Abstract:
Disclosed is a method for preparing an anode active material comprising a core
composed of a crystalline carbon-based material, and a composite coating layer
composed of one or more materials selected from the group consisting of low crystalline
5 carbon and amorphous carbon, and silicon oxide enabling intercalation and
deintercalation of ions, the method comprising (a) mixing a precursor for a raw material
of the one or more materials selected from the group consisting of low crystalline
carbon and amorphous carbon with silicon oxide enabling intercalation and
deintercalation of ions, followed by purification, to prepare a mixture for coating, (b)
10 mixing the mixture for coating with a crystalline carbon-based material to prepare a
core-shell precursor comprising the raw material mixture for coating applied to the core
composed of the crystalline carbon-based material, and (c) baking the core-shell
precursor to carbonize the raw material of the one or more materials selected from the
group consisting of low crystalline carbon and amorphous carbon into the one or more
15 materials selected from the group consisting of low crystalline carbon and amorphous
carbon.
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Notices, Deadlines & Correspondence
6 205 LG Chem Sawon Apt.
381 42 Doryong dong Yuseong gu
Daejeon 305 340
3. HAN JungMin
B 301 Daeseong Topsville
997 31 Hwagok 6 dong Gangseo gu
Seoul 157 916
Specification
[DESCRIPTION]
METHOD FOR PREPARING ANODE ACTIVE MATERIAL
[TECHNICAL FIELD]
The present invention relates to a method for preparing an anode active
5 material. More specifically, the present invention relates to a method for preparing an
anode active material comprising a core composed of a crystalline carbon-based
material and a composite coating layer composed of one or more materials selected
from the group consisting of low crystalline carbon and amorphous carbon, and silicon
oxide enabling intercalation and deintercalation of ions, through a process including
10 mixing a precursor for a raw material of the one or more materials selected from the
group consisting of low crystalline carbon and amorphous carbon with silicon oxide
enabling intercalation and deintercalation of ions, followed by purification, to prepare a
mixture for coating, mixing the mixture for coating with a crystalline carbon-based
material to prepare a core-shell precursor comprising the raw material mixture for
15 coating applied to the core composed of the crystalline carbon-based material, and
baking the core-shell precursor to carbonize the raw material of the one or more
materials selected from the group consisting of low crystalline carbon and amorphous
carbon into the one or more materials selected from the group consisting of low
crystalline carbon and amorphous carbon.
-1-
[BACKGROUND ART]
Technological development and increased demand for mobile equipment have
led to a sharp rise in the demand for secondary batteries as energy sources. Among
these secondary batteries, lithium secondary batteries having high energy density and
5 voltage, long cycle lifespan and low self-discharge are commercially available and
widely used.
In addition, increased interest in environmental issues has brought about a great
deal of research associated with electric vehicles (EVs), hybrid electric vehicles (HEVs)
and plug-in hybrid electric vehicles as alternatives to vehicles using fossil fuels such as
10 gasoline vehicles and diesel vehicles which are major causes of air pollution. Nickelmetal
hydride (Ni-MH) secondary batteries are generally used as power sources of
electric vehicles (EVs) and hybrid electric vehicles (HEVs). However, a great deal of
study associated with use of lithium secondary batteries with high energy density,
discharge voltage and power stability is currently underway and some are commercially
15 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,
and a porous separator interposed therebetween.
-2-
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
materials thereof. Use of silicon compounds, sulfur compounds and the like has also
5 been considered.
However, lithium secondary batteries have various problems, in particular,
problems associated with fabrication and driving properties of an anode.
First, regarding fabrication of an anode, a carbon-based material generally used
as an anode active material is highly hydrophobic and thus has problems of low
10 miscibility with a hydrophilic solvent and low dispersion uniformity of solid
components in the process of preparing a slurry for electrode fabrication. In addition,
this hydrophobicity of the anode active material complicates impregnation of highly
polar electrolytes in the battery fabrication process. The electrolyte impregnation
process is a bottleneck in the battery fabrication process, thus greatly decreasing
15 productivity.
In order to solve these problems, addition of a surfactant to an anode, an
electrolyte or the like is suggested. However, disadvantageously, the surfactant may
have side effects on driving properties of batteries.
