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
including a core including a crystalline carbon-based material and a composite coating
layer including at least one material selected from the group consisting of low
crystalline carbon and amorphous carbon and a metal and/or a non-metal capable of
intercalating and deintercalating ions through a procedure including mixing a
10 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 metal and/or nonmetal
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-shell precursor in which the mixture for
15 coating is coated on the core including 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 having
high energy density, high discharge voltage and stable output is currently underway and
some are commercially available.
15 A lithium secondary battery has a structure in which a non-aqueous electrolyte
containing a lithium salt is impregnated into an electrode assembly including 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 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 unifofmity 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 polat 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 or the like as an additive to an anode, an electrolyte or
the like has been suggested as a possible solution to such 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
anode active material induces an initial irreversible reaction since a solid
lb 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 therefore 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.
S 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, the present inventors have developed, as described below, an anode
5 active material with a unique structure which can simultaneously solve various
problems associated with the anode fabrication process and 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 preparing such an anode
10 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 including a core including a crystalline carbon-
15 based material and a composite coating layer including at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon and a
metal andlor a non-metal capable of intercalating and deintercalating ions, the method
including (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 metal and/or non-metal 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 including the crystalline carbon-
5 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 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
10 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
material selected from the group consisting of low crystalline carbon and amorphous
15 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 metal and/or a non-metal capable of intercalating and
deintercalating ions, which exhibits relatively high hydrophilicity, are directly mixed
with a crystalline carbon-based material, the material for preparing at least one
20 material selected from the group consisting of low crystalline carbon and amorphous
w carbon and the metal andor non-metal 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 uniform mixture of such materials is
coated on a core including a crystalline carbon-based material. Therefore, a domain
5 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 metal andor a non-metal capable of intercalating and deintercalating ions are
formed on a composite coating 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
10 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 metal and/or a non-metal
capable of intercalating and deintercalating ions, followed by purification to prepare a
15 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, including a material for preparing at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon and a
metal and/or a non-metal capable of intercalating and deintercalating ions, is coated on
20 a core including 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
I I composite coating layer, which includes a matrix including one component selected
I ~ from at least one material selected from the group consisting of low ~ crystalline carbon
I
I
I 5 and amorphous carbon and a metal and/or a non-metal capable of intercalating and
I
deintercalating ions and a filler including a remaining component selected therefrom,
the filler being incorporated in the matrix, covers a core including a crystalline carbonbased
material.
Generally, a carbon-based material is classified into graphite having a complete
10 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
15 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
petroleum-based material, a coal-based material, or a mixture of petroleum and coalbased
materials. For example, petroleum-based pitch is obtained by purifying (i.e.,
5 removing impurities from) 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 metal and/or a non-metal capable of intercalating and deintercalating
ions, followed by purification.
Specifically, the purification process of the pitch solution includes the
10 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
cooling and grinding. The coating mixture may be obtained through these processes.
Especially, when the metal and/or non-metal capable of intercalating and
15 deintercalating ions is added in the pitch solution step, uniform dispersion of the metal
and/or non-metal capable of intercalating and deintercalating ions can be
advantageously maximized, as compared to when the metal and/or non-metal 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
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.
, 5 The type of the metal and/or non-metal 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 metal and/or non-metal does not have
negative effects upon operating properties of batteries while exhibiting, depending on
material selection, high hydrophilicity and polarity relative to the at least one material
10 selected from the group consisting of low crystalline carbon and amorphous carbon.
The metal and/or non-metal is preferably Si, Sn or the like. These materials may be
used singly or as a mixture of two or more thereof.
Although Si may be applied directly or in the form of an alloy to provide a
high-capacity lithium secondary battery anode, it is difficult to commercialize such an
15 anode due to rapid variation in volume during chargeldischarge. However, when Si is
used in the form of a composite with one or more materials selected from the group
consisting of low crystalline carbon and amorphous carbon to provide a coating layer of
a graphite core according to the present invention, it is possible to achieve improvement
in anode capacity in addition to the effects described above..
Although Sn may also be used directly or in the form of an alloy for a lithium
secondary battery anode, such an anode employing Sn is not yet commercially
available. However, similar to Si, when Sn is used in the form of a composite with
one or more materials selected fiom the group consisting of low crystalline carbon and
5 amorphous carbon to provide a coating layer of a graphite core, it is possible to achieve
improvement in anode capacity in addition to the effects described above.
When an anode active material is used with Si andlor Sn, which imparts high
capacity, being employed for a surface coating layer as described above, it is possible to
achieve high capacity as compared to when a general carbon-based anode active
10 material is used alone.
In one embodiment, the metal andlor non-metal may be an alloy of Si and Sn.
The type and component contents of the alloy of Si and Sn are not particularly limited
so long as the alloy is capable of intercalating and deintercalating ions. Examples of
the alloy include. Sio.96Srn.04.
15 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 including a metal and/or a non-metal
capable of intercalating and deintercalating ions may be incorporated in a matrix
C including at least one material selected from the group consisting of low crystalline
carbon and amorphous carbon.
