Specification
ANODE ACTIVE MATERIAL AND SECONDARY BATTERY COMPRISING
THE SAME
5 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 metal and/or a nonmetal
capable of intercalating and deintercalating ions, 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 metal and/or a non-metal capable of intercalating and deintercalating ions;
15 and a filler comprising the other component, incorporated in the matrix.
' Technological development and increased demand for mobile equipment have
led to rapid increase in the demand for secondary batteries as energy sources. Among
these secondary batteries, lithium secondary batteries having high energy density and
voltage, long cycle span and low self-discharge are commercially available and widely
5 used.
In addition, increased interest in environmental issues has brought about a great
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 main causes of air pollution. These electric
10 vehicles generally use nickel-metal hydride (Ni-MH) secondary batteries as power
sources. However, a great deal of study associated with use of lithium secondary
batteries with high energy density, discharge voltage and power stability is currently
underway and some are commercially available.
A lithium secondary battery has a structure in which a non-aqueous electrolyte
15 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.
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 and use of silicon compounds, sulfur compounds and the like is also
considered.
However, lithium secondary batteries have various problems, in particular,
5 problems associated with fabrication and driving properties of an anode.
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
10 of the anode active material complicates impregnation of highly polar electrolytes in the
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 surfactant as an additive to an
anode, an electrolyte or the like is suggested. However, disadvantageously, the
15 surfactant may have side effects on driving properties of batteries.
Meanwhile, regarding driving properties of anode, disadvantageously, 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 chargeldischarge process (activation process), and
Ilr battery capacity is reduced due to exhaustion of the electrolyte caused by removal
(breakage) and regeneration of the SEI layer during a continuous chargeldischarge
process.
In order to solve these problems, various methods such as formation of an SEI
5 layer through stronger bonding, or formation of an oxide layer on the surface of the
anode active material have been attempted. These methods have properties unsuitable
for commercialization such as deterioration in electric conductivity caused by the oxide
layer and deterioration in productivity caused by additional processes. Also, there still
exists a problem in that growth of dendrite lithium on the surface of the anode active
10 material may still cause short-circuit.
Accordingly, there is an increasing need for secondary batteries capable of
solving these problems.
15 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
solve the problems as described above, the present inventors discovered that, when an
-4-
* anode active material is produced by forming a composite coating layer on a crystalline
carbon-based core, various problems associated with anode fabrication process and
battery driving properties can be simultaneously solved. The present invention has
been completed, based on this discovery.
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
10 low crystalline carbon and amorphous carbon, and a metal and/or a non-metal capable
of intercalating and deintercalating ions, 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 metal and/or a non-metal capable of intercalating and deintercalating ions; and a filler
15 comprising the other component, incorporated in the matrix.
As such, the anode active material having a structure in which the core
comprising a crystalline carbon-based material is coated with the composite coating
layer having a matridfiller structure comprising one or more materials selected from the
group consisting'of low crystalline carbon and amorphous carbon, and a metal and/or a
-5-
* non-metal capable of intercalating and deintercalating ions can solve the problems in
the related art, based on specific active material structure and components.
First, the surface of the metal and/or non-metal capable of intercalating and
deintercalating ions comprised as a matrix or filler component iin the composite coating
5 layer is at least partially exposed on the surface of the anode active material and is
oxidized, thus becoming more hydrophilic. Accordingly, the metal and/or non-metal
capable of intercalating and deintercalating ions exhibits high miscibility with a
hydrophilic solvent in a slurry for fabrication of an anode according to the type of
materials used, thus improving dispensability in solid components in the slurry.
10 Accordingly, when an anode is fabricated by applying this slurry to a current collector,
distribution uniformity between components such as binder and the anode active
material can be improved and superior electrode properties can thus be obtained.
The improvement in uniformity of the metal and/or non-metal capable of
intercalating and deintercalating ions can minimize a decrease in bonding strength
15 between the slurry and the partial current collector which occurs on the non-uniform
electrode. The dmetal and/or non-metal capable of intercalating and deintercalating
ions improves affinity between the active material layer and the surface of the current
collector, 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
20 the active material layer fiom the current collector.
