U.S. patent application number 13/529679 was filed with the patent office on 2012-10-18 for method for manufacturing metal electrode having transition metallic coating layer and metal electrode manufactured thereby.
This patent application is currently assigned to Samsung Electro-Mechanics Co., Ltd.. Invention is credited to Jun-Hee Bae, Hyun-Chul Jung, Hak-Kwan KIM, Seung-Hyun Ra.
Application Number | 20120262844 13/529679 |
Document ID | / |
Family ID | 42730959 |
Filed Date | 2012-10-18 |
United States Patent
Application |
20120262844 |
Kind Code |
A1 |
KIM; Hak-Kwan ; et
al. |
October 18, 2012 |
METHOD FOR MANUFACTURING METAL ELECTRODE HAVING TRANSITION METALLIC
COATING LAYER AND METAL ELECTRODE MANUFACTURED THEREBY
Abstract
It is to provide a method for manufacturing a metal electrode
having transition metal oxide coating layer and a metal electrode
manufactured thereby, which eliminates a contact resistance problem
and simultaneously improves electric conductivity of the electrode
by using a one body electrode, which is not requiring separate
current collector and binder, and further maintains
pseudo-capacitance from the redox reaction by coating the metal
surface with a transition metal oxide.
Inventors: |
KIM; Hak-Kwan; (Hanam-si,
KR) ; Ra; Seung-Hyun; (Seongnam-si, KR) ; Bae;
Jun-Hee; (Suwon-si, KR) ; Jung; Hyun-Chul;
(Yongin-si, KR) |
Assignee: |
Samsung Electro-Mechanics Co.,
Ltd.
Gyunggi-do
KR
|
Family ID: |
42730959 |
Appl. No.: |
13/529679 |
Filed: |
June 21, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12511806 |
Jul 29, 2009 |
8226808 |
|
|
13529679 |
|
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|
|
Current U.S.
Class: |
361/502 ;
174/126.2; 205/122; 977/762; 977/890; 977/948 |
Current CPC
Class: |
Y02E 60/13 20130101;
H01G 11/28 20130101; H01L 29/41 20130101; H01L 28/65 20130101; H01G
11/02 20130101; B82Y 10/00 20130101; H01G 11/86 20130101; H01G
11/46 20130101; H01G 11/26 20130101 |
Class at
Publication: |
361/502 ;
174/126.2; 205/122; 977/762; 977/890; 977/948 |
International
Class: |
H01B 5/00 20060101
H01B005/00; H01G 9/058 20060101 H01G009/058; C23C 28/00 20060101
C23C028/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 10, 2009 |
KR |
10-2009-0020314 |
Claims
1-4. (canceled)
5. A metal electrode having a transition metal oxide coating layer
manufactured according to a method for manufacturing a metal
electrode having a transition metal oxide coating layer comprising:
preparing an anode aluminum oxide template or polymer casting mold
having more than two micropores; forming a metal substrate by
sputtering a first metal at one side where the opening parts of the
micropores of the aluminum template or the polymer casting mold
are; forming more than two metal nanowire arrays by filling a
second metal into the micropores of the aluminum template or the
polymer casting mold by using an electroplating method; exposing
the metal nanowire arrays arranged perpendicularly on the metal
substrate by removing the aluminum template or the polymer casting
mold; and coating the side where the metal nanowire arrays are
arranged on the metal substrate and the side where the metal
nanowire arrays are exposed with a transition metal oxide by an
immersion method.
6. A metal electrode comprising: a metal substrate composed of a
first metal; more than two metal nanowire arrays arranged
perpendicularly on the metal substrate and composed of a second
metal; and a transition metal oxide coating layer coated on the
side where the metal nanowire arrays are arranged on the metal
substrate and the side where the metal nanowire arrays are
exposed.
7. The metal electrode of claim 6, wherein the first metal and the
second metal are identical.
8. The metal electrode of claim 6, wherein the first metal and the
second metal are independently selected from the group consisting
of Cu, Ag, Au, Ni, Cr, Sn, Cd, Pb, Rd, Pt, Pd, In, Ru, Mn, Zn, Co
and an alloy thereof.
9. The metal electrode of claim 6, wherein the transition metal
oxide oxide is selected from the group consisting of MnO.sub.2,
RuO.sub.2, CoO and NiO.
10. A supercapacitor comprising the metal electrode of claim 5.
11. A supercapacitor comprising the metal electrode of claim 6.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Divisional of U.S. application Ser.
