Specification
WO 2006/068428 PCT/KR2005/004450
ORGANIC/INORGANIC COMPOSITE MICBOPOROUS MEMBRANE AND
ELECTROCHEMICAL DEVICE PREPARED THEREBY
Technical Field
The present invention relates to a novel
organic/inorganic composite porous separator that can show
excellent thermal safety, electrochemical safety and lithium
ion conductivity and a high degree of swelling with
electrolyte, compared to conventional polyolefin-based
separators, and an electrochemical device comprising the
same, which ensures safety and has improved quality.
Background Art
Recently, there is increasing interest in energy
storage technology. Batteries have been widely used as energy-
sources in portable phones, camcorders, notebook computers,
PCs and electric cars, resulting in intensive research and
development for them. In this regard, electrochemical devices
are the subject of great interest. Particularly, development
of rechargeable secondary batteries is the focus of
attention.
Among the currently used secondary batteries, lithium
secondary batteries, developed in early 1990's, have a drive
voltage and an energy density higher than those of
conventional batteries using aqueous electrolytes (such as
Ni-MH batteries, Ni-Cd batteries and H2SO4-Pb batteries) , and
thus are spotlighted in the field of secondary batteries.
However, lithium secondary batteries have problems related to
their safety, due to ignition and explosion caused by the use
of organic electrolytes, and are manufactured by a
complicated process. Lithium ion polymer batteries, appearing
more recently, solve the above-mentioned disadvantages of
1
WO 2006/068428 PCT/KR2005/004450
secondary lithium ion batteries, and thus become one of the
most potent candidates of next generation batteries. However,
such secondary lithium ion polymer batteries still have low
capacity compared to secondary lithium ion batteries.
Particularly, they show insufficient discharge capacity at
low temperature. Hence, there is an imminent need for the
improvement of secondary lithium ion batteries.
A lithium ion battery is manufactured by coating a
cathode active material (e.g. LiCoO2) and an anode active
material (e.g. graphite), which have crystal structures
including interstitial volumes, onto the corresponding
current collector (i.e. aluminum foil and copper foil,
respectively) to provide a cathode and an anode. Then, a
separator is interposed between both electrodes to form an
electrode assembly, and an electrolyre is injected into the
electrode assembly. During a charge cycle of the battery,
lithium intercalated into the crystal structure of the
cathode active material is deintercalated, and then
intercalated into the crystal structure of the anode active
material. On the other hand, during a discharge cycle,
lithium intercalated into the anode active material is
deintercalated again, and then intercalated back into the
crystal structure of the cathode. As charge/discharge cycles
are repeated, lithium ions reciprocate between the cathode
and the anode. In this regard, a lithium ion battery is also
referred to as a rocking chair battery.
Such batteries have been produced by many battery
producers. However, most lithium secondary batteries have
different safety characteristics depending on several
factors. Evaluation of and security in safety of batteries
are very important matters to be considered. Particularly,
users should be protected from being damaged by
2
WO 2006/068428 PCT/KR2005/004450
malfunctioning batteries. Therefore, sarety of batteries is
strictly restricted in terms of ignition and combustion of
batteries by safety standards.
Many attempts have been made to solve the problem
related to the safety of a battery. However, ignition of a
battery, caused by a forced internal short circuit due to
external impacts (particularly, in the case of a customer-
abused battery) cannot be solved yet.
Recently, US Patent No. 6,432,586 discloses a
polyolefin-based separator coated with an inorganic layer
such as calcium carbonate, silica, etc., so as to prevent an
internal shorn circuit, caused by dendrite growth inside of a
battery. However, the polyoiefin-based separator merely using
conventional inorganic particles cannot provide significant
improvement in the safety of a battery, when the battery
experiences an internal short circuit due to external
impacts. There is no mechanism for preventing such problem in
the separator. Additionally, the inorganic particle layer
disclosed in the above patent is not particularly defined in
terms of the thickness, pore size and porosity. Moreover, the
inorganic particles used in the separator have no lithium
conductivity, and thus cause a significant drop in the
quality of a battery.
