KR101658351B1 - Super capacitor electrode material and preparing method thereof - Google Patents
Super capacitor electrode material and preparing method thereof Download PDFInfo
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- KR101658351B1 KR101658351B1 KR1020150050236A KR20150050236A KR101658351B1 KR 101658351 B1 KR101658351 B1 KR 101658351B1 KR 1020150050236 A KR1020150050236 A KR 1020150050236A KR 20150050236 A KR20150050236 A KR 20150050236A KR 101658351 B1 KR101658351 B1 KR 101658351B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
A method for producing a nanocomposite for a supercapacitor electrode material comprising a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite, and a method for fabricating a nanocomposite comprising the metal oxide nanosheet-layered double hydroxide- graphene nanosheet composite Lt; / RTI >
Description
The present invention is directed to a method of making a nanocomposite for a super capacitor electrode material comprising a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite, and a method of fabricating the nanocomposite comprising the metal oxide nanosheet-layered double hydroxide- To a super capacitor electrode material.
Electrochemical capacitors are devices that store electrical energy by forming an electrical double layer between the surface of the electrode and the electrolyte. In this case, electricity is not generated by a chemical action like a battery, but because it is made by an electric double layer, it does not damage the electrode itself, and its lifetime is almost infinite. In addition, since the charging and discharging time is not long, a large amount of current can be stored in a short time. This device is therefore an important electrical storage material when high power is needed. Supercapacitors can be classified as electrical double layer capacitors (EDLC) and pseudo capacitors depending on the mechanism of energy storage. In particular, pseudo-capacitors can exhibit larger non-recoatable capacities using additional oxidation-reduction reactions. The layered double hydroxide [(M 1 -x 2+ M x 3 + (OH) 2 ) (A x / n n - ) · mH 2 O] (layered double hydroxide, LDH) Have been of interest for their reactivity and non-reactivity. However, the low electrical conductivity of the LDH hinders electron transfer, which makes it impossible to charge and discharge quickly. Therefore, compound formation with graphene, which has high electrical conductivity and wide specific surface area, is expected to improve the electrochemical activity of LDH.
Korean Patent No. 10-1371288 discloses a method for producing a manganese oxide / graphene nanocomposite comprising synthesizing a manganese oxide / graphene nanocomposite through a liquid phase reaction at a room temperature, a method for producing a manganese oxide / A graphene nanocomposite, an electrode material containing the graphene nanocomposite, and an electrode for a supercapacitor.
The present invention is directed to a method of making a nanocomposite for a super capacitor electrode material comprising a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite, and a method of fabricating the nanocomposite comprising the metal oxide nanosheet-layered double hydroxide- Thereby providing a supercapacitor electrode material.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
According to a first aspect of the present invention, there is provided a method for producing a mixed colloid solution, comprising: mixing a graphene oxide nanosheet colloid and a metal oxide nanosheet colloid to prepare a mixed colloidal solution; And a step of synthesizing a layered double hydroxide in the mixed colloid solution and then reducing the graphene oxide to obtain a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite. And a manufacturing method thereof.
The second aspect of the present invention provides a supercapacitor electrode material comprising a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite, produced according to the manufacturing method according to one aspect of the present invention.
According to any one of the above-mentioned means for solving the problems, since the graphene nanosheet has a negative charge, it can easily form a compound with a layered double hydroxide (LDH) having a positive charge, and not only provides a support on which LDH can grow crystal It can reinforce low conductivity, which is a disadvantage of LDH. In addition, the metal oxide nanosheets in addition to graphene can additionally provide a support on which LDH can be formed, and can easily form a compound with LDH since it has a negative charge. When used as a supercapacitor electrode material, the oxidation- The non-discharge capacity can be improved.
According to any one of the above-mentioned means for solving the problems, by using the rigid nature of the metal oxide nanosheet, hybridization with the graphene nanosheet forms an appropriate size hole size capable of penetrating ions of the electrolyte, Can be increased.
1 shows an X-ray diffraction (XRD) pattern of a CoAl-LDH / RGO / MnO 2 composite synthesized with different contents of graphene nanosheets and MnO 2 nanosheets in one embodiment of the present invention.
Of Figure 2 a and b are, in one embodiment of the present application, CoAl-LDH / RGO / MnO 2 (TEM) image of the composite, and FIG. 2C is a fast Fourier transform (FFT) image obtained by filtering the TEM image in one embodiment of the present invention.
Figure 3a, in one embodiment of the present application, a scanning electron microscope (SEM) image of a CoAl-LDH / RGO / MnO 2 complex.