-6-
* Similarly, the metal andor non-metal capable of intercalating and
deintercalating ions 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
5 and considerably improving battery productivity.
Second, the metal andor non-metal capable of intercalating and deintercalating
ions comprised as a matrix or filler component in the composite coating layer minimizes
deterioration in electrical conductivity which may be induced by presence of material
incapable of intercalating and deintercalating ions.
10 Also, in a case of a lithium secondary battery, growth of lithium dendrites may
occur, since the crystalline carbon-based material serving as a core has a similar electric
potential to lithium, but this growth can be inhibited by coating the metal andor nonmetal
capable of intercalating and deintercalating ions on the surface of the crystalline
carbon-based material at a high oxidation-reduction level,
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
a composite coating layer comprising: a matrix comprising one component (for example,
amorphous carbon) selected from one or more materials selected from the group
consisting of low crystalline carbon and amorphous carbon and a metal andfor a nonmetal
capable of intercalating and deintercalating ions; and a filler comprising the other
5 component (for example, a metal and/or a non-metal capable of intercalating and
deintercalating ions), incorporated in the matrix.
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
10 planes of carbon are arrayed in a layer form), and hard carbon having a structure in
which the low-crystalline structures are mixed with non-crystalline parts.
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 low-
15 crystalline carbon, amorphous carbon, or a mixture thereof.
Meanwhile, the metal and/or non-metal capable of intercalating and
deintercalating ions, which is another compone,nt constituting the composite coating
layer in the present invention, exhibits relatively high hydrophilicity and polarity to one
C or more materials selected from the group consisting of low crystalline carbon and
amorphous carbon and thus improves mix preparation or electrolyte impregnation.
For realization of this improvement, the metal and/or non-metal capable of
intercalating and deintercalating ions are preferably exposed in at least a part of the
5 surface of the composite coating layer.
Also, such hydrophilicity may be derived from inherent properties of the metal
and/or non-metal capable of intercalating and deintercalating ions, or partial oxidization
of the metal and/or non-metal capable of intercalating and deintercalating ions during
exposure of the metal and/or non-metal to air. That is, the metal and/or non-metal
10 have a particle shape, while the surface thereof has relatively high hydrophilicity due to
bonding to oxygen. This surface oxidization may occur upon exposure of the metal
and/or non-metal to air in the battery fabrication process without separate treatment.
Preferably, examples of the metal and/or non-metal include Si, Sn and the like.
This material may be used alone or in combination thereof.
15 Si may be used as a metal or an alloy for a high-capacity lithium secondary
battery anode and is not commercially available due to rapid variation in volume during
chargeldischarge. However, according to the present invention, when Si is used as a
composite with one or more materials selected from the group consisting of low
Ub crystalline carbon and amorphous carbon for a coating layer of a graphite core, the
effects described above as well as improvement in anode capacity can be achieved.
Sn may be also used as a metal or alloy for a lithium secondary battery anode,
but is not yet commercially available. However, similar to Si, Sn is used as a
5 composite with one or more materials selected fiom the group consisting of low
crystalline carbon and amorphous carbon as the coating layer of the graphite core, the
effects described above as well as improvement in anode capacity can be achieved.
As described above, by using Si and/or Sn which exerts high capacity when
used as the anode active material for the surface coating layer, high capacity can be
10 obtained as compared to a case in which a general carbon-based anode active material is
used alone.
In one embodiment, the metal and/or non-metal may be an alloy of Si and Sn.
There is no particular limitation as to the type and component contents of the alloy of Si
and Sn so long as the alloy is capable of intercalating and deintercalating ions.
15 In the present invention, the structure of the composite coating layer may be
determined, depending on components of matrix and filler.