In a second exemplary structure, a filler including at least one material selected
from the group consisting of low crystalline carbon and amorphous carbon may be
5 incorporated in a matrix including a metal and/or a non-metal 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
10 have independent phases.
In the composite coating layer, the mixture ratio of the at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon and
the metal andfor non-metal capable of intercalating and deintercalating ions is not
particularly limited so long as the intended effects of the present invention (as described
15 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 metal
and/or non-metal 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
0 (b), the material for preparing the at least one material selected from the group
consisting of low crystalline carbon and amorphous carbon and the metal and/or nonmetal
capable of intercalating and deintercalating ions may be mixed in a ratio from
2:9 to 18:l on a weight basis when the carbonization yield is 50% in the process of
5 carbonizing the material for preparing carbon.
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 due to
10 formation of the composite coating layer are not easily 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 is
not easily formed, thereby causing capacity reduction.
In the present invention, the core-shell precursor is calcined in step (c) to form
15 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 metal and/or non-metal
capable of intercalating and deintercalating ions is not converted. In a preferred
20 embodiment, the material for preparing amorphous carbon may have a carbonization
-13-
II,
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.
5 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 matrixlfiller
structure including at least one material selected from the group consisting of low
crystalline carbon and amorphous carbon and a metal andlor a non-metal capable of
10 intercalating and deintercalating ions is coated on a core including a crystalline carbonbased
material.
First, the surface of the metal and/or non-metal capable of intercalating and
deintercalating ions included as a matrix or filler component in the composite coating
layer is at least partially exposed on the surface of the anode active material and is
15 oxidized, thus becoming more hydrophilic. Accordingly, the metal and/or non-metal
capable of intercalating and deintercalating ions exhibits, depending on the material
type thereof, a high affinity for a hydrophilic solvent in a slurry for anode fabrication,
thereby improving dispersion of solid components in the slurry. Thus, when an anode
is fabricated by applying the slurry to a current collector, distribution uniformity
Q 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 a metal and/or a non-metal capable of
intercalating and deintercalating ions can minimize decrease in the bonding strength
5 between the active material layer and a partial current collector which occurs on a nonuniform
electrode. Basically, the metal and/or non-metal capable of intercalating and
deintercalating ions 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
10 internal resistance caused by separation of the active material layer from the current
collector.
Similarly, the metal and/or non-metal capable of intercalating and
deintercalating ions, which is included in the composite coating layer, imparts
hydrophilicity to at least a part of the anode active material. This greatly reduces
15 impregnation time of the highly polar electrolyte in the electrode fabrication process,
thereby considerably improving battery productivity.
Second, the metal and/or non-metal capable of intercalating and deintercalating
ions, which is 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
5 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 metal and/or nonmetal
capable of intercalating and deintercalating ions at a high oxidation-reduction
potential.
The present invention also provides an anode mix including the anode active
10 material.
The anode mix according to the present invention includes 1 to 20% by weight
of a binder, and optionally includes 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
15 ' 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.
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, ~ e t j e nb lack, channel black, furnace black, lamp black and thermal black,
5 conductive fibers such as carbon fibers and metallic fibers, metallic powders such as
- carbon fluoride, aluminum and nickel powders, 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
10 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
15 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.
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
5 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 that is added to improve
adhesion of an active material to a current collector. The adhesion promoter may be
added in an amount of not more than 10% by weight, relative to the binder. Examples
10 of the adhesion promoter 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
15 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
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 current collector
may include fine irregularities on the surface thereof so as to enhance adhesion of anode
5 active materials. In addition, the current collector may be provided 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
secondary battery, including the anode.
The lithium secondary battery has a structure in which a non-aqueous
10 electrolyte containing a lithium salt is impregnated into an electrode assembly including
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
15 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.
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
5 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 including 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
10 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,My02 (in which M=Co,
Mn, Al, Cu, Fe, Mg, By Cr, Zn or Ga, the lithium nickel-based oxide including at least
one of the elements, and 0.01
An anode active material was produced and a coin-type half-cell was fabricated
in the same manner as in Example 1, except that silicon was not added during pitch
15 production and thus only pitch was used as a coating material.
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 pitch and silicon were mixed in a
weight ratio of 1 :9.
Since the carbonization yield of the pitch is 50%, the content of silicon is
5 greater than 90% based on the total amount of carbon and silicon.
During pitch production, silicon was not added and the graphite, pitch, and
silicon were simultaneously mixed in a weight ratio of 90:8:2. This mixture was
10 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-type half-cell was
fabricated therefrom.
15 Electrolyte impregnation properties were evaluated using electrodes fabricated
in accordance with Examples 1 to 3 and Comparative Examples 1 to 3. The electrode
was rolled 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
-27-
@
into the surface of the electrode after being dropped on the surface was measured.
Results are shown in Table 1 below.
Table I
As can be seen from Table 1, the electrodes using an anode active material
5 coated with a carbodmetal 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 Comparative
Example 1. The reason for this is that the metal surface of the anode active material
was partially oxidized to have hydrophilicity, enabling the highly polar electrolyte to
10 rapidly permeate between particles.