Brief Description of the Drawings
The foregoing and other objects, features and
advantages of the present invention will become more apparent
from the following detailed description when taken in
conjunction with the accompanying drawings in which:
FIG. 1 is a schematic view showing an organic/inorganic
composite porous separator according to the present
invention, and the function thereof in a battery;
3
WO 2006/068428 PCT/KR2005/004450
FIG. 2a and FIG. 2b are photographs taken by a Scanning
Electron Microscope (SEM) showing the organic/inorganic
composite porous separator (PVdF-CTFE/BaTiCb) according to
Example 1, wherein FIG. 2a and FIG. 2b show the active layer
and separator substrate, respectively;
FIG. 3 is a photograph taken by SEM showing the
composite separator according to Comparative Example 2,
wherein the composite separator comprises inorganic particles
and a polymer, the polymer being present in a higher
proportion than the inorganic particles;
FIG. 4 is a graph showing variations in ion
conductivity depending on the mixing ratio of inorganic
particles and a binder polymer that form the
organic/inorganic composite porous separator according to the
present invention;
FIG. 5a and FIG. 5b are photographs showing the results
for a heat shrinking test of separators, wherein FIG. 5a and
FIG. 5b show a currently used PE separator, and the
organic/inorganic composite porous separator (PVdF-
CTFE/BaTiO3) according to Example 1, respectively, after each
of the separators is maintained at 150 °C for 1 hour;
FIG. 6a and FIG. 6b are photographs showing the results
for a pseudo internal short circuit test of separators,
wherein FIG. 6a and FIG. 6b show a currently used PE
separator, and the organic/inorganic composite porous
separator (PVdF-CTFE/BaTiO3) according to Example 1,
respectively;
FIG. 7 is a graph showing variations in voltage of each
of the lithium secondary batteries including the
organic/inorganic composite porous separator (PVdF-
CTFE/BaTiO3) according to Example 1 and the currently used PE
4
WO 2006/068428 PCT/KR2005/004450
separator according to Comparative Example 1, after local
crush that causes an artificial internal short circuit;
FIG. 8a and FIG. 8b are photographs showing the results
for the battery safety test, after local crush that causes an
artificial internal short circuit, wherein FIG. 8a and FIG.
8b show the currently used PE separator according to
Comparative Example 1 and the organic/inorganic composite
porous separator (PVdF-CTFE/BaTiO3) according to Example 1,
respectively; and
FIG. 9a and FIG. 9b are graphs showing the results for
the safety test of batteries after overcharge, wherein FIG.
9a and FIG. 9b show the currently used PE separator according
to Comparative Example 1 and the organic/inorganic composite
porous separator (PVdF-CTFE/BaTiO3) according to Example 1,
respectively.
Disclosure of the Invention
The present inventors have found that an
organic/inorganic composite porous separator, formed by using
(1) a polyolefin-based separator substrate, (2) inorganic
particles and (3) a binder polymer, improves thermal safety
of a conventional polyolefin-based separator. Additionally,
we have found that because the organic/inorganic composite
porous separator has pore structures present both in the
polyolefin-based separator substrate and in an active layer
formed of the inorganic particles and the binder polymer
coated on the separator substrate, it provides an increased
volume of space, into which a liquid electrolyte infiltrates,
resulting in improvements in lithium ion conductivity and
degree of swelling with electrolyte. Therefore, the
organic/inorganic composite porous separator can improve the
5
WO 2006/068428 PCT/KR2005/004450
quality and safety of an electrochemical device using the
same as a separator.
We have also found that when inorganic particles having
piezoelectricity derived from a high dielectric constant
and/or inorganic particles having lithium ion conductivity
are used as the inorganic particles that form the active
layer, it is possible to prevent a complete short circuit
between both electrodes by the inorganic particles, even if
the separator in a battery is broken due to external impacts.
It is also possible to solve the problem related to safety,
such as explosion of a battery, by reducing the voltage of a
battery gradually due to the flow of electric current, caused
by the lithium conductivity and/or piezoelectricity of the
inorganic particles.
Therefore, it is an object of the present invention to
provide an organic/inorganic composite porous separator, a
method for manufacturing the same and an electrochemical
device comprising the same.
According to an aspect of the present invention, there
is provided an organic/inorganic composite porous separator,
which comprises (a) a polyolefin-based separator substrate;
and (b) an active layer formed by coating at least one region
selected from the group consisting of a surface of the
substrate and a part of pores present in the substrate with a
mixture of inorganic particles and a binder polymer, wherein
the inorganic particles in the active layer are
interconnected among themselves and are fixed by the binder
polymer, and interstitial volumes among the inorganic
particles form a pore structure. There is also provided an
electrochemical device (preferably, a lithium secondary
battery) comprising the same.
