KR20210054670A - 1 dimension electroconductive nickel-metal-organic frameworks and super capacitor electrode comprising the same - Google Patents

Abstract

The present invention relates to a one-dimensional electrically conductive Ni-organic structure, in which an organic ligand containing a substituted or unsubstituted C6 to C30 aryl-tetramine and Ni are repeatedly bonded in a straight chain. Accordingly, the one-dimensional Ni-organic structure of the present invention has excellent electrical conductivity, and is applied to a supercapacitor having high specific capacitance by being introduced as a positive electrode material of an energy storage device.

Description

One-dimensional electroconductive Ni-organic structure and super capacitor electrode comprising the same {1 dimension electroconductive nickel-metal-organic frameworks and super capacitor electrode comprising the same}

The present invention relates to a one-dimensional electrically conductive Ni-organic structure and a super capacitor electrode including the same.

The electric double layer capacitor (EDLC) is a charge storage device that physically attaches ions to the surface of a conductive electrode. Supercapacitors with high capacitance are attracting much attention due to their high power density, fast charging time, low maintenance cost, and long cycle life. In general, capacitance is proportional to the surface area of the conductive electrode. Therefore, activated carbon having a large surface area has been generally used as an electrode material, but a low energy density compared to a battery should be improved. Accordingly, new pseudo-capacitive nanomaterials that electrochemically store energy through surface redox reactions have been extensively studied as electrodes that increase both power and energy density. As a result, to date, transition metal oxides, conductive polymers, and hetero atom-doped carbonaceous materials have been proposed as pseudo-capacitive electrode materials. Among various pseudocapacitive nanomaterials, transition metal oxides have shown potential as electrode materials due to their high theoretical capacity, low cost, and reversibility. In particular, _{cheap hybrid electrodes such as MnO 2} /carbon and CoO/carbon exhibited a fast and stable redox reaction.

On the other hand, metal-organic frameworks (MOF) assembled with metal ions and organic ligands have well-arranged nanostructures with high surface area and functionality. The secondary building units representing the MOF's expansion point are mostly composed of metal oxide clusters. Therefore, carbonization of MOF in an inert atmosphere produces metal oxides in carbonaceous materials. This material has a large surface area with good dispersion of metal oxides on carbon. MOF-derived metal oxides/carbons represent promising platform applications in the field of clean energy. _{For example, Mn 2} O ₃ /graphene derived from Mn-MOFs showed a high specific capacitance and long cycle capacity of 471 Fg ^-1 in 0.5 M Na ₂ SO _{4, and interestingly,} Pyrolysis produced well-defined metal oxides with improved pseudo-capacitive properties. _{For example, the mixed metal Co 3} O ₄ /NiCo ₂ O ₄ produced by pyrolysis of ZIF-67/Ni-Co LDH (layered double hydroxide) in air has a high ^{972 Fg -1} at a current density ^{of 5Ag -1.} It shows the specific capacitance.

U.S. Patent No. 7880026

2016, p.351-357

An object of the present invention is to introduce a one-dimensional metal-organic structure having excellent electrical conductivity as an anode electrode material of an energy storage device, thereby applying it to a supercapacitor having a high specific capacitance.

According to an aspect of the present invention,

There is provided a one-dimensional electrically conductive Ni-organic structure in which an organic ligand including a substituted or unsubstituted C6 to C30 aryltetramine and Ni are repeatedly bonded in a straight chain.

The one-dimensional electrically conductive Ni-organic structure may be for an electrode of a super capacitor.

The aryltetraamine is substituted or unsubstituted benzene-tetramine, substituted or unsubstituted naphthalene-tetramine, substituted or unsubstituted anthracene-tetramine, Substituted or unsubstituted tetracene-tetramine, substituted or unsubstituted pentacene-tetramine, substituted or unsubstituted phenanthrene-tetramine, substituted or Unsubstituted pyrene-tetramine, substituted or unsubstituted chrysene-tetramine, substituted or unsubstituted perylene-tetramine, substituted or unsubstituted Fluorene-tetramine (fluorene-tetramine), substituted or unsubstituted coronene-tetramine (coronene-tetramine), and substituted or unsubstituted ovalene-tetraamine (ovalene-tetramine) can be any one selected from have.

The aryltetraamine may be any one selected from the following compounds 1 to 7.

The one-dimensional electrically conductive Ni-organic structure may have an electrical conductivity of 3.0 to 4.0 S/m at room temperature.

