ELECTRODE WITH ORGANIC/INORGANIC COMPOSITE AND
ELECTROCHEMICAL DEVICE COMPRISING THE SAME
Technical Field
The present invention relates to an identifiable
electrode that allows users to easily identify the origin or
kind of the electrode itself or an electrochemical device
using the same electrode. Also, the present invention relates
to an electrochemical device using the above electrode.
Background Art
Electrochemical devices are power sources for electronic
appliances, etc. As the use of batteries is enlarged to
applications for the storage of energy for portable
telephones, camcorders, notebook computers, personal computers
and electric vehicles, efforts on the research and development
of batteries are increasingly embodied.
Meanwhile, since the electrochemical devices have been
in increasing demand, counterfeits thereof have been
distributed more and more. Such counterfeits have lower safety
than authentic products. However, when an electrochemical
device causes explosion due to the counterfeit, it is
difficult to check the authenticity of the device. Therefore,
there has been an imminent need for a method for checking the
authenticity of an electrochemical device.
According to the prior art, there has been suggested a
method for checking the authenticity of an electrochemical
device by incorporating a semiconductor capable of
communicating with the main body of an electronic appliance
into the electrochemical device. However, the above method
requires an additional space for housing the semiconductor
inside the device, so that the space for receiving electrodes
inside the device grows smaller. This ultimately results in a
drop in the capacity of a battery. Additionally, such
introduction of a semiconductor into the electrochemical
device causes degradation of the productivity and cost-
efficiency.
Disclosure
Technical Problem
Therefore, the present invention has been made in view
of the above-mentioned problems. It is an object of the
present invention to provide an electrode comprising an
organic/inorganic composite into which inorganic particle(s)
having a unique spectrum or color pattern is (are) introduced
according to a predetermined rule, so that the electrode or an
electrochemical device using the same allows users to identify
its origin or kind.
Technical solution
In order to achieve the above-mentioned object, there is
provided an electrode comprising an organic/inorganic
composite introduced onto either surface or both surfaces
thereof, the organic/inorganic composite comprising inorganic
particle or aggregates thereof having a unique spectrum or
color pattern according to a predetermined rule, and a polymer
capable of interconnecting and fixing the inorganic particles.
Also, there is provided an electrochemical device comprising
the above electrode. Further, there is provided a method for
identifying the origin or kind of the electrode itself or the
electrochemical device comprising the same by using the
electrode.
Hereinafter, the present invention will be explained in
more detail.
In general, an electrochemical device comprises a
cathode, an anode, a separator and an electrolyte. The above
constitutional elements have been developed to have various
structural characteristics in order to improve the quality of
the device. For example, an organic/inorganic composite may be
introduced onto the surface of an electrode. The
organic/inorganic composite serves as a separator, is bound
firmly to the interface with an electrode, and has little
possibility of heat shrinking. Thus, it is possible to improve
the quality and safety of the device.
The organic/inorganic composite may comprise inorganic
particle(s); and a polymer capable of interconnecting and
fixing the inorganic particles. As the inorganic particles,
white inorganic particles, such as alumina, silica or titania,
have been used widely. Moreover, there is no disclosure of
such organic/inorganic composites used to identify the origin
or kind of the electrode or electrochemical device.
According to the present invention, inorganic
particle(s) having a unique spectrum or color pattern is(are)
introduced into the organic/inorganic composite as the
inorganic component according to a predetermined rule, so as
to make the electrode itself identifiable.
Each kind of inorganic particle has its unique spectrum
or color pattern. Therefore, when such inorganic particle(s)
is(are) introduced into an organic/inorganic composite
according to a predetermined rule, the electrode comprising
the same organic/inorganic composite can be identifiable like
a trademark.
Herein, the above "predetermined rule" means a specific
spectrum (peak position and intensity) and/or color pattern
determined preliminarily so that the organic/inorganic
composite or electrode according to the present invention can
be distinguished from the others manufactured by a third
party. Particularly, the specific spectrum (peak position and
intensity) and/or color pattern may be variable depending on
the number, kind, content, etc. of the inorganic particles
used in the organic/inorganic composite. For example, it is
possible to control the peak position and intensity by using
one or more kinds of inorganic particles and by adjusting the
amounts of the particles. Otherwise, it is possible to control
the color pattern by using one or more kinds of inorganic
particles capable of developing a color in the visible light
or non-visible light range; or one or more kinds of inorganic
particles capable of developing a color or undergoing a color
change under a specific chemical condition (e.g. temperature,
oxidation state, etc.). Further, it is possible to control
both the spectrum and the color pattern by using at least two
kinds of inorganic particles in combination or by varying the
arrangement of the particles.