6
WO 2006/068428 PCT/KR2005/004450
According to another aspect of the present invention,
there is provided a method for manufacturing an
organic/incrganic composite porous separator, which includes
the steps of: (a) dissolving a binder polymer into a solvent
to form a polymer solution; (b) adding inorganic particles
having lithium ion conductivity to the polymer solution
obtained from step (a) and mixing them; and (c) coating the
mixture of inorganic particles with a binder polymer obtained
from step (b) onto at least one region selected from the
group consisting of a surface of the substrate and a part of
the pores present in the substrate, followed by drying.
Hereinafter, the present invention will be explained in
more detail.
The present invention is characterized by providing a
novel organic/inorganic composite porous separator, which
shows excellent thermal safety, electrochemical safety and
lithium ion conductivity, and a high degree of swelling with
electrolyte, compared to a polyolefin-based separator
currently used as a separator for batteries.
The organic/inorganic composite porous separator is
obtained by coating an active layer comprising inorganic
particles and a binder polymer on a polyolefin-based
separator substrate. Herein, the pores present in the
separator substrate itself and a uniform pore structure
formed in the active layer by the interstitial volumes among
the inorganic particles permit the organic/inorganic
composite porous separator to be used as a separator.
Additionally, if a polymer capable of being gelled when
swelled with a liguid electrolyte is used as the binder
polymer component, the organic/inorganic composite porous
separator can serve also as an electrolyte.
7
WO 2006/068428 PCT/KR2005/004450
Particular characteristics of the organic/ inorganic
composite porous separator are as follows.
(1) Conventional composite separators, formed by
coating inorganic particles or a mixture of inorganic
particles and a binder polymer onto a conventional polyclefin
separator have no pore structure or, if any, have an
irregular pore structure having a pore size of several
angstroms. Therefore, they cannot serve sufficiently as
spacers, through which lithium ions can pass (see FIG.3).
Additionally, in order to form a microporous structure, most
of such conventional separators are subjected to extraction
with a plasticizer so that a microporous structure can be
formed in a gel type polymer electrolyte, resulting in
degradation in the quality of a battery.
On the contrary, the organic/inorganic composite porous
separator according to the present invention has uniform pore
structures both in the active layer and the polyolefin-based
separator substrate, as shown in FIGs. 2 and 3, and the pore
structures permit lithium ions to move smoothly therethrough.
Therefore, it is possible to introduce a large amount of
electrolyte through the pore structures, so as to obtain a
high degree of swelling with electrolyte, resulting in
improvement in the quality of a battery.
(2) Although conventional polyolefin-based separators
cause heat shrinking at high temperature because they have a
melting point of 120-140°C (see FIG.5a), the organic/inorganic
composite porous separator, comprising the inorganic
particles and the binder polymer, does not cause heat
shrinking due to the heat resistance of the inorganic
particles (see FIG.5b). Therefore, an electrochemical device
using the above organic/inorganic composite porous separator
prevents a complete internal short circuit between a cathode
8
WO 2006/068428 PCT/KR2005/004450
and an anode by the organic/inorganic composite porous active
layer, even when the separator is broken under extreme
conditions caused by internal or external factors, such as
high temperature, overcharge, external impacts, etc. Even if
a short circuit occurs, the region of short circuit can be
inhibited from extending throughout: the battery. As a result,
it is possible to significantly improve the safety of a
battery.
(3) Conventional separators or polymer electrolytes are
formed in the shape of free standing films and then assembled
together with electrodes. On the contrary, the
organic/inorganic composite porous separator according to the
present invention is formed by coating the active layer
directly on the surface of a polyolefin-based separator
substrate, so that the pores on the surface of the
polyolefin-based separator substrate and the active layer can
be anchored to each other, thereby providing a firm physical
bonding between the active layer and the porous substrate.
Therefore, problems related to mechanical properties such as
brittleness can be improved. Additionally, such increased
interfacial adhesion between the porous substrate and the
active layer can decrease the interfacial resistance. In
fact, the organic/inorganic composite porous film according
to the present invention includes the organic/inorganic
composite active layer bonded organically to the polyolefin-
based separator substrate. Additionally, the active layer
does not affect the pore structure present in the polyolefin-
based substrate, so that the structure can be maintained.
Further, the active layer itself has a uniform pore structure
formed by the inorganic particles (see FIGs. 2 and 3).
Because the above-mentioned pore structures are filled with a
liquid electrolyte injected subsequently, interfacial
9
WO 2006/068428 PCT/KR2005/004450
resistance generated among the inorganic particles or between
the inorganic particles and the binder polymer can be
decreased significantly.