The BET surface area of the one-dimensional electrically conductive Ni-organic structure ^{may be 85 to 95 m 2} /g.

The total pore volume of the one-dimensional electrically conductive Ni-organic structure ^{may be 0.35 to 0.40 m 2} /g.

The one-dimensional electrically conductive Ni-organic structure may have a mesoporous volume of 85 to 95% of the total pore volume, and the remainder may be a micro pore volume.

According to another aspect of the present invention,

A super capacitor electrode including the one-dimensional electrically conductive Ni-organic structure is provided.

According to another aspect of the present invention,

(a) preparing a nickel-containing solution in which a nickel precursor and ammonium hydroxide are dissolved in an organic solvent;

(b) preparing a solution containing an aryltetraamine in which aryltetraamine-tetrahydrochloride is dissolved in an organic solvent; And

(c) synthesizing a one-dimensional electrically conductive Ni-organic structure by mixing the nickel-containing solution and the aryltetraamine-containing solution to heat treatment. A method for producing a one-dimensional electrically conductive Ni-organic structure is provided.

The nickel precursor may be any one selected from nickel nitrate, nickel acetylacetonate, nickel acetylacetate, nickel acetate, nickel halide, and nickel hydroxide.

The organic solvent is any one selected from dimethyl sulfoxide (DMSO), dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and triethyl phosphate (TEP). I can.

The aryltetraamine is substituted or unsubstituted benzene-tetramine, substituted or unsubstituted naphthalene-tetramine, substituted or unsubstituted anthracene-tetramine, Substituted or unsubstituted tetracene-tetramine, substituted or unsubstituted pentacene-tetramine, substituted or unsubstituted phenanthrene-tetramine, substituted or Unsubstituted pyrene-tetramine, substituted or unsubstituted chrysene-tetramine, substituted or unsubstituted perylene-tetramine, substituted or unsubstituted Fluorene-tetramine, substituted or unsubstituted coronene-tetramine, and substituted or unsubstituted ovalene-tetramine. have.

The aryltetraamine may be any one selected from the following compounds 1 to 7.

The heat treatment in step (c) may be performed at a temperature of 50 to 80°C.

The heat treatment in step (c) may be performed for 1 to 3 hours.

According to another aspect of the present invention,

A method of manufacturing a supercapacitor electrode comprising a method of manufacturing a one-dimensional electrically conductive Ni-organic structure according to any one of claims 9 to 15 is provided.

The one-dimensional Ni-organic structure of the present invention has excellent electrical conductivity and can be applied to a supercapacitor having a high specific capacitance by introducing it as an anode electrode material of an energy storage device.

1 is a flowchart sequentially showing a method of manufacturing a one-dimensional Ni-organic structure of the present invention.
2 shows an SEM image of Experimental Example 1.
3 is an X-ray diffraction (XRD) analysis result of Experimental Example 2.
4 is a measurement result of _{the N 2} adsorption isotherm of Experimental Example 3.
5 is a result of charging and discharging evaluation in Experimental Example 4. FIG.

The present invention is intended to illustrate specific embodiments and to be described in detail in the detailed description, since various transformations may be applied and various embodiments may be provided. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

The "substituted" means at least one hydrogen atom is deuterium, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C1 to C30 halogenated alkyl group, a C6 to C30 aryl group, a C1 to C30 heteroaryl group, C1 to C30 alkoxy group, C3 to C30 cycloalkoxy group, C1 to C30 heterocycloalkoxy group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryloxy group, C1 to C30 heteroaryloxy group, silyloxy Group (-OSiH ₃ ), -OSiR ¹ H ₂ (R ¹ is a C1 to C30 alkyl group or C6 to C30 aryl group), -OSiR ¹ R ² H (R ¹ and R ² are each independently a C1 to C30 alkyl group or C6 To C30 aryl group), -OSiR ¹ R ² R ³ , (R ¹ , R ² , and R ³ are each independently C1 to C30 alkyl group or C6 to C30 aryl group), C1 to C30 acyl group, C2 to C30 acyl Oxy group, C2 to C30 heteroaryloxy group, C1 to C30 sulfonyl group, C1 to C30 alkylthiol group, C3 to C30 cycloalkylthiol group, C1 to C30 heterocycloalkylthiol group, C6 to C30 arylthiol group, C1 to C30 heteroarylthiol group, C1 to C30 phosphate amide group, silyl group (SiR ¹ R ² R ³ ₎ (R ¹ , R ² , and R ³ are each independently a hydrogen atom, C1 to C30 alkyl group or C6 to C30 aryl group ), amine group (-NRR') (wherein R and R'are each independently a hydrogen atom, a substituent selected from the group consisting of a C1 to C30 alkyl group, and a C6 to C30 aryl group), a carboxyl group, a halogen group, It means substituted with a substituent selected from the group consisting of a cyano group, a nitro group, an azo group, and a hydroxy group.