-3-
t
I 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
5 battery capacity is reduced due to exhaustion of the electrolyte 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
10 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.
Furthermore, it is not easy to form oxide layers having different physical
properties on a non-polar anode active material and thus formation of a uniform oxide
15 layer inevitably increases process cost.
Accordingly, there is an increasing need for methods capable of ultimately
solving these problems.
[DISCLOSURE]
-4-
[TECHNICAL PROBLEM]
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 experiments to
•
5 solve the problems as described above, the present inventors developed an anode active
material having a specific structure capable of solving both various problems associated
with an anode production process and many problems associated with battery operation
properties, i.e., an anode active material having a specific coating layer formed on a
crystalline carbon-based core and newly developed a method for effectively producing
10 an anode active material through a simple process. The present invention has been
completed based on these developments.
[TECHNICAL SOLUTION]
In accordance with one aspect of the present invention, provided is a method
for preparing an anode active material comprising a core composed of a crystalline
15 carbon-based material, and a composite coating layer composed of one or more
materials selected from the group consisting of low crystalline carbon and amorphous
carbon, and silicon oxide enabling intercalation and deintercalation of ions, the method
comprising: (a) mixing a precursor for a raw material of the one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon with
-5-
silicon oxide enabling intercalation and deintercalation of ions, followed by
purification, to prepare a mixture for coating; (b) mixing the mixture for coating with a
crystalline carbon-based material to prepare a core-shell precursor comprising the raw
material mixture for coating applied to the core composed of the crystalline carbon-
5 based material; and (c) baking the core-shell precursor to carbonize the raw material of
the one or more materials selected from the group consisting of low crystalline carbon
and amorphous carbon into the one or more materials selected from the group consisting
of low crystalline carbon and amorphous carbon.
The crystalline carbon-based material, which is the core component, and one or
10 more materials selected from the group consisting of low crystalline carbon and
amorphous carbon are highly hydrophobic. In addition, generally, the raw material
(raw materials of one or more materials selected from the group consisting of low
crystalline carbon and amorphous carbon) converted into one or more materials selected
from the group consisting of low crystalline carbon and amorphous carbon by baking is
15 also highly hydrophobic. Accordingly, when the raw material of one or more
materials selected from the group consisting of low crystalline carbon and amorphous
carbon and silicon oxide enabling intercalation and deintercalation of ions and having
relatively high hydrophilicity are mixed with the crystalline carbon-based material, it is
difficult to homogeneously mix the raw material of one or more materials selected from
20 the group consisting of low crystalline carbon and amorphous carbon with the silicon
-6-
oxide enabling intercalation and deintercalation of ions arid it is tfius difficult to prepare
a desired core-shell precursor having a structure in which the homogeneous mixture is
applied to a core comprising a crystalline carbon-based material. For this reason, a
domain comprising the one or more materials selected from the group consisting of low
5 crystalline carbon and amorphous carbon as a main component and a domain
comprising silicon oxide enabling intercalation and deintercalation of ions as a main
component are present in the composite coating layer composed of the anode active
material obtained after baking and all the desired effects of the present invention are not
exerted.
10 On the other hand, according to the present invention, first, the precursor for
the raw material of one or more materials selected from the group consisting of low
crystalline carbon and amorphous carbon is mixed with silicon oxide enabling
intercalation and deintercalation of ions, followed by purification to prepare a mixture
for coating, and the mixture is mixed with the crystalline carbon-based material. As a
15 result, it is possible to obtain a core-shell precursor having a structure in which the
homogeneous mixture for coating comprising the raw material of one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon, and
silicon oxide enabling intercalation and deintercalation of ions is applied to the core
comprising the crystalline carbon-based material.
-7-
When the core-shell precursor thus obtained is baked, it is possible to obtain an
anode active material having a structure in which the core comprising the crystalline
carbon-based material is surrounded with the composite coating layer comprising a
matrix composed of one component of one or more materials selected from the group
5 consisting of low crystalline carbon and amorphous carbon and silicon oxide enabling
intercalation and deintercalation of ions, and a filler composed of the other component.
In general, a carbon-based material is classified into graphite having a
complete layered crystal structure such as natural graphite, soft carbon having a lowcrystalline
layered crystal structure (graphene structure in which hexagonal honeycomb
10 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.