(4) Polyolefin-based separators coated with a layer
comprising a metal oxide or a mixture of a metal oxide with a
polymer have been disclosed according to the prior art.
However, most of such conventional separators comprise no
binder polymer for supporting and interconnecting inorganic
particles. Even if a polymer is used in such conventional
separators, the polymer should have been used in a great
amount, so that such conventional separators have no pore
structures or have a non-uniform pore region in the polymer,
and thus cannot serve sufficiently as separators, through
which lithium ions can pass (see, FIG. 4) . Additionally,
there is no correct understanding with regard to the physical
properties, particle diameter and homogeneity of the
inorganic particles and a pore structure formed by the
inorganic particles. Therefore, such separators according to
the prior art have a problem in that they cause degradation
in the quality of a battery. More particularly, when the
inorganic particles have a relatively large diameter, the
thickness of an organic/inorganic coating layer obtained
under the same solid content increases, resulting in
degradation in mechanical properties. Additionally, in this
case, there is a great possibility of internal short circuit
during charge/discharge cycles of a battery due to an
excessively large pore size. Further, due to the lack of a
binder that serves to fix the inorganic particles on the
substrate, a finally formed film is deteriorated in terms of
mechanical properties, and is not suitable to be applied in a
practical battery assemblage process. For example,
10
WO 2006/068428 PCT/KR2005/004450
conventional separators according to the prior art may not be
amenable to a lamination process.
On the contrary, the present inventors have recognized
that controlling the porosity and pore size of the
organic/inorganic composite porous separator is one of the
factors affecting the quality of a battery. Therefore, we
have varied and optimized the particle diameter of the
inorganic particles or the mixing ratio of the inorganic
particles with the binder polymer. In fact, it was shown by
the following Experimental Examples chat the
organic/inorganic composite porous separator according to the
present invention, which comprises a pore structure formed by
the interstitial volumes among the inorganic particles on the
polyolefin-based separator substrate, has a significantly
higher ion conductivity, as compared to a conventional
composite separator having an artificial pore structure
formed in a polymer film on the polyolefin-based separator
substrate (see FIG. 4). Additionally, according to the
present invention, the binder polymer used in the active
layer can serve sufficiently as a binder so as to
interconnect and stably fix the inorganic particles among
themselves, between the inorganic particles and the surface
of the heat resistant porous substrate, and between the
inorganic particles and a part of the pores in the substrate,
thereby preventing degradation in mechanical properties of a
finally formed organic/inorganic composite porous separator.
(5) The organic/inorganic composite porous separator
according to the present invention can provide excellent
adhesion by controlling the mixing ratio of the components
forming the active layer, i.e. the mixing ratio of the
inorganic particles with the binder polymer. Therefore, it is
possible to facilitate assemblage of a battery.
11
WO 2006/068428 PCT/KR2005/004450
In the organic/inorganic composite porous film
according to the present invention, one component present in
the active layer formed on the surface of the polyolefin-
based separator substrate or on a part of the pores in the
substrate is inorganic particles currently used in the art.
The inorganic particles permit an interstitial volume to be
formed among them, thereby serving no form micropores and to
maintain the physical shape as a spacer. Additionally,
because the inorganic particles are characterized in that
their physical properties are not changed even at a high
temperature of 200 "C or higher, the organic/inorganic
composite porous separator using the inorganic particles can
have excellent heat resistance.
There is no particular limitation in the inorganic
particles, as long as they are electrochemically stable. In
other words, there is no particular limitation in the
inorganic particles that may be used in the present
invention, as long as they are not subjected to oxidation
and/or reduction at the range of drive voltages (for example,
0~5 V based on Li/Li+) of a battery, to which they are
applied. Particularly, it is preferable to use inorganic
particles having ion conductivity as high as possible,
because such inorganic particles can improve ion conductivity
and quality in an electrochemical device. Additionally, when
inorganic particles having a high density are used, they have
a difficulty in dispersion during a coating step and may
increase the weight of a battery to be manufactured.
Therefore, it is preferable to use inorganic particles having
a density as low as possible. Further, when inorganic
particles having a high dielectric constant are used, they
can contribute to increase the dissociation degree of an
electrolyte salt in a liquid electrolyte, such as a lithium
12
WO 2006/068428 PCT/KR2005/004450
salt, thereby improving the ion conductivity of the
electrolyte.
For these reasons, it is preferable to use inorganic
particles having a high dielectric constant of 5 or more,
preferably of 10 or more, inorganic particles having lithium
conductivity, inorganic particles having piezoelectricity, or
mixtures thereof.