In addition, two adjacent substituents among the substituents may be fused to form a saturated or unsaturated ring.

“Amine group” includes an amino group, an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group, and may be represented by -NRR', wherein R and R'are each independently a hydrogen atom , A C1 to C30 alkyl group, and a C6 to C30 aryl group.

“Aryl groups” include monocyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

In the aryl group, the number of ring atoms is the sum of the number of carbon atoms and the number of non-carbon atoms.

Hereinafter, a one-dimensional electrically conductive Ni-organic structure of the present invention will be described.

The one-dimensional electrically conductive Ni-organic structure of the present invention includes a substituted or unsubstituted C6 to C30 aryltetramine.

The one-dimensional electrically conductive Ni-organic structure is characterized in that it is for an electrode of a super capacitor.

The aryltetraamine is substituted or unsubstituted benzene-tetramine, substituted or unsubstituted naphthalene-tetramine, substituted or unsubstituted anthracene-tetramine, Substituted or unsubstituted tetracene-tetramine, substituted or unsubstituted pentacene-tetramine, substituted or unsubstituted phenanthrene-tetramine, substituted or Unsubstituted pyrene-tetramine, substituted or unsubstituted chrysene-tetramine, substituted or unsubstituted perylene-tetramine, substituted or unsubstituted Fluorene-tetramine, substituted or unsubstituted coronene-tetramine, substituted or unsubstituted ovalene-tetramine, etc. The scope is not limited thereto.

Preferably, the aryltetraamine may be any one selected from the following compounds 1 to 7.

The one-dimensional electrically conductive Ni-organic structure may have an electrical conductivity of 3.0 to 4.0 S/m at room temperature.

The BET surface area of the one-dimensional electrically conductive Ni-organic structure ^{may be 85 to 95 m 2} /g.

The total pore volume of the one-dimensional electrically conductive Ni-organic structure ^{may be 0.35 to 0.40 m 2} /g.

The one-dimensional electrically conductive Ni-organic structure may have a mesoporous volume of 85 to 95% of the total pore volume, and the remainder may be a micro pore volume.

The present invention provides a super capacitor electrode including the one-dimensional electrically conductive Ni-organic structure.

1 is a flowchart sequentially showing a method of manufacturing a one-dimensional electrically conductive Ni-organic structure of the present invention of the present invention. Hereinafter, a method of manufacturing a one-dimensional electrically conductive Ni-organic structure of the present invention will be described with reference to FIG. 1.

First, a nickel precursor and ammonium hydroxide are dissolved in an organic solvent to prepare a nickel-containing solution (step a).

The nickel precursor may be any one selected from nickel nitrate, nickel acetylacetonate, nickel acetylacetate, nickel acetate, nickel halide, and nickel hydroxide.

The organic solvent may be dimethyl sulfoxide (DMSO), dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), triethyl phosphate (TEP), and the like.

to the next, Aryltetraamine - Tetrahydrochloride A solution containing aryltetraamine dissolved in an organic solvent is prepared (step b).

The aryltetraamine is substituted or unsubstituted benzene-tetramine, substituted or unsubstituted naphthalene-tetramine, substituted or unsubstituted anthracene-tetramine, Substituted or unsubstituted tetracene-tetramine, substituted or unsubstituted pentacene-tetramine, substituted or unsubstituted phenanthrene-tetramine, substituted or Unsubstituted pyrene-tetramine, substituted or unsubstituted chrysene-tetramine, substituted or unsubstituted perylene-tetramine, substituted or unsubstituted Fluorene-tetramine, substituted or unsubstituted coronene-tetramine, substituted or unsubstituted ovalene-tetramine, etc. The scope is not limited thereto.

The aryltetraamine may be any one selected from the following compounds 1 to 7.

The organic solvent may be dimethyl sulfoxide (DMSO), dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), triethyl phosphate (TEP), and the like.