In a preferred embodiment, the crystalline carbon-based material which is the
core component of the present invention may be graphite, or a mixture of graphite and
low crystalline carbon, and one of the composite coating layer components may be low-
15 crystalline carbon, amorphous carbon or a mixture thereof.
A preferred example of the precursor for the raw material of one or more
materials selected from the group consisting of low crystalline carbon and amorphous
carbon is a pitch solution. In general, pitch is classified into petroleum-based pitch
and coal-based pitch and the precursor is derived from a coal-based material, a
-8-
petroleum-based material, or a petroleum/coal-based mixture. For example, since the
petroleum-based pitch is obtained by refining a crude oil and purifying an impurity
component from the remaining high-boiling point residue, a highly homogeneous
mixture for coating can be prepared by mixing the pitch solution with silicon oxide
5 enabling intercalation and deintercalation of ions, followed by purification.
Specifically, the purification of the pitch solution is carried out by adding a part
of components and removing impurities such as hydrocarbons and sulfur having a
relatively low boiling point by thermal treatment under an inert atmosphere at a
temperature of 350°C to 700°C, followed by cooling and grinding. Through this
10 process, the mixture for coating can be obtained.
In particular, when the hydrophilic material comprising silicon oxide enabling
intercalation and deintercalation of ions is added to the pitch solution, uniformity of
dispersion of silicon oxide enabling intercalation and deintercalation of ions can be
maximized, as compared to a case in which silicon oxide enabling intercalation and
15 deintercalation of ions is simply mixed with pitch.
Various types of solutions may be used as the pitch solution. For example, a
liquid having low viscosity as well as a solution being in a substantial solid state due to
high viscosity may be used. In some cases, a solution partially containing a solid may
be also used.
-9-
t
! Meanwhile, silicon oxide enabling intercalation and deintercalation of ions
i
which is another component constituting the composite coating layer in the present
invention exhibits relatively high hydrophilicity and polarity to one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon and
5 thus provides improved properties in terms of mix preparation or electrolyte
impregnation.
A preferred example of the silicon oxide is a substance represented by SiOx.
For example, SiC>2 hardly intercalates and deintercalates lithium ions used for lithium
secondary batteries. Accordingly, in the formula, x satisfies 0.1 < x < 1.5 and is more
10 preferably 0.5 < x < 1.3 in order to maintain the structure of silicon oxide and facilitate
intercalation and deintercalation of ions.
In the present invention, the structure of the composite coating layer may be
determined depending on matrix and filler components.
In a first exemplary structure, a filler comprising silicon oxide enabling
15 intercalation and deintercalation of ions 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
-10-
i
incorporated in a matrix comprising silicon oxide enabling intercalation and
deintercalation of ions.
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
5 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
content of the silicon oxide enabling intercalation and deintercalation of ions are not
10 particularly limited so long as the intended effects of the present invention (described
above) can be exerted. In a preferred embodiment, in the composite coating layer after
the carbonization of step (c), one or more materials selected from the group consisting
of low crystalline carbon and amorphous carbon and silicon oxide enabling intercalation
and deintercalation of ions may be mixed with each other at a ratio of 1:9 to 9:1, based
15 on weight. Accordingly, when a carbonization yield is 50% in the process of
carbonizing the raw material of carbon, i.e., the raw material of one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon may
be mixed with silicon oxide enabling intercalation and deintercalation of ions at a ratio
of 2:9 to 18:1, based on weight in the mixture for coating of step (b).
-11-
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
excessively small, effects caused by formation of the composite coating layer may not
5 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, disadvantageous^, the
desired core-composite coating layer structure may not be formed and capacity may be
deteriorated.
For formation of the composite coating layer, in step (c), the core-shell
10 precursor is baked. The baking is preferably carried out under an inert atmosphere or
an anoxic atmosphere at 600 to 2,000°C and enables the raw material of amorphous
carbon to be carbonized and converted into amorphous carbon, while silicon oxide
enabling intercalation and deintercalation of ions is not converted. In a preferred
embodiment, the raw material of the amorphous carbon has a carbonization yield of
15 about 20 to 80% and the carbonization yield may have various values depending on the
composition of the raw material of amorphous carbon.
The present invention also provides an anode active material prepared by the
method.