In a first exemplary structure, a filler comprising a metal and/or a non-metal
capable of intercalating and deintercalating ions is incorporated in a matrix comprising
I one or more materials selected from the group consisting of low crystalline carbon and
I
amorphous carbon.
In this case, as described above, in order to obtain the effects of hydrophilicity,
the filler comprising a metal andlor a non-metal capable of intercalating and
5 deintercalating ions is preferably exposed in at least a part of the surface of the
composite coating layer.
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
incorporated in a matrix comprising a metal and/or a non-metal capable of intercalating
10 and deintercalating 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
independent phases, the content of the matrix component is not necessarily greater than
the content of the filler component.
15 Accordingly, when the metal and/or the non-metal capable of intercalating and
deintercalating ions forms a composite as a matrix, the metal andor non-metal capable
of intercalating and deintercalating ions is exposed in at least a part of the surface of the
composite coating layer, and the anode active material may thus have hydrophilicity,
exerting the effects described above.
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 metal andor non-metal capable of intercalating and deintercalating ions
are not particularly limited so long as the intended effects of the present invention
5 (described above) can be exerted. 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 metal andor non-metal capable of
intercalating and deintercalating ions may be 5 to 90% by weight, based on the total
10 amount of the composite coating layer.
The amount (coating amount) of the composite coating layer is preferably 0.1
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
15 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.
The present invention also provides an anode mix comprising #he anode active
20 material.
* The anode mix according to the present invention comprises 1 to 20% by
weight of a binder, and optionally comprises 0 to 20% by weight of a conductive
material, based on the total weight of the anode mix.
Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene
5 fluoride (PVdF), cellulose, polyvinyl alcohol, 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
* Company), Ketjen Black EC series (available from Armak Company), Vulcan XC-72
(available fiom 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 component such as viscosity controller or adhesion promoter may be
further optionally added singly or in combination of two or more types.
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, 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.
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 v. 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.
* 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
comprise other components such as binder or conductive material described above
associated with the configuration of the anode.
The cathode current collector is generally manufactured to have a thickness of
3 to 500 w. 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
' examples thereof include, but are not limited to, layered compounds such as lithium
cobalt oxide (LiCoO2) or lithium nickel oxide (LiNi02) 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 LiNil-yMy02(i n 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, 0.015y50.7); lithium nickel cobalt manganese composite
oxides represented by Lil+zNib&C~l -(b+c+d)MdO(2-e)sAuec h as Lil+zNil13C~~,3Mn1~302
or Lil+zNio,4Mno.4Coo.20(i2n which -0.55zF0.5, 0.1310.8, 0.15~50.8, OidF0.2,
OIe50.2, b+c+d I
An anode active material was produced and a coin-type half cell was fabricated
in the same manner as Example 1, except that only pitch was used, without using
silicon.
An anode active material was produced and a coin-type half cell was fabricated
in the same manner as Example 1, except that pitch and silicon were mixed at a weight
ratio of 1 : 9.
The carbon yield of the pitch was 50% and the content of the silicon was
higher than 90% based on the total amount of carbon and silicon.
Electrolyte impregnation properties of the electrodes fabricated in accordance
5 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 for which 1
micrometer of a 1M LiPF6 electrolyte solution in a carbonate solvent dropped on the
surface of the electrode was completely permeated into the surface was measured.
Results are shown in Table 1 below.
As can be seen from Table 1, the electrodes using an anode active material
coated with a carbonlmetal composite according to Examples 1 and 2 of the present
invention exhibited considerably short electrolyte impregnation times, as compared to
Comparative Example 1 of electrode using an anode active material coated with only
15 carbon. The reason for this is that the metal surface of the anode active material
surface was partially oxidized and became hydrophilic, enabling the highly polar
electrolyte to be rapidly permeated into particles.
-23-
Comp. Ex. 2
93
Comp. Ex. 1
142
Impregnation
time (sec)
Ex. 1
92
Ex. 2
95
Chargeldischarge 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
5 0.1C to 5 mV and then maintained in a CV mode at 5 mV, charging was completed
when a 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, 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
10 to 0.5C. The results are shown in Table 2 below.