Then, the nickel-containing solution and Aryltetraamine One-dimensional electrical conductivity by mixing and heating the contained solution Ni -Synthesize the organic structure (step c).

The heat treatment is preferably performed at a temperature of 50 to 80°C, and more preferably may be performed at a temperature of 60 to 70°C.

The heat treatment is preferably performed for 1 to 3 hours, and more preferably may be performed for 1.5 to 2.5 hours.

The present invention provides a method of manufacturing a supercapacitor electrode including a method of manufacturing a one-dimensional electrically conductive Ni-organic structure.

In particular, although not explicitly described in the following examples, in the method for producing a one-dimensional electrically conductive Ni-organic structure according to the present invention, in step (a), the organic solvent type, the nickel precursor type, and the step (b) , Aryltetraamine type, organic solvent type, in step (c), while changing the mixing conditions, heating temperature and time conditions to prepare a one-dimensional electrically conductive Ni-organic structure.

The performance was confirmed by performing an electrochemical property test on the electrode including the one-dimensional electrically conductive Ni-organic structure thus prepared. As a result, unlike in other conditions and other numerical ranges, only when all of the following conditions were satisfied, the charge/discharge characteristics were measured to be remarkably high. Such manufacturing conditions are as follows.

In step (a), dimethyl sulfoxide (DMSO) is used as the organic solvent, nickel nitrate is used as the nickel precursor, and in step (b), dimethyl sulfoxide (DMSO) is used as the organic solvent, and aryltetra As the amine, any one of compounds 1 to 7 is used, and in step (c), the heat treatment is performed at 50 to 80° C. for 1 to 3 hours, and without stirring.

Hereinafter, an embodiment according to the present invention will be described in detail.

[ Example ]

Example 1: 1-dimensional electrical conductivity Ni - MOF synthesis

In 3 ml of degassed DMSO in a 15 ml scintillation vial, a solution of Ni(NO ₃ ) ₂ .6H ₂ O (40 mg, 0.137 mmol) and 14M NH ₄ OH (0.8 ml) was dissolved in 3 ml of degassed DMSO. ,2,4,5-benzenetetramine tetrahydrochloride(BTA·4HCl) (39mg, 0.137mmol) was added to the dissolved solution. The reaction mixture was heated at 65° C. for 2 hours without stirring. The black precipitated product was centrifuged, washed twice with ethanol, and dried under vacuum.

The synthesis reaction scheme of Example 1 is shown in Scheme 1 below.

[Scheme 1]

Example 2: 1-dimensional electrical conductivity MOF Electrode manufacturing

The one-dimensional electroconductive MOF synthesized according to Example 1 was pulverized to prepare Ni-MOF powder. Next, Ni-MOF powder was mixed with Super P, which is a conductive carbon, in a mortar bowl at a ratio of 1:1 and mixed using a pestle. A PTFE binder was mixed in a well-mixed Ni-MOF and Super P mixture in a weight ratio of 8:2, and then pressed using a mortar and a mortar to prepare an electrode. The prepared electrode was formed to a thickness of about 150 μm using a roller.

[ Experimental example ]

Experimental example One: SEM Image and electrical conductivity measurement

The SEM image of the Ni-MOF prepared according to Example 1 is shown in FIG. 2. SEM images were obtained by HITACHI S-4800.

Referring to FIG. 1, it can be seen that in the Ni-MOF prepared according to Example 1, one-dimensional Ni-MOF strands are well formed, and one-dimensional strands having a width of about 400 nm form a cluster.

On the other hand, the Ni-MOF powder prepared according to Example 1 was made into pellets with a size of 3 cm, and the electrical conductivity was measured by placing a sample between gold electrodes by a 2-probe method. As a result, the electrical conductivity was measured to be 3.5 S/m.

Experimental example 2: X-ray diffraction ( XRD ) analysis

3 shows the results of XRD analysis of N-MOF prepared according to Example 1.

According to this, it was confirmed that it has a one-dimensional structure according to the (110), (02-1), (012) (21-1) (033) peaks.

Experimental example 3: N ₂ Adsorption isotherm measurement

To calculate the BET surface area, the N ₂ adsorption isotherm was measured at 77 K using a BELSORP-MAX instrument, and the sample was activated at 250° C. before measuring the _{N 2 adsorption isotherm.} The results are shown in Fig. 4 and Table 1 below.