-12-
*
The anode active material prepared by the method has a structure in which the
core comprising a crystalline carbon-based material is coated with a 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 silicon oxide
5 enabling intercalation and deintercalation of ions can solve the problems in the related
art, based on specific active material structure and components.
First, silicon oxide enabling intercalation and deintercalation of ions,
comprised as the matrix or filler component in the composite coating layer, exhibits
high affinity to the hydrophilic solvent in the slurry for producing the anode due to
10 molecular structural properties of oxide, thereby improving dispersability of the solid in
the slurry. Accordingly, when the anode is produced by applying the slurry to a
current collector, distribution uniformity between components such as a binder and the
anode active material is improved and superior electrode properties can thus be
obtained.
15 The improvement in uniformity caused by the hydrophilic material can
minimize a partial decrease in bonding strength between the slurry and the current
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, as well as bonding strength between the active material layer and the current
-13-
*
collector and thereby solves a problem of increase in internal resistance caused by
separation of the active material layer from the current collector.
Similarly, the silicon oxide enabling intercalation and deintercalation of ions
comprised in the composite coating layer imparts relatively high hydrophilicity to at
5 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.
Second, the silicon oxide enabling intercalation and deintercalation of ions
comprised as a matrix or filler in the composite coating layer minimizes a problem of
10 deterioration in electrical conductivity which may be induced by presence of materials
enabling intercalation and deintercalation of ions.
Also, 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 voltage
similar to lithium, but this growth can be inhibited by coating silicon oxide enabling
15 intercalation and deintercalation of ions on the surface of the crystalline carbon-based
material at a high oxidation-reduction potential.
The present invention also provides an anode mix comprising the anode active
material.
-14-
The anode mix according to the present invention comprises 1 to 20% by
weight of a binder and optionally 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, carboxymethylcellulose (CMC), starch,
hydroxypropylcellulose, regenerated cellulose, polyvinyl pyrollidone,
tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymers
(EPDM), sulfonated EPDM, styrene butadiene rubbers, fluoro-rubbers, various
copolymers, and polymer-saponified polyvinyl alcohol.
10 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,
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
15 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
conductive materials may include various acetylene black products (available from
Chevron Chemical Company, Denka Singapore Private Limited and Gulf Oil
-15-
*
Company), Ketjen Black EC series (available from Armak Company), Vulcan XC-72
(available from Cabot Company) and Super P (Timcal Co.).
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
5 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.
Other components such as viscosity controllers or adhesion promoters may be
added alone or in combination.
10 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
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 to improve adhesion of an
active material to a current collector and is present in an amount of 10% by weight,
based on the binder and examples thereof include oxalic acid, adipic acid, formic acid,
acrylic acid derivatives and itaconic acid derivatives.
-16-
t
The present invention also provides an anode for secondary batteries in which
the anode mix is applied to a current collector.
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,
5 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 fun. Any anode current collector may be used without particular limitation so long
as it has suitable conductivity without causing adverse chemical changes in the
fabricated battery. Examples of the anode current collector include copper, stainless
10 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
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
15 non-woven fabrics.
The present invention also provides a secondary battery comprising the anode
and the battery is preferably a lithium secondary battery.
-17-
*
The lithium secondary battery has a structure in which a lithium salt-containing
non-aqueous electrolyte is impregnated into 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
associated with the configuration of the anode.
The cathode current collector is generally manufactured to have a thickness of
3 to 500 p . 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 surfaces 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
-18-
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
10 In the process of preparing pitch having a carbonization yield of 50% as a raw
material for low crystalline carbon, silicon oxide (SiO) having relatively high
hydrophilicity to a pitch precursor, enabling intercalation and deintercalation of ions
and having a mean particle diameter of about 100 nm was added to the pitch precursor,
followed by purification, to prepare a pitch/silicon oxide composite. A ratio of pitch to
15 silicon oxide was 8:1, based on weight. The pitch/silicon oxide composite (A) was
homogeneously mixed with graphite (B) having a mean particle diameter of 20 p , as a
raw material for the core at a weight ratio of A:B=9:91. This mixture was thermallytreated
under a nitrogen atmosphere in an electric furnace at 1,200°C for 2 hours.