Therefore, according to the present invention, it is
possible to identify the origin or kind of the electrode
itself or the electrochemical device comprising the same by
checking the spectrum and/or color pattern of the
organic/inorganic composite. Particularly, according to the
present invention, the electrode itself functions as a means
for identification. Thus, no additional space for an
identification means is required, thereby preventing a drop in
the capacity of the electrochemical device. Also, the
identification method according to the present invention may
be applied to counterfeits made only inside the
electrochemical device.
There is no particular limitation in the inorganic
particle used in the present invention, as long as the
particle has its unique spectrum or color pattern.
For example, the inorganic particle includes: (i)
inorganic particles having a unique spectrum or color pattern
in the visible light range; (ii) inorganic particles having a
unique spectrum or color pattern in the non-visible light
range; or (iii) inorganic particles having a unique spectrum
or color pattern under a specific chemical condition (e.g.
temperature or oxidation state). Additionally, inorganic
particles used in paints or pigments, or phosphor particles
used in display devices or lamps may be used in the present
invention.
Non-limiting examples of the inorganic particle having a
unique spectrum or color pattern, such as a white, black,
yellow, orange, brown, red, violet, blue, green, gray, pink or
fluorescent color, in the visible light range (a wavelength
range of 380~770nm) are as follows:
(a) white: Al203, ZnO, ZnS, Si02, Zr02, Sn02, CeO2, MgO,
CaO, Y203, TiO2, Sb2O3, BaTiO3, SrTiO3, Pb(Zr,Ti)O3 (PZT), Pb1-
xLaxZr1-yTiyO3 (PLZT), etc.
(b) black: Fe3O4, (Co, Ni)0-(Cr, Fe)2O3, etc.
(c) yellow: PbCrO4, ZnCrO4, BaCrO4, CdS, FeO(OH) nH2O,
TiO2-NiO-Sb2O3, Pb(CN)2, Ca2PbO4, Al, Fe, Sn-2PbO-Sb2O5, V-SnO2, V-
ZrO2, Pr-ZrSiO4, CrSbO4 or Cr2WO6-TiO2, ZrSO4 coated CdS or
(CdZn)S, etc.
(d) orange: PbCrO4 PbO, PbCrO4 PbMoO4 PbSO4, etc.
(e) brown: Fe2O3+FeO, Fe2O3+MnO2+Mn3O4, ZnO • (Al, Cr,
Fe)2O3, etc.
(f) red: Fe2O3, Pb3O4, HgS, CdS+CdSe, CdS+HgS, 2Sb2S3
Sb2O3, etc.
(g) violet: Co3(PO4)2, CO3(PO4)2 4H2O, CO3(PO4)2 8H2O, etc.
(h) blue: 3NaAl Si04 Na2S2, Fe4 [Fe (CN6) 3] nH2O, CoO nAl2O3,
CoO nSnO2 mMgO, Co3O4+SiO2+Al2O3+Fe2O3+NiO+MnO, CoO-nAl203 or (Co,
Zn)O-nAl2O3, 2 (Co, Zn)O -SiO2, V-ZrSiO4, etc.
(i) green: Cr2O3, Cr2O(OH)4, Cu(CH3CO2)2 3CuO(AsO2)2, CoO-
ZnO-MgO, (Co, Zn)0 • (Al, Cr)2O3, 3CaO-Cr2O3 -3SiO2, (Al, Cr)2O3,
etc.
(j) gray: Sb-SnO2, Co,Ni-ZrSiO4, etc.
(k) pink: Mn, P-a-Al2O3, ZnO • (Al, Cr)2O3, Cr-CaO -SnO2
•SiO2, Fe-ZrSiO4, Cr,Co-CaO • Sn02 -SiO2, ZrSiO4 coated Cd (S, Se),
etc.
(1) fluorescent color: ZnS, Zn2SiO4, (Zn,Cd)S, CaS, SrS,
CaWO4, etc.
(m) others: SiC (green and/or black), Si3N4 (white), etc.
Although there is no particular limitation in the size
of the inorganic particle, the inorganic particle preferably
has a size of 0.001 /zm~10 //m. If the size is less than 0.01 im,
the pores formed by the inorganic particles are too small.
Thus, it may be difficult to transfer lithium ions through the
organic/inorganic composite. If the size is greater than 10 im,
the resultant electrode has an increased thickness.
Meanwhile, a polymer capable of interconnecting and
fixing the inorganic particles may be used a binder polymer
currently used in the art. The polymer serves as a binder that
interconnects and stably fixes the inorganic particles among
themselves, and between the inorganic particles and the
surface of an electrode active material, and thus prevents
degradation in mechanical properties of a final resultant
organic/inorganic composite.