No. 12/511,806 filed on Jul. 29, 2009, which claims the benefit of
Korean Patent Application No. 10-2009-0020314 filed with the Korean
Intellectual Property Office on Mar. 10, 2009, the disclosures of
which are incorporated herein by reference.
BACKGROUND
[0002] 1. Technical Field
[0003] It relates to a method for manufacturing a metal electrode
having a transition metal oxide coating layer and a metal electrode
manufactured thereby.
[0004] 2. Description of the Related Art
[0005] Higher value-added businesses which collect and use various
and useful information in real time by employing IT equipments
receive attentions and stable energy supply for securing
reliability of such systems becomes an important factor in the
information-oriented society. These IT equipments and electrical
devices include electric circuit boards and each circuit board has
a capacitor which stores an electric charge and releases it when
required and thus stabilizes energy flow in the circuit. This
capacitor has a very short charge/discharge time, a long lifetime
and a high power density but generally a very low energy density.
This disadvantage of low energy density causes many limitations on
its use as an energy storage device.
[0006] However, electrochemical capacitors, supercapacitors or
ultracapacitors, which have started to be commercialized in Japan,
Russia, USA, etc. since 1995, are under development in all
countries of the world to provide higher energy density as next
generation energy storage devices along with secondary
batteries.
[0007] A supercapacitor can be broadly classified into 3 categories
depending on the electrode and the mechanism: (1) an electric
double layer capacitor(EDLC) which employs activated carbon as an
electrode and is based on an electric double layer electric charge
absorption mechanism; (2) a metal oxide electrode
pseudocapacitor(or redox capacitor) which employs a transition
metal oxide and a conductive polymer as an electrode material and
is based on a pseudo-capacitance mechanism; and (3) a hybrid
capacitor which combines the features of both electrochemical and
electrolytic capacitors. Among them, the EDLC-type supercapacitor
using activated carbons is currently used the most.
[0008] The supercapacitor is composed of an electrode, an
electrolyte, a current collector, and a separator and is based on
the electrochemical mechanism which stores energy through
absorption of electrolyte ions on the electrode surface by
migrating along with the electric field when voltages are applied
on the both ends of a unit cell electrode. Since the specific
capacitance is proportional to the specific surface area, the
supercapacitor improves energy(storage) density through the use of
an activated carbon electrode, which is a porous material. An
electrode is manufactured by preparing slurry including a carbon
electrode material, a carbon conductive material and a polymer
binder and coating the slurry on a current collector. Here, it is
important to improve adhesiveness to the current collector and
reduce contact resistance at the same time and further lower
internal contact resistance between activated carbons by changing a
ratio or kind of the binder, the conductive material and the
electrode material.
[0009] When a pseudocapacitor using a metal oxide electrode
material is used, the transition metal oxide exhibits higher
capacity and higher power density compared to activated carbons.
Recently, it has been reported that amorphous hydrate electrodes
exhibit much higher specific capacitance.
[0010] Since the electric capacitance is proportional to the
specific surface area, it is needed to use an electrode material
having high specific surface which is the most essential factor to
improve a capacitance of a supercapacitor. In addition, it is
needed to have high conductivity, electrochemical inactivity, easy
forming and processability and the like. Carbon materials which
satisfy such properties have been widely used the most. Examples of
such porous carbon materials may include activated carbon,
activated carbon fiber, amorphous carbon, carbon aerogel or carbon
carbon composite, carbon nanotube and the like. However, even
though such activated carbons have high specific surface area,
effective pores of the activated carbon are only about 20% because
most pores are micropores of which diameter is about 20 nm or less
and which cannot do much for an electrode role. Since the electrode
is prepared from slurry which is formed by mixing a binder, a
carbon conducting material and a solvent, etc. an actual effective
contact area between an electrode and an electrolyte is decreased.
There are further drawbacks such as uneven electric capacitance and
contact resistance between an electrode and a current
collector.
[0011] KR patent application no. 2003-0099761 discloses a method
for manufacturing an electrode for supercapacitors by using a metal
oxide, instead of using a binder, to increase effective contact
area but it still has drawbacks such as low conductivity, contact
resistance and high manufacturing cost, etc.
SUMMARY
[0012] It is to provide a method for manufacturing a metal
electrode for supercapacitors having a transition metal oxide
coating layer on the surface and optimizing surface area in which
the metal electrode is one body electrode since a current collector
and a binder are not separately used, and a metal electrode
manufactured thereby.