During thermal treatment, the pitch was softened and carbonized, and at the same time,
-23-
i
was coated on a graphite surface in the form of silicon oxide and a composite, to
prepare an anode active material with a core-shell structure, coated with the
carbon/silicon oxide composite.
The anode active material, SBR and CMC were mixed in a weight ratio of
5 active material : SBR : CMC = 97.0 : 1.5 : 1.5 to prepare a slurry and the slurry was
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.
10
An anode active material was prepared and a coin-type half cell was fabricated
in the same manner as in Example 1, except that the weight ratio of pitch to silicon
oxide was 8:2 and the weight ratio of the silicon oxide composite to the graphite was
10:90.
15
Graphite, pitch and silicon oxide were simultaneously mixed at a weight ratio
of 91:8:1 without adding silicon oxide in the process of preparing the pitch. This
mixture was thermally treated under a nitrogen atmosphere in an electric furnace, an
-24-
anode active material was prepared and a coin-type half cell was fabricated in the same
manner as in Example 1.
An anode active material was prepared and a coin-type half cell was fabricated
5 in the same manner as in Example 1, except that silicon dioxide (SiC^) having a mean
particle diameter of about 100 nm was used, instead of silicon oxide (SiO).
An anode active material was prepared and a coin-type half cell was fabricated
in the same manner as in Example 1, except that only pitch was used as a coating
10 material without adding silicon oxide (SiO) in the process of preparing the pitch.
Experimental Example 1>
Electrolyte impregnation properties of the electrodes fabricated in accordance
with Examples 1 and 2, and Comparative Examples 1 to 3 were evaluated. The
electrode was roll-pressed to have a porosity of about 23% and a time taken for 1
15 microliter ([i£) of a 1M LiPF6 electrolyte solution in a carbonate solvent dropped on the
surface of the electrode to completely permeate to the surface was measured. Results
are shown in Table 1 below.
-25-
Ex. 1 Ex. 2 Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3
Impregnation
. 88 86 91 93 142
time (sec)
As can be seen from Table 1, the electrodes using an anode active material
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 Comparative Example 3 of the electrode using an anode active material
5 surface-coated with carbon alone. The reason for this is that the highly polar
electrolyte can be rapidly permeated into particles by coating the surface of the anode
active material with a hydrophilic material.
Experimental Example 2>
Charge/discharge properties were evaluated using the coin-type half cells
10 fabricated in accordance with Examples 1 and 2 and Comparative Examples 1 to 3.
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, and charging was completed
when current density reached 0.01 C. During discharge, the cells were discharged in a
CC mode at a current density of 0.1 C to 1.5V. As a result, charge/discharge capacity
15 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.
-26-
Ex. 1 Ex. 2 Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3
Charge capacity
, , J 398.2 405.3 398.3 387.7 385.1
(mAh/g)
Discharge
capacity 368.7 374.1 368.1 357.1 356.6
(mAh/g)
Efficiency (%) 92A 923 92A 92l 92^6
Capacity
maintenance
(%) after 50 91 90 85 82 78
charge/discharge
cycles
As can be seen from Table 2 above, the anode active materials coated with a
composite containing silicon oxide (SiO) as a hydrophilic material according to
Examples 1 and 2 of the present invention exhibited high capacity maintenance after 50
5 charge/discharge cycles and high efficiency, as compared to Comparative Example 2
using silicon dioxide (S1O2) as a hydrophilic material. The reason for this is that when
silicon dioxide is used, a content of oxygen that irreversibly reacts with lithium is high,
efficiency is decreased and lithium oxide prepared during this reaction increases surface
resistance of the anode active material.
10 Also, it could be seen that the anode active materials according to Examples 1
and 2 exhibited considerably high capacity maintenance after 50 charge/discharge
cycles, as compared to the anode active material surface-coated with only carbon
-27-
according to Comparative Example 3. The reason for this is that the hydrophilic
material performing the same function as SEI forms a strong bond with a core material
via carbon and thereby inhibits removal of the SEI layer in the repeated
charge/discharge process. In addition, a material having high charge/discharge voltage
5 is coated, thereby preventing precipitation of lithium and improving ion conductivity.
On the other hand, when, like in Comparative Example 1, graphite and pitch
were simply mixed with each other without adding the hydrophilic material in the
process of preparing the pitch, the hydrophilic material was not uniformly distributed on
the surface of graphite but was instead concentrated thereon, the electrode was entirely
10 non-uniform and had low capacity maintenance after 50-cycle charge/discharge.