Charge capacity
(mWg)
Discharge
capacity
(mAh/g)
Efficiency (%)
Capacity
maintenance
(%) after 50
chargeldischarge
cycles
Ex. 1
444.6
410.8
92.4
89
Ex. 2
411.7
380.8
92.5
8 8
Comp. Ex. 1
385.1
356.6
92.6
78
Comp. Ex. 2
675.0
591.3
87.6
48
As can be seen from Table 2 above, anode active materials coated with a
carbonlmetal composite according to Examples 1 and 2 of the present invention
exhibited high discharge capacity and high capacity maintenance after 50
chargeldischarge cycles, as compared to Comparative Example 1 (anode active material
5 coated only with carbon). The reason for this is that a metal material is uniformly
distributed as a composite with carbon on the graphite surface and can realize high
theoretical discharge capacity. Also, a composite in which the metal and carbon are
homogeneously mixed was coated on the graphite surface and electric conductivity can
thus be maintained in spite of variation in volume caused by chargeldischarge. Also, a
10 part of the metal surface is oxidized and is thus converted into a hydrophilic material
performing the same function as SEI, which forms a strong bond with a core material
via carbon and thereby inhibits removal of the SEI layer in the repeated
chargeldischarge process. Also, a material having high chargeldischarge voltage is
coated, thereby preventing precipitation of lithium and improving ion conductivity.
15 Also, when the content of silicon is considerably higher than that of carbon as
in Comparative Example 2, electrical conductivity was decreased, resistance of the
electrode was considerably increased, side effects of electrolyte were increased and
capacity maintenance (%) after 50 chargeldischarge cycles was considerably low due to
great variation in volume of silicon during chargeldischarge.
As apparent from the fore-going, the anode active material according to the
present invention is effective in greatly improving a battery fabrication process,
minimizing deterioration in electric conductivity and considerably inhibiting
5 deterioration battery lifespan, through a specific core/composite coating layer structure
and can minimize performance and safety problems associated with lithium
precipitation through presence of material having a high oxidation-reduction level on
the surface of the active material.
Although the preferred embodiments of the present invention have been
10 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.
[claim 1] An anode active material for secondary batteries, capable of
intercalating and deintercalating ions, 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 metal and/or a
non-metal capable of intercalating and deintercalating ions,
wherein the composite coating layer comprises:
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 metal and/or a non-metal capable of intercalating and deintercalating ions; 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 metal
andfor non-metal capable of intercalating and deintercalating ions is exposed in at least
a part of the surface of the composite coating layer.
[claim 4] The anode active material according to claim 1, wherein the metal
5 and/or non-metal capable of intercalating and deintercalating ions comprises at least one
selected from the group consisting of Si and Sn.
[claim 5] The anode active material according to claim 4, wherein the metal
and/or non-metal capable of intercalating and deintercalating ions is an alloy of Si and
Sn.
10 [claim 6] The anode active material according to claim 1, wherein the
composite coating layer has a structure in which a filler comprising a metal and/or a
non-metal capable of intercalating and deintercalating ions is incorporated in a matrix
comprising one or more materials selected from the group consisting of low crystalline
carbon and amorphous carbon.
15 [claim 7] 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 metal and/or a non-metal capable of
intercalating and deintercalating ions.
IY [claim 8] The anode active material according to claim 1, wherein an amount of
the composite coating layer is 0.1 to 20% by weight, based on the total amount of the
anode active material.
[claim 9] An anode mix comprising the anode active material according to any
5 one of claims 1 to 8.
[claim 10] An anode for secondary batteries in which the anode mix according to
claim 9 is applied to a current collector.
[claim 11] A secondary battery comprising the anode for secondary batteries
according to claim 10.
10 [claim 12] The secondary battery according to claim 11, wherein the battery is a
lithium secondary battery.
[claim 13] A battery pack comprising the secondary battery according to claim