Figure 3b, according to one embodiment of the invention, the element mapping (mapping) image of a CoAl-LDH / RGO / MnO 2 complex.
Figure 4 shows the Raman spectrum of a CoAl-LDH / RGO / MnO 2 complex in one embodiment of the invention.
FIG. 5 is a graph showing the Mn K-edge absorption near-edge structure (XANES) of a CoAl-LDH / RGO / MnO 2 complex in one embodiment of the present invention.
FIG. 6 is a BET (specific surface area) graph of a CoAl-LDH / RGO / MnO 2 complex in one embodiment of the present invention.
7 is a cyclic current and voltage graph of a CoAl-LDH / RGO / MnO 2 complex in one embodiment of the present invention.
8 is a graph of cycle stability of a CoAl-LDH / RGO / MnO 2 complex in one embodiment of the present invention.
Figure 9 is, in one embodiment of the present application, a graph of the resistance CoAl-LDH / RGO / MnO 2 complex.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.
Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.
Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.
Throughout this specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without departing from the other elements unless specifically stated otherwise.
The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.
The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.
Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.
Throughout this specification, the description of "A and / or B" means "A or B, or A and B".
Throughout this specification, the term "graphene " means that a plurality of carbon atoms are linked together by a covalent bond to form a polycyclic aromatic molecule, wherein the carbon atoms linked by the covalent bond are 6-membered rings A 5-membered ring, and / or a 7-membered ring. Thus, the sheet formed by the graphene may be viewed as a single layer of carbon atoms covalently bonded to each other, but may not be limited thereto. The sheet formed by the graphene may have various structures, and the structure may vary depending on the content of the 5-membered ring and / or the 7-membered ring which may be contained in the graphene. When the sheet formed by the graphene is a single layer, they may be laminated to form a plurality of layers, and the side end portion of the graphene sheet may be saturated with hydrogen atoms, but the present invention is not limited thereto.
Throughout the specification, the term "graphene oxide" is also referred to as graphene oxide and may be abbreviated as "GO ". But it may include, but is not limited to, a structure in which a functional group containing oxygen such as a carboxyl group, a hydroxyl group, or an epoxy group is bonded on a single layer graphene.
Hereinafter, embodiments of the present invention are described in detail, but the present invention is not limited thereto.
According to a first aspect of the present invention, there is provided a method for producing a mixed colloid solution, comprising: mixing a graphene oxide nanosheet colloid and a metal oxide nanosheet colloid to prepare a mixed colloidal solution; And a step of synthesizing a layered double hydroxide in the mixed colloid solution and then reducing the graphene oxide to obtain a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite. And a manufacturing method thereof.
In one embodiment of the present invention, the graphene nanosheet has a negative charge, so that it can easily form a compound with an LDH (layered double hydroxide) having a positive charge, and can provide a support on which LDH can grow crystal, The low conductivity, which is a disadvantage, can be reinforced.
In one embodiment of the present invention, the metal oxide nanosheet can additionally provide a support on which LDH can be formed together with the graphene, and can easily form a compound with LDH since it has a negative charge.
In one embodiment of the present invention, when the nanocomposite for supercapacitor electrode material is used as a supercapacitor electrode material, the non-discharge capacity can be improved through oxidation-reduction reaction.
In one embodiment of the present invention, the metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite refers to a composite of a metal oxide nanosheet, a layered double hydroxide, and a graphene nanosheet, Layered double hydroxides, and graphene nanosheets may be hybridized to form nanoscale composites, but are not limited thereto.
In one embodiment of the invention, the metal oxide nanosheet may be a metal oxide nanosheet comprising a material selected from the group consisting of MnO 2 , TiO 2 , Ru oxide, Rh oxide, and combinations thereof. But may not be limited.
In one embodiment of the present invention, the metal oxide nanosheets and the graphene nanosheets may be, but not limited to, those which act as a support in the synthesis of the layered double hydroxides, respectively.
In one embodiment of the present invention, the layered double hydroxide may comprise, but is not limited to, a metal layered double hydroxide represented by the following general formula 1:
[Formula 1]
[M II (1-x) M III x (OH) 2 ] [A n- ] x / n .zH 2 O;
In the
In one embodiment of the present invention, the metal layered double hydroxide has a layered structure including +2 valence and +3 valence metal ions, wherein +2 is substituted with a +3 valence ion, Is positively charged. Therefore, the negative ions (A n- ) are stabilized in the spaces between the layers in order to maintain the charge of the whole material as neutral. Such a layered metal double hydroxide is generally prepared by a precipitation reaction in an aqueous solution or a precipitation-ion exchange reaction.