[0013] There is an aspect to provide a method for manufacturing a
metal electrode having a transition metal oxide coating layer
including: preparing an anode aluminum oxide template or polymer
casting mold having more than two micropores; forming a metal
substrate by sputtering a first metal at one side where the opening
parts of the micropores of the aluminum template or the polymer
casting mold are; forming more than two metal nanowire arrays by
filling a second metal into the micropores of the aluminum template
or the polymer casting mold by using an electroplating method;
exposing the metal nanowire arrays arranged perpendicularly on the
metal substrate by removing the aluminum template or the polymer
casting mold; and coating the side, where the metal nanowire arrays
are perpendicularly arranged on the metal substrate, and the side,
where the metal nanowire arrays are exposed, with a transition
metal oxide by an immersion method.
[0014] According to an embodiment, the the first metal and the
second metal may be identical.
[0015] According to an embodiment, the first metal and the second
metal may be independently chosen from Cu, Ag, Au, Ni, Cr, Sn, Cd,
Pb, Rd, Pt, Pd, In, Ru, Mn, Zn, Co and an alloy thereof.
[0016] According to an embodiment, the transition metal oxide may
be chosen from MnO.sub.2, RuO.sub.2, CoO and NiO.
[0017] There is another aspect to provide a metal electrode having
a transition metal oxide coating layer manufactured by the method
described above.
[0018] There is still another aspect to provide a metal electrode
including: a metal substrate composed of a first metal; more than
two metal nanowire arrays arranged perpendicularly on the metal
substrate and composed of a second metal; and a transition metal
oxide coating layer coated on the side where the metal nanowire
arrays are arranged on the metal substrate and the side where the
metal nanowire arrays are exposed.
[0019] According to an embodiment, the the first metal and the
second metal may be identical. When they are identical, a one body
metal electrode may be obtained.
[0020] According to an embodiment, the first metal and the second
metal may be independently chosen from Cu, Ag, Au, Ni, Cr, Sn, Cd,
Pb, Rd, Pt, Pd, In, Ru, Mn, Zn, Co and an alloy thereof.
[0021] According to an embodiment, the transition metal oxide may
be chosen from MnO.sub.2, RuO.sub.2, CoO and NiO.
[0022] There is still another aspect to provide a supercapacitor
including the metal electrode described above.
[0023] According to an embodiment, the metal electrode,
manufactured by the above described method, eliminates a contact
resistance problem and simultaneously improves electric
conductivity of the electrode by using a one body electrode, which
is not requiring separate current collector and binder, and further
maintains pseudo-capacitance from the redox reaction by coating the
metal surface with a transition metal oxide. In addition, the metal
electrode may have superior power density, which has a high effect
on supercapacitor's characteristics, to conventional ones since a
metal itself is used as an electrode and thus the electric
conductivity of the metal has 10.sup.9 times better than that of
the metal oxide.
Further, the surface area of the electrode may be optimized by
forming more than two metal nanowire arrays with using an anode
aluminum oxide template or polymer casting mold. Here, diameters of
the metal nanowire arrays may be controlled by controlling
diameters of micropores of the anode aluminum oxide template or
polymer casting mold. Lengthes of the metal nanowire arrays may be
also controlled by controlling electrochemical parameters such as
supplied current density and suppling time, etc. during the
electroplating process.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 illustrates a method for manufacturing a metal
electrode according to an embodiment.
[0025] FIG. 2 is an enlarged sectional view of a part of an metal
electrode manufactured by an embodiment.
DETAILED DESCRIPTION
[0026] Hereinafter, a metal electrode having a transition metal
oxide coating layer according to an embodiment and a manufacturing
method thereof will be described in more detail.
[0027] As illustrated in FIG. 1, a method for manufacturing a metal
electrode having a transition metal oxide coating layer according
to an embodiment may include (a) preparing an anode aluminum oxide
template or polymer casting mold 10 having more than two
micropores; (b) forming a metal substrate 20 by sputtering a first
metal at one side where the opening parts of the micropores of the
aluminum template or the polymer casting mold are; (c) forming more
than two metal nanowire arrays 30 by filling a second metal into
the micropores of the aluminum template or the polymer casting mold
by using an electroplating method; (d) exposing the metal nanowire
arrays arranged perpendicularly on the metal substrate by removing
the aluminum template or the polymer casting mold; and (e) coating
40 the side, where the metal nanowire arrays are arranged on the
metal substrate, and the side, where the metal nanowire arrays are
exposed, with a transition metal oxide by an immersion method.
