.
10
Ex. 1 Ex. 2 Comp. Ex. 1 Comp. Ex. 2
Charge 6 ca,p acit3y 382.6 382.1 385.1 357.9
(mAh/g)
Discharge
capacity 353.5 353.1 356.6 325.3
(mAh/g)
Efficiency (%) 92A 92A 92^ 9(h9
Capacity
maintenance
(%) after 50 89 88 78 62
charge/discharge
cycles
As can be seen from Table 2 above, the anode active materials coated with the
carbon/hydrophilic material composite according to Examples 1 and 2 of the present
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invention exhibited high capacity maintenance after 50 charge/discharge cycles and
high efficiency, as compared to the anode active material coated with only carbon
according to Comparative Example 1. The reason for this is that the hydrophilic
material performing the same function as an SEI layer forms a strong bond with a core
5 material via carbon and thereby inhibits removal of the SEI layer in the repeated
charge/discharge process. Also, a material having high charge/discharge voltage is
coated, thereby preventing precipitation of lithium and improving ion conductivity.
It could be seen that, in the case of Comparative Example 2 in which a content
of the hydrophilic material (C) that does not react with lithium was considerably high,
10 discharge capacity was considerably low, electrical resistance of the surface of the
anode active material was increased and capacity maintenance was deteriorated after 50
charge/discharge cycles.
[INDUSTRIAL APPLICABILITY]
As apparent from the fore-going, the anode active material according to the
15 present invention is effective in greatly improving a battery fabrication process,
minimizing deterioration in electrical conductivity, and considerably inhibiting
breakage of the SEI layer and deterioration in battery lifespan, through a specific
core/composite coating layer structure.
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Although the preferred embodiments of the present invention have been
disclosed for illustrative purposes, those skilled in the art will appreciate that various
modifications, additions and substitutions are possible, without departing from the
scope and spirit of the invention as disclosed in the accompanying claims.
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[CLAIMS]
I Claim l ] An anode active material for secondary batteries, capable of
intercalating and deintercalating ions, the anode active material comprising:
a core comprising a crystalline carbon-based material; and
5 a composite coating layer comprising one or more materials selected from the
group consisting of low crystalline carbon and amorphous carbon, and a hydrophilic
material,
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wherein the composite coating layer comprises: j
a matrix comprising one component selected from one or more materials
10 selected from the group consisting of low crystalline carbon and amorphous carbon, and a hydrophilic material; and
a filler comprising the other component, incorporated in the matrix.
[Claim 2] The anode active material according to claim 1, wherein the
crystalline carbon-based material comprises one or more of graphite and low crystalline
15 carbon.
[Claim 3] The anode active material according to claim 1, wherein the
hydrophilic material is at least one selected from oxides, nitrides and carbides that
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exhibit relatively high hydrophilicity to one or more materials selected from the group
consisting of low crystalline carbon and amorphous carbon and do not react with
i lithium.
[Claim 4] The anode active material according to claim 3, wherein the oxide is
5 at least one selected from the group consisting of aluminum oxide, magnesium oxide
and zirconium oxide.
[Claim 5] The anode active material according to claim 3, wherein the nitride is
silicon nitride.
[Claim 61 The anode active material according to claim 3, wherein the carbide is
10 at least one selected from the group consisting of silicon carbide and cobalt carbide.
[Claim 7] The anode active material according to claim 1, wherein the
composite coating layer has a structure in which a filler comprising a hydrophilic
material is incorporated in a matrix comprising one or more materials selected from the
group consisting of low crystalline carbon and amorphous carbon.
15 [Claim 8] The anode active material according to claim 1, wherein the
composite coating layer has a structure in which a filler comprising one or more
materials selected from the group consisting of low crystalline carbon and amorphous
carbon is incorporated in a matrix comprising a hydrophilic material.
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[Claim 9] The anode active material according to claim 1, wherein an amount of
the composite coating layer is 0.5 to 20% by weight, based on the total amount of the
anode active material.
[Claim 101 An anode mix comprising the anode active material according to any I
5 one of claims 1 to 9.
[Claim 11 ] An anode for secondary batteries in which the anode mix according to
claim 10 is applied to a current collector. I
[Claim 12] A secondary battery comprising the anode for secondary batteries
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according to claim 11.
10 [Claim 13] The secondary battery according to claim 12, wherein the battery is a
lithium secondary battery.
[Claim 14] A battery pack comprising the secondary battery according to claim
13 as a unit battery.
[Claim 15] The battery pack according to claim 14, wherein the battery pack is a
15 lithium ion secondary battery pack for vehicles or power storage.