Impregnation
ti-he (sec)
Chargeldischarge properties were evaluated using the coin-type half-cells
fabricated in accordance with Examples 1 to 3 and Comparative Examples 1 to 3.
Ex. 3
89
15 Specifically, during charge, the cells were charged in a CC mode at a current density of
Ex. 1
8 8
0.1 C to 5 mV and were then maintained in a CV mode at 5 mV and charging was
Comp. Ex.
1
142
Ex. 2
90
completed when current density reached 0.01 C. During discharge, the cells were
-28-
Comp. Ex.
2
92
-
Comp. Ex.
3
92
C
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.
5 Table 2
As can be seen fiom Table 2 above, anode active materials coated with a
Charge capacity
Discharge capacity
(mAWg)
Efficiency (%)
Capacity
maintenance (%)
after 50
chargeldischarge
cycles
carbodmetal composite according to Examples 1 to 2 of the present invention exhibited
high discharge capacity and high capacity maintenance after 50 chargeldischarge cycles,
Ex. 1
447.4
414.3
92.6
92
as compared to an anode active material coated only with carbon as in Comparative
10 Example 1. The reasons for this are as follows. A metal material was unifomly
Ex. 2
416.1
384.5
92.4
93
distributed in the form of a composite with carbon on the graphite surface, thus realizing
high theoretical discharge capacity of metal materials. In addition, a composite in
which the metal and carbon were homogeneously mixed was coated on the graphite
surface and electric conductivity can thus be maintained in spite of variation in volume
-29-
Ex. 3
411.7
380.8
92.5
90
Comp.
Ex. 1
385.1
356.6
92.6
78
Comp.
Ex. 2
675.0
591.3
87.6
48
Comp.
Ex. 3
444.6
410.8
92.4
87
e due to chargeldischarge. In addition, the metal surface of the anode active material
-
was partially oxidized such that it was converted into a hydrophilic material having the
same function as an SEI, which formed a strong bond with a core material via carbon,
thereby inhibiting removal of, the SEI layer in repeated chargeldischarge cycles. In
5 addition, a material having a high chargeldischarge voltage was coated to prevent
precipitation of lithium and improve ion conductivity.
Also, when the content of silicon was considerably higher than that of carbon
as in Comparative Example 2, electrical conductivity was decreased due to great
variation in the volume of silicon during chargeldischarge and thus resistance of the
10 electrode was greatly increased and side reactions of electrolyte were increased, with
the result that capacity maintenance after 50 chargeldischarge cycles was considerably
lower than the examples.
It can also be seen that, when silicon was simply mixed with graphite and pitch
rather than adding silicon during pitch production as in Comparative Example 3, the
15 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 fiom the above description, advantageously, the method
according to the present invention can effectively prepare an anode active material with
a unique structure in which a composite coating layer including at least one material
selected from the group consisting of low crystalline carbon and amorphous carbon and
5 a metal andfor a non-metal capable of intercalating and deintercalating ions is formed
on the outer surface of a core including a crystalline 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
10 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
5 carbon and amorphous carbon and a metal and/or a non-metal 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 metal andlor non-metal capable of intercalating and deintercalating ions,
10 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
rL
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
of low crystalline carbon and amorphous carbon and the metal and/or non-metal
capable of intercalating and deintercalating ions, the filler comprising a remaining
5 component selected therefrom.
[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
10 low crystalline carbon and amorphous carbon is a pitch solution.
[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 metal and/or non-
15 metal capable of intercalating and deintercalating ions comprises at least one selected
from the group consisting of Si and Sn.
[claim 71 The method according to claim 6, wherein the metal and/or nonmetal
capable of intercalating and deintercalating ions is an alloy of Si and Sn.
[claim 8 1 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 91 The method according to claim 1, wherein the composite coating
5 layer has a structure in which a filler comprising the metal andfor non-metal capable of
intercalating and deintercalating ions is incorporated in a matrix comprising amorphous
carbon.
(claim 101 The method according to claim 1, wherein the composite coating
layer has a structure in which a filler comprising amorphous carbon is incorporated in a
10 matrix comprising the metal andlor non-metal capable of intercalating and
deintercalating ions.
[claim 11 1 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
15 and the metal and/or non-metal capable of intercalating and deintercalating ions are
mixed in a ratio from 1 :9 to 9: 1 on a weight basis.
I ~ l a i m12 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 131 An anode active material prepared using the method according to
any one of claims 1 to 12.
[ ~ l ~1r41n An anode for secondary batteries in which an anode mix comprising
the anode active material according to claim 13 is applied to a current collector.
5 (Claim 151 A secondary battery comprising the anode for secondary batteries
.Ir +
according to claim 14, .ss
. .
[claim 161 The secondary battery according to claim 15, where& the battery is a , ,
. . lithium secondary battery.
. .
(Claim 171 A middle or large-sized battery pack comprising the secondary
10 battery according to claim 16 as a unit cell.
Dated this July 12, 2013
ATTORNEY FOR THE APPLICANT[S]