The polymer preferably has a glass transition
temperature (Tg) of between -200°C and 200"C in order to
improve mechanical properties such as flexibility and
elasticity of a final resultant organic/inorganic composite.
Additionally, the polymer preferably shows a high degree
of swelling with an electrolyte by being gelled when
impregnated with an electrolyte, and more preferably has a
solubility parameter between 15 and 4 5 MPa1/2.
Non-limiting examples of the polymer that may be used in
the present invention include polyvinylidene fluoride-co-
hexafluoropropylene, polyvinylidene fluoride-co-
trichloroethylene, polymethylmethacrylate, polyacrylonitrile,
polyvinylpyrrolidone, polyvinylacetate, polyethylene-co-vinyl
acetate, polyimide, polyethylene oxide, cellulose acetate,
cellulose acetate butyrate, cellulose acetate propionate,
cyanoethylpullulan, cyanoethylpolyvinylalcohol,
cyanoethylcellulose, cyanoethylsucrose, pullulan,
carboxylmethyl cellulose, polyvinylalcohol or mixtures
thereof.
There is no particular limitation in the ratio of the
inorganic particles to the polymer forming the
organic/inorganic composite according to the present
invention. The ratio may be controlled in a range of
10:90~99:1 (on the weight basis), and preferably of
50:50~99:1 (on the weight basis), depending on the thickness
and physical properties of the finally formed electrode and
the content of the inorganic particles defined by the
predetermined rule.
The organic/inorganic composite according to the present
invention may further comprise other additives.
Meanwhile, the organic/inorganic composite according to
the present invention has pores. The pores can be capable of
lithium ion conduction when they are subsequently impregnated
with an electrolyte. The pores may be formed among the
inorganic particles, between inorganic particles and polymers,
or by an entangled structure of the polymers. Additionally,
the pore has a size depending on the size of the inorganic
particles.
The electrode according to the present invention
comprises the organic/inorganic composite bound to either
surface or both surfaces thereof. For example, the electrode
according to the present invention may comprise the
organic/inorganic composite entangled with the pores of the
electrode by the polymers. In this case, the organic/inorganic
composite is preferably introduced to a predetermined
thickness (more preferably to a thickness of 1~10 μm), along
the thickness direction of the electrode so that the
organic/inorganic composite is sufficiently impregnated with
the electrolyte and can function also as an electrolyte. For
reference, FIG. 1 shows the electrode having the
organic/inorganic composite introduced onto either surface or
both surfaces thereof according to the present invention.
One embodiment of the method for manufacturing the
electrode according to the present invention comprises the
steps of: (a) dissolving a polymer capable of functioning as a
binder into a solvent to provide a first, mixed solution; (b)
adding at least one kind of the aforementioned inorganic
particles to the first mixed solution of step (a) and mixing
them to provide a second mixed solution; and (c) coating the
second mixed solution onto the surface of an electrode,
followed by drying.
Although there is no particular limitation in the
solvent used in step (a), the solvent preferably has a
solubility parameter similar to the solubility of the polymer
and a low boiling point in order to facilitate uniform mixing
and removal of the solvent.
Non-limiting examples of such solvents include acetone,
tetrahydrofuran, methylene chloride, chloroform,
dimethylformamide, N-methyl-2-pyrrolidone (NMP), cyclohexane,
water and mixtures thereof.
Meanwhile, in step (b), it is preferred to perform
crushing of the inorganic particles after at least one kind of
the aforementioned inorganic particles is added to the first
mixed solution. The time for crush is suitably 1-20 hours. The
particle size of the crushed particles ranges preferably from
0.01 and 10 μm. Conventional crush methods, preferably a method
using a ball mill may be used.
And, in step (c), the conventional coating methods known
to one skilled in the art may be used. It is possible to use
various processes including dip coating, die coating, roll
coating, comma coating or combinations thereof.
Meanwhile, there is no particular limitation in the
electrode into which the organic/inorganic composite is
introduced, as long as the electrode is one currently used in
electrochemical devices. In general, the electrode comprises
an electrode active material bound to a current collector.
The electrode active material may include a cathode
active material and an anode active material.
Non-limiting examples of the cathode active material
include: lithium transition metal composite oxides, including
LiMxOy (wherein M= Co, Ni, Mn, CoaNibMnc) , such as lithium
manganese composite oxides (e.g. LiMn2O4) , lithium nickel
oxides (e.g. LiNiO2) , lithium cobalt oxides (e.g. LiCo02) , or
other oxides containing other transition metals partially
substituting for manganese, nickel and cobalt; chalcogenide
(e.g. manganese dioxide, titanium disulfide, molybdenum
disulfide, etc.); or the like. Among these examples, LiCo02,
LiNiO2, LiMnO2, LiMn2O4, Li (NiaCobMnc) O2 (wherein 0