[0028] In step (a), the anode aluminum oxide template (AAO) or
polymer casting mold, formed with more than two micropores having
several tens to several hundreds nanometer of a diameter, is
prepared.
[0029] Manufacturing the anode aluminum oxide template (AAO) or
polymer casting mold formed with more than two micropores and
controlling size of micropores may be carried by any method
well-known in this field and thus detail description is omitted.
The casting mold may have 20 nm to 200 nm of a diameter.
[0030] In step (b), the metal substrate may be formed by sputtering
a first metal on one side where the opening parts of the micropores
of the casting mold are.
[0031] The first metal may be chosen from Cu, Ag, Au, Ni, Cr, Sn,
Cd, Pb, Rd, Pt, Pd, In, Ru, Mn, Zn, Co and an alloy thereof. The
first metal may be formed as a metal layer to function as a
substrate so that it is able to arrange more than two metal
nanowire arrays perpendicularly. This metal substrate may function
as a current collector at the same time by connecting the more than
two metal nanowire arrays.
[0032] In step (c), the more than two metal nanowire arrays 30 may
be formed by filling a second metal into the micropores of the
casting mold by using an electroplating method.
[0033] The second metal may be chosen from Cu, Ag, Au, Ni, Cr, Sn,
Cd, Pb, Rd, Pt, Pd, In, Ru, Mn, Zn, Co and an alloy thereof. The
first and second metal may be identical. When the electroplating is
carried by placing the casting mold to an electroplating solution,
the second metal is filled into the micropores through the opening
parts of those micropores of the casting mold and thus the metal
nanowire array can be formed.
[0034] In step (d), the metal metal nanowire arrays arranged
perpendicularly may be exposed on the metal substrate by removing
the aluminum or polymer casting mold.
[0035] The aluminum or polymer casting mold may be removed by an
etching treatment in an etching solution which is able to dissolve
the casting mold.
[0036] In step (e), the transition metal oxide coating layer may be
formed by coating the side where the metal nanowire arrays are
arranged perpendicularly on the metal substrate and the side where
the metal nanowire arrays are exposed by the immersion method.
[0037] The transition metal oxide may be chosen from MnO.sub.2,
RuO.sub.2, CoO, NiO and the like.
[0038] A metal electrode manufactured by the method for
manufacturing a metal electrode having a transition metal oxide
coating layer according to an embodiment may include: a metal
substrate composed of a first metal; more than two metal nanowire
arrays arranged perpendicularly on the metal substrate and composed
of a second metal; and a transition metal oxide coating layer
coated on the side where the metal nanowire arrays are arranged on
the metal substrate and the side where the metal nanowire arrays
are exposed.
[0039] The metal electrode may be suitable for supercapacitors by
being used as an anode, a cathode, or both electrodes. A
supercapacitor according to an embodiment may optimize an effective
contact area between an electrolyte and an active material to
increase capacitance and improve a rate for charge/discharge
process of a capacitor due to easy ion diffusion. It also
eliminates a contact resistance since a current collector and an
electrode is a single body.
[0040] Hereinafter, although more detailed descriptions will be
given by examples, those are only for explanation and there is no
intention to limit the invention.
EXAMPLE
[0041] 1) An anode aluminum oxide template(AAO template) having
more than two micropores with 20-200 nm of a diameter was
prepared.
[0042] 2) A copper substrate having 1-50 .mu.m of thickness was
formed on one side where the opening parts of the micropores of the
template are by using a sputtering apparatus.
[0043] 3) The anode aluminum oxide template having the copper
substrate formed on one side and the opening parts of the
micropores on the one side was performed for the electroplating by
placing into a copper electroplating solution and supplying current
to fill copper into the micropores.
[0044] 4) The template formed with the copper nanowire array was
immersed into a 0.1 M to 5 M NaOH solution for 10 minutes to 1 hour
to remove the aluminum mold and dried to expose the copper nanowire
array.
[0045] 5) The side, where the copper nanowire arrays arranged
perpendicularly on the copper substrate were exposed, was coated
with MnO.sub.2 by the immersion method to form a transition metal
oxide coating layer. An electrode having the transition metal oxide
coating layer was manufactured as in FIG. 2.
[0046] While it has been described with reference to particular
embodiments, it is to be appreciated that various changes and
modifications may be made by those skilled in the art without
departing from the spirit and scope of the embodiment herein, as
defined by the appended claims and their equivalents.
* * * * *