In general, a material having piezoelectricity means
one, which is an insulator under normal pressure, but allows
current flow due to the change of its internal structure,
when a certain range of pressure is applied thereto. The
inorganic particles having piezoelectricity show a high
dielectric constant of 100 or more. They are charged
positively on one surface while being charged negatively on
the other surface, when they are drawn or compressed under
the application of a certain range of pressure. Hence, the
inorganic particles having piezoelectricity cause an electric
potential difference between both surfaces thereof.
When the inorganic particles having the above
characteristics are used in the porous active layer, a
cathode and an anode are prevented from being in direct
contact with each other by the inorganic particles coated on
the separator, when an internal short circuit occurs between
both electrodes due to external impacts such as local crush,
a nail, or the like. Additionally, as shown in FIG. 1, such
piezoelectricity of the inorganic particles can permit
generation of a potential difference in the particles,
thereby allowing electron movements, i.e. minute flow of
electric current between both electrodes. Therefore, it is
possible to accomplish a slow decrease in the voltage of a
battery and to improve the safety of a battery (see FIG. 7).
Heretofore, separators coated with conventional inorganic
13
WO 2006/068428 PCT/KR2005/004450
particles could prevent explosion of a battery due to the
inorganic particles, when an internal short circuit occurred
between both electrodes by external impacts. However, in the
case of a battery using such conventional separators, the
battery is present practically in a state of latent danger,
because it is internally damaged but maintains the potential
between both electrodes due to the lack of the
electroconductivity of the inorganic particles. Thus, the
battery may have a possibility of ignition or explosion with
time, or when a secondary impact is applied thereto. In the
organic/inorganic composite porous separator according to the
present invention, the above-mentioned problems can be solved
satisfactorily. Particular non-limiting examples of the
inorganic particles having piezoelectricity include BaTiO3,
Pb(Zr,Ti)O3 (PZT) , Pbi-xLaxZri-yTiyOs (PLZT), PB (Mg3Nb2/3) O3-PbTiO3
(PMN-PT), hafnia (HfO2) , or mixtures thereof.
As used herein, "inorganic particles having lithium ion
conductivity" refer to inorganic particles containing lithium
elements and having a capability of conducting lithium ions
without storing lithium. Inorganic particles having lithium
ion conductivity can conduct and move lithium ions due to
defects present in their structure, and thus can improve
lithium ion conductivity of a battery and contribute to
improve the quality of a battery. Non-limiting examples of
such inorganic particles having lithium ion conductivity
include: lithium phosphate (Li3PO4) , lithium titanium
phosphate (LixTiy (PO4) 3, 0;GeyPzSw, 0
Documents
Orders
| Section |
Controller |
Decision Date |
|
|
|
Application Documents
| # |
Name |
Date |
| 1 |
abstract-02122-kolnp-2007.jpg |
2011-10-07 |
| 1 |
HEARING ADJOURNMENT [17-04-2017(online)].pdf |
2017-04-17 |
| 2 |
2122-kolnp-2007-form 18.pdf |
2011-10-07 |
| 2 |
Form 3 [14-10-2016(online)].pdf |
2016-10-14 |