[INDUSTRIAL APPLICABILITY]
As apparent from the fore-going, the anode active material according to the
present invention has a specific structure in which a composite coating layer comprising
one or more materials selected from the group consisting of low crystalline carbon and
15 amorphous carbon, and silicon oxide enabling intercalation and deintercalation of ions
is formed on an outer surface of a core comprising a crystalline carbon-based material,
thus being effective in preparation of an anode active material.
Although the preferred embodiments of the present invention have been
disclosed for illustrative purposes, those skilled in the art will appreciate that various
-28-
*
modifications, additions and substitutions are possible, without departing from the
scope and spirit of the invention as disclosed in the accompanying claims.
-29-
[CLAIMS!
[Claim l l A method for preparing an anode active material comprising a core
composed of a crystalline carbon-based material, and a composite coating layer
composed of one or more materials selected from the group consisting of low crystalline
5 carbon and amorphous carbon, and silicon oxide enabling intercalation and
deintercalation of ions, the method comprising:
(a) mixing a precursor for a raw material of the one or more materials selected
from the group consisting of low crystalline carbon and amorphous carbon with silicon
oxide enabling intercalation and deintercalation of ions, followed by purification, to
10 prepare a mixture for coating;
(b) mixing the mixture for coating with a crystalline carbon-based material to
prepare a core-shell precursor comprising the raw material mixture for coating applied
to the core composed of the crystalline carbon-based material; and
(c) baking the core-shell precursor to carbonize the raw material of the one or
15 more materials selected from the group consisting of low crystalline carbon and
amorphous carbon into the one or more materials selected from the group consisting of
low crystalline carbon and amorphous carbon.
-30-
[Claim 2] The anode active material according to claim 1, wherein the composite
coating layer has a structure in which, in a matrix comprising one component selected
from one or more materials selected from the group consisting of low crystalline carbon
and amorphous carbon, and silicon oxide enabling intercalation and deintercalation of
5 ions, a filler comprising the other component is incorporated.
[Claim 3] The anode active material according to claim 1, wherein the crystalline
carbon-based material comprises one or more of graphite and low crystalline carbon.
[Claim 4] The anode active material according to claim 1, wherein the precursor for
the raw material of the one or more materials selected from the group consisting of low
10 crystalline carbon and amorphous carbon is a pitch solution.
[Claim 5] The anode active material according to claim 1, wherein the precursor is
derived from a coal-based material, a petroleum-based material or a petroleum/coalbased
mixture.
[Claim 6] The anode active material according to claim 1, wherein the silicon oxide
15 enabling intercalation and deintercalation of ions is represented by the following
formula:
SiOx
wherein x satisfies 0.1 < x < 1.5.
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t
[Claim 7] The anode active material according to claim 6, wherein x satisfies 0.5 <
x<1.3.
[Claim 8] The anode active material according to claim 1, wherein the baking is
carried out under an inert atmosphere or an anoxic atmosphere at 600 to 2,000°C.
5 [Claim 9] The anode active material according to claim 1, wherein the composite
coating layer has a structure in which a filler comprising silicon oxide enabling
intercalation and deintercalation of ions is incorporated in a matrix comprising one or
more materials selected from the group consisting of low crystalline carbon and
amorphous carbon.
10 [Claim 10] 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 silicon oxide enabling intercalation and
deintercalation of ions.
15 [Claim 11] The anode active material according to claim 1, wherein, in the
composite coating layer after the carbonization of step (c), the one or more materials
selected from the group consisting of low crystalline carbon and amorphous carbon and
a hydrophilic material comprising the silicon oxide enabling intercalation and
deintercalation of ions are mixed with each other in a weight ratio of 1:9 to 9:1.
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[Claim 12J 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 13] An anode, active material prepared by the method according to any one
5 of claims 1 to 12.
[Claim 14] 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.
[Claim 15] A secondary battery comprising the anode for secondary batteries
according to claim 14.
10 [Claim 16] The secondary battery according to claim 15, wherein the battery is a
lithium secondary battery.
[Claim 17] A middle- or large-sized battery pack comprising the secondary battery
according to claim 16 as a unit battery.