In one embodiment of the invention, wherein the M II is in the Ca 2 +, Mg 2 +,
In one embodiment of the present invention, the manufacturing method may include, but is not limited to, a step of centrifuging and washing after reducing the graphene oxide.
In one embodiment of the present invention, the manufacturing method may include, but is not limited to, a step of drying after the washing step.
In one embodiment of the present invention, the temperature of the mixed colloidal solution may be about 100 ° C or less, but the present invention is not limited thereto. For example, the production temperature of the mixed colloidal solution may be from about 0 캜 to about 100 캜, from about 10 캜 to about 100 캜, from about 30 캜 to about 100 캜, from about 50 캜 to about 100 캜, From about 0 캜 to about 30 캜, from about 0 캜 to about 10 캜, from about 0 캜 to about 90 캜, from about 0 캜 to about 70 캜, from about 0 캜 to about 50 캜, Or from about 10 < 0 > C to about 40 < 0 > C.
In one embodiment of the present invention, the metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite may include, but not limited to, CO 3 2 - ions or molecules of water between layers.
The second aspect of the present invention provides a supercapacitor electrode material comprising a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite prepared according to the manufacturing method according to the first aspect of the present invention.
In one embodiment of the invention, the metal oxide nanosheet may be a metal oxide nanosheet comprising a material selected from the group consisting of MnO 2 , TiO 2 , Ru oxide, Rh oxide, and combinations thereof. But may not be limited.
In one embodiment of the present invention, the metal oxide nanosheets and the graphene nanosheets may be, but not limited to, those which act as a support in the synthesis of the layered double hydroxides, respectively.
In one embodiment of the present invention, the layered double hydroxide may comprise, but is not limited to, a metal layered double hydroxide represented by the following general formula 1:
[Formula 1]
[M II (1-x) M III x (OH) 2 ] [A n- ] x / n .zH 2 O;
In the
In one embodiment of the invention, the M II is selected from the group consisting of Ca 2+ , Mg 2+ , Zn 2+ , Ni 2+ , Mn 2+ , Co 2+ , Fe 2+ , Cu 2+ , comprises a metal cation selected from the group consisting of, wherein M III is comprised of a Fe 3 +, Al 3 +, Cr 3 +, Mn 3 +, Ga 3 +, Co 3 +, Ni 3 +, and combinations thereof But are not limited to, metal cations selected from the group consisting of:
In one embodiment of the present invention, the non-conducting capacity of the supercapacitor electrode material may be about 700 F / g or more, but the present invention is not limited thereto. For example, the non-conducting capacity of the supercapacitor electrode material can be at least about 700 F / g, at least about 800 F / g, at least about 900 F / g, at least about 1000 F / g, at least about 1,100 F / But may be, but not limited to, greater than or equal to 1,200 F / g.
In one embodiment of the present invention, the increase in the non-electrochemical capacity may be based on an oxidation-reduction reaction, but the present invention is not limited thereto. For example, the oxidation-reduction reaction may be an oxidation-reduction reaction of Co (II) / Co (III) in the oxidation-reduction reaction of M II contained in the layered double hydroxide (LDH) .
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following Examples.
[ Example ]
< Example One: Grapina Oxide (GO) Nanosheet Synthesis >
The GO was synthesized from graphite using the Hummer's method. 2 g of graphite was added to 46 mL of sulfuric acid, and 6 g of KMnO 4 was added while stirring at 20 캜 or lower. After the reaction was allowed to proceed at 35 DEG C for 2 hours, an excess of distilled water was slowly added to the mixture, followed by reaction for 15 minutes. After that, 280 mL of distilled water and 5 mL of 30% H 2 O 2 were slowly added to the reaction mixture, and the color of the mixture turned to light brown. The mixture was settled by centrifugation, washed with 500 mL of 1:10 HCl (v / v%) and dried for 2 to 3 days. Finally, the dried mixture was dispersed in water at a concentration of 0.05 wt% to prepare a GO colloid.
< Example 2: MnO 2 Synthesis of nanosheet>
K 2 CO 3 (3 g) and Mn 2 O 3 (7 g) were finely pulverized together and then K 0 .45 MnO 2 was synthesized by reacting with oxygen gas at 800 ° C. for 30 hours. H 0 .13 MnO 2 · 0.7H 2 O was prepared by reacting for 10 days using a 100 mL of
< Example 3: CoAl - LDH / RGO / MnO 2 Synthesis>
250 mL of tertiary distilled water was mixed with 10 mM CoCl 2 .6H 2 O, 5 mM AlCl 2 .6H 2 O, and 45 mM urea. At this time, while refluxing while flowing nitrogen gas, all the obtained powder was dissolved, and then GO colloid and MnO 2 colloid were added at the same time, and the mixture was heated to 97 ° C and reacted for 24 hours. At this time, the GO was reduced to RGO (reduced graphene oxide) by urea. The obtained product was centrifuged at 6,000 rpm and washed with tertiary distilled water and ethanol. Finally, the product was dried in an oven at 30 < 0 > C.