| 3 |
Other Patent Document [14-10-2016(online)].pdf |
2016-10-14 |
| 3 |
02122-kolnp-2007-priority document.pdf |
2011-10-07 |
| 4 |
2122-KOLNP-2007_EXAMREPORT.pdf |
2016-06-30 |
| 4 |
02122-kolnp-2007-pct request form.pdf |
2011-10-07 |
| 5 |
2122-KOLNP-2007-(11-05-2016)-FORM 6.pdf |
2016-05-11 |
| 5 |
02122-kolnp-2007-international search report.pdf |
2011-10-07 |
| 6 |
2122-KOLNP-2007-(28-02-2014)-CLAIMS.pdf |
2014-02-28 |
| 6 |
02122-kolnp-2007-international publication.pdf |
2011-10-07 |
| 7 |
2122-KOLNP-2007-(28-02-2014)-CORRESPONDENCE.pdf |
2014-02-28 |
| 7 |
02122-kolnp-2007-form 5.pdf |
2011-10-07 |
| 8 |
2122-KOLNP-2007-(28-02-2014)-DRAWINGS.pdf |
2014-02-28 |
| 8 |
02122-kolnp-2007-form 3.pdf |
2011-10-07 |
| 9 |
02122-kolnp-2007-form 1.pdf |
2011-10-07 |
| 9 |
2122-KOLNP-2007-(28-02-2014)-FORM-13.pdf |
2014-02-28 |
| 10 |
02122-kolnp-2007-drawings.pdf |
2011-10-07 |
| 10 |
2122-KOLNP-2007-(28-02-2014)-FORM-2.pdf |
2014-02-28 |
| 11 |
02122-kolnp-2007-description complete.pdf |
2011-10-07 |
| 11 |
2122-KOLNP-2007-(28-02-2014)-OTHERS.pdf |
2014-02-28 |
| 12 |
02122-kolnp-2007-correspondence others.pdf |
2011-10-07 |
| 12 |
2122-KOLNP-2007-(28-02-2014)-PA.pdf |
2014-02-28 |
| 13 |
02122-kolnp-2007-correspondence others 1.1.pdf |
2011-10-07 |
| 13 |
2122-KOLNP-2007-1-(28-02-2014)-CORRESPONDENCE.pdf |
2014-02-28 |
| 14 |
02122-kolnp-2007-claims.pdf |
2011-10-07 |
| 14 |
2122-KOLNP-2007-1-(28-02-2014)-OTHERS.pdf |
2014-02-28 |
| 15 |
02122-kolnp-2007-abstract.pdf |
2011-10-07 |
| 15 |
02122-kolnp-2007-assignment.pdf |
2011-10-07 |
| 16 |
02122-kolnp-2007-abstract.pdf |
2011-10-07 |
| 16 |
02122-kolnp-2007-assignment.pdf |
2011-10-07 |
| 17 |
2122-KOLNP-2007-1-(28-02-2014)-OTHERS.pdf |
2014-02-28 |
| 17 |
02122-kolnp-2007-claims.pdf |
2011-10-07 |
| 18 |
02122-kolnp-2007-correspondence others 1.1.pdf |
2011-10-07 |
| 18 |
2122-KOLNP-2007-1-(28-02-2014)-CORRESPONDENCE.pdf |
2014-02-28 |
| 19 |
02122-kolnp-2007-correspondence others.pdf |
2011-10-07 |
| 19 |
2122-KOLNP-2007-(28-02-2014)-PA.pdf |
2014-02-28 |
| 20 |
02122-kolnp-2007-description complete.pdf |
2011-10-07 |
| 20 |
2122-KOLNP-2007-(28-02-2014)-OTHERS.pdf |
2014-02-28 |
| 21 |
02122-kolnp-2007-drawings.pdf |
2011-10-07 |
| 21 |
2122-KOLNP-2007-(28-02-2014)-FORM-2.pdf |
2014-02-28 |
| 22 |
02122-kolnp-2007-form 1.pdf |
2011-10-07 |
| 22 |
2122-KOLNP-2007-(28-02-2014)-FORM-13.pdf |
2014-02-28 |
| 23 |
02122-kolnp-2007-form 3.pdf |
2011-10-07 |
| 23 |
2122-KOLNP-2007-(28-02-2014)-DRAWINGS.pdf |
2014-02-28 |
| 24 |
2122-KOLNP-2007-(28-02-2014)-CORRESPONDENCE.pdf |
2014-02-28 |
| 24 |
02122-kolnp-2007-form 5.pdf |
2011-10-07 |
| 25 |
2122-KOLNP-2007-(28-02-2014)-CLAIMS.pdf |
2014-02-28 |
| 25 |
02122-kolnp-2007-international publication.pdf |
2011-10-07 |
| 26 |
2122-KOLNP-2007-(11-05-2016)-FORM 6.pdf |
2016-05-11 |
| 26 |
02122-kolnp-2007-international search report.pdf |
2011-10-07 |
| 27 |
2122-KOLNP-2007_EXAMREPORT.pdf |
2016-06-30 |
| 27 |
02122-kolnp-2007-pct request form.pdf |
2011-10-07 |
| 28 |
Other Patent Document [14-10-2016(online)].pdf |
2016-10-14 |
| 28 |
02122-kolnp-2007-priority document.pdf |
2011-10-07 |
| 29 |
Form 3 [14-10-2016(online)].pdf |
2016-10-14 |
| 29 |
2122-kolnp-2007-form 18.pdf |
2011-10-07 |
| 30 |
HEARING ADJOURNMENT [17-04-2017(online)].pdf |
2017-04-17 |
| 30 |
abstract-02122-kolnp-2007.jpg |
2011-10-07 |