The CoAl-LDH / RGO / MnO 2 sample obtained in this example was named as shown in Table 1 according to the mass ratio of GO and MnO 2 added. For example, CAGM0 sample shall contain a content of RGO of CoAl-LDH and 7.7% by weight, CAGM2 sample and containing MnO 2 content of RGO, and 0.2% by weight of CoAl-LDH, 7.5% by weight, CAGM5 sample CoAl-LDH, 7.2 wt% RGO, and 0.5 wt% MnO 2 , and finally the
1 is an X-ray diffraction (XRD) pattern of a CoAl-LDH / RGO / MnO 2 nanocomposite synthesized with different graphene nanosheets and MnO 2 nanosheets contents ((i) CoAl- ) RGO, (iii) CAGMO, (iv) CAGM2, (v) CAGM5, and (vi) CAGM10. The X-ray diffraction (XRD) pattern of FIG. 1 is very sharp, indicating that the crystallinity of the synthesized LDH is remarkably excellent. The intensity of the (003) and (006) diffraction peaks is particularly strong, indicating that the LDH crystals have grown only on a particular axis. In addition, the interlayer distance (d003) was 0.759 nm, indicating that CO 3 2 - ions and water molecules were intercalated between the layers. On the other hand, no peak indicating RGO and MnO 2 is observed, indicating that the graphene nanosheet and the MnO 2 nanosheet are not re-aggregated and are well preserved.
2 (a) and 2 (b) are transmission electron microscope (TEM) images of a CoAl-LDH / RGO / MnO 2 composite CAGM10 and FIG. 2 c is a fast Fourier transform to be. The red line, the blue line and the green line in Figs. 2 (a) and 2 (c) show MnO 2 nanosheets, CoAl-LDH and RGO, respectively. 2B is an enlarged image of the black square portion of FIG. 2A. 2, LDH, graphene nanosheets, and MnO 2 nanosheets were well hybridized. It was confirmed that CoAl-LDH, RGO, and MnO 2 nanosheets exist together through the FFT image of FIG. 2 (c).
Figure 3a, CoAl-LDH / and RGO / MnO scanning electron microscope (SEM) image of the second conjugate, Figure 3b, CoAl-LDH / RGO /
4, CoAl-LDH / RGO / MnO 2 (I) CAGMO, (ii) CAGM2, (iii) CAGM5, (iv) CAGM10, (v) GO, (vi) RGO, and (vii) CoAl-LDH. From the graph of FIG. 4, it can be seen that GO is well reduced to RGO. In addition, the peak corresponding to LDH in the synthesized CoAl-LDH / RGO / MnO 2 can not be confirmed, indicating that LDH and graphene are strongly bound to each other.
FIG. 5 is a graph showing the X-ray absorption near-edge structure (XANES) of the CoAl-LDH / RGO / MnO 2 composite CAGM10. K 0 .45 MnO 2 , (iii) Mn 2 O 3 , and (iv) β-MnO 2 . K 0 .45 MnO 2 , it was found that the conventional structure was well maintained. It was also found that trivalent and tetravalent Mn had an oxidized state in which Mn was appropriately mixed through the position of peak B.
FIG. 6 is a BET (specific surface area) graph of a CoAl-LDH / RGO / MnO 2 composite. ((I) CoAl- LDH, (ii) RGO, (iii) CAGM0, (iv) CAGM2, vi) CAGM10]. CoAl-LDH was 14 m 2 / g,
7 is a cyclic current and voltage graph of a CoAl-LDH / RGO / MnO 2 composite. The peak at 0.15 V and 0.28 V to 0.3 V is the peak due to the oxidation-reduction reaction of Co (II) / Co (III). The area of the graph indicates that the CAGM5 compound has a larger non-reactive capacity than the CoAl-LDH / RGO (CAGMO) compound. As shown in Table 2, CoAl-LDH showed 606 F / g, CAGM0 had 723 F / g, and CAGM5 had 986 F / g.
8 is a graph of cycle stability of a CoAl-LDH / RGO / MnO 2 composite. The graph shows that all materials are stable up to 5,000 cycles.
Figure 9 is, CoAl-LDH / RGO /
It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .
Claims (7)
Mixing the mixed colloidal solution with a metal cation-containing solution to synthesize a layered double hydroxide and then reducing the graphene oxide to obtain a metal oxide nanosheet-layered double hydroxide-graphene nanosheet composite
/ RTI >
Wherein the metal oxide nanosheet and the graphen nanosheet each function as a support in synthesizing the layered double hydroxide.
Method for manufacturing nanocomposite for super capacitor electrode material.
Wherein the metal oxide nanosheet is a metal oxide nanosheet comprising a material selected from the group consisting of MnO 2 , TiO 2 , Ru oxide, Rh oxide, and combinations thereof. .
Wherein the layered double hydroxide comprises a metal layered double hydroxide represented by the following general formula 1:
[Formula 1]
[M II (1-x) M III x (OH) 2 ] [A n- ] x / n .zH 2 O;
In the general formula 1,
M < II > is a +2 valent metal cation,
M III is a +3 metal cation,
A n- is an anion selected from the group consisting of hydroxide ions (OH - ), nitrate ions (NO 3 - ), PO 4 3 - , HPO 4 2 - , H 2 PO 4 -
0 < x < 1,
n is 1, 2, or 3,
z is a number of from 0.1 to 15;
Wherein M II is a Ca 2 +, Mg 2 +, Zn 2 +, Ni 2 +, Mn 2 +, Co 2 +, Fe 2 +, Cu 2 +, and a metal cation selected from the group consisting of a combination of and wherein M III comprises a metal cation selected from the group consisting of + 3 Fe, Al 3 +, Cr 3+, Mn + 3, Ga + 3, Co + 3, Ni + 3, and combinations thereof Wherein the nanocomposite material is a nanocomposite material for a supercapacitor electrode material.
Wherein the metal oxide nanosheet and the graphen nanosheet each function as a support for the layered double hydroxide.
Super capacitor electrode material.
Wherein the non-recoatable capacity of the supercapacitor electrode material is at least 700 F / g.
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| CN105776261B (en) * | 2016-01-07 | 2017-06-23 | 北京化工大学 | A kind of fast preparation method of Multilevel-structure hydrotalcite and graphene oxide composite material |
| KR101965195B1 (en) * | 2016-04-06 | 2019-04-03 | 이화여자대학교 산학협력단 | Layered inorganic nanosheet-graphene composite, and preparing method of the same |
| CN106206056B (en) * | 2016-07-29 | 2018-01-23 | 武汉理工大学 | A kind of cobalt aluminum hydrotalcite/fluorinated graphene composite and preparation method thereof |
| CN106298282A (en) * | 2016-08-16 | 2017-01-04 | 哈尔滨工业大学 | The one-dimensional TiO of a kind of raising2the method of nanotube capacitive property |
| KR101975445B1 (en) * | 2017-10-31 | 2019-05-07 | 이화여자대학교 산학협력단 | Nanosheet hybrid, preparing method of the same, and supercapacitor using the same |
| US10193139B1 (en) * | 2018-02-01 | 2019-01-29 | The Regents Of The University Of California | Redox and ion-adsorbtion electrodes and energy storage devices |
| KR102158681B1 (en) | 2018-10-15 | 2020-09-22 | 이화여자대학교 산학협력단 | Layered double hydroxide nanosheet, method for producing the same, and electrode for supercapacitor including the same |
| KR102189302B1 (en) * | 2019-01-29 | 2020-12-09 | 이화여자대학교 산학협력단 | Method of producing transition metal oxide nanosheet, photocatalyst hybridized with the nanosheet, and electrode material including nanohybrid of the nanosheet with layered double hydroxide |
| KR102244214B1 (en) * | 2019-09-05 | 2021-04-27 | 단국대학교 천안캠퍼스 산학협력단 | Layered structue having excellent hydrogen proton conductivity and method for preparation the same |
| KR102353610B1 (en) | 2020-08-03 | 2022-01-20 | 연세대학교 산학협력단 | Manufacturing method for multilayerd hetero structure comprising a hybrid conductive layer |
| KR20220016662A (en) | 2020-08-03 | 2022-02-10 | 연세대학교 산학협력단 | MANUFACTURING METHOD FOR MULTILAYERD g-C3N4/MoS2 STRUCTURE |
| KR102353606B1 (en) | 2020-08-06 | 2022-01-20 | 연세대학교 산학협력단 | MANUFACTURING METHOD FOR MULTILAYERD g-C3N4/TiO2 STRUCTURE WITH DEFECT NANOSTRUCTURE |
| KR102366563B1 (en) * | 2020-11-24 | 2022-02-23 | 한국에너지기술연구원 | Hybrid composite comprising metal-organic framework and two-dimensional sheet |
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