As a result of calculating the specific surface area, total pore volume, micro pore volume, and mesopore volume through a nitrogen adsorption isotherm, it can be seen that the 1-dimensional electroconductive MOF prepared according to Example 1 has a higher ratio of large mesopores than micro pores there was. This high ratio of mesopores means that ion transport to the electrode can be facilitated.

BET surface area (m ² /g) Total void volume (cm ³ /g) Micro pore volume (cm ³ /g) Meso void volume (cm ³ /g) 89.3 0.3819 0.0027 0.3792

Experimental example 4: Charging and discharging evaluation

The Ni-MOF/Super P/PTFE electrode prepared in this way according to Example 2 was cut to a size corresponding to about 5 mg, and the cut electrode was _{compatible with lithium foil, glass fiber separator, and 1M LiPF 6} EC/DMC electrolyte. A secondary battery coin cell was manufactured using 2032 Coincell parts, and the characteristics of the secondary battery were evaluated using an electrochemical measurement and evaluation equipment (charger/discharger).

For the electrochemical evaluation of the electrode prepared according to Example 2, a lithium half-cell was assembled, and ^{a voltage range of 0.0 to 3.0 V (vs. Li +} /Li) at a C-rate of 50 mA/g. The charge/discharge curve of the initial cycle was obtained at and is shown in FIG. 5.

According to this, the one-time charge/discharge capacity was 1145.2/1375.9 mAh g ^-1 , respectively, and showed a Coulombic efficiency (CE) of 120%. In addition, the two charge/discharge capacities were 1169.0/1108.6 mAh g ^-1 , respectively, and had a Coulomb efficiency of 94.8%.

In the above, embodiments of the present invention have been described, but those of ordinary skill in the relevant technical field add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. It will be possible to variously modify and change the present invention by means of the like, and it will be said that this is also included within the scope of the present invention.

Claims (17)

One-dimensional electrically conductive Ni-organic structure in which an organic ligand containing a substituted or unsubstituted C6 to C30 aryltetramine and Ni are repeatedly bonded in a straight chain. The method of claim 1,
The one-dimensional electrically conductive Ni-organic structure is a one-dimensional electrically conductive Ni-organic structure, characterized in that for the electrode of a super capacitor. The method of claim 1,
The aryltetraamine is substituted or unsubstituted benzene-tetramine, substituted or unsubstituted naphthalene-tetramine, substituted or unsubstituted anthracene-tetramine, Substituted or unsubstituted tetracene-tetramine, substituted or unsubstituted pentacene-tetramine, substituted or unsubstituted phenanthrene-tetramine, substituted or Unsubstituted pyrene-tetramine, substituted or unsubstituted chrysene-tetramine, substituted or unsubstituted perylene-tetramine, substituted or unsubstituted Fluorene-tetramine, substituted or unsubstituted coronene-tetramine, and substituted or unsubstituted ovalene-tetramine. One-dimensional electrically conductive Ni-organic structure characterized by. The method of claim 3,
The aryltetraamine is one-dimensional electrically conductive Ni-organic structure, characterized in that any one selected from the following compounds 1 to 7.

The method of claim 3,
The one-dimensional electrically conductive Ni-organic structure has an electrical conductivity of 3.0 to 4.0 S/m at room temperature. The method of claim 1,
The one-dimensional electrically conductive Ni-organic structure, characterized in that the BET surface area of the one-dimensional electrically conductive Ni-organic structure is 85 to 95 m ^{2 /g.} The method of claim 1,
One-dimensional electrically conductive Ni-organic structure, characterized in that the total pore volume of the one-dimensional electrically conductive Ni-organic structure is 0.35 to 0.40 m ^{2 /g.} The method of claim 7,
The one-dimensional electrically conductive Ni-organic structure is a one-dimensional electrically conductive Ni-organic structure, characterized in that the mesopores volume is 85 to 95% of the total pore volume and the remainder is the micro pore volume. A super capacitor electrode comprising the one-dimensional electrically conductive Ni-organic structure of any one of claims 1 to 8. (a) preparing a nickel-containing solution in which a nickel precursor and ammonium hydroxide are dissolved in an organic solvent;
(b) preparing a solution containing an aryltetraamine in which aryltetraamine-tetrahydrochloride is dissolved in an organic solvent; And
(c) synthesizing a one-dimensional electrically conductive Ni-organic structure by mixing the nickel-containing solution and the aryltetraamine-containing solution to heat treatment. The method of claim 10,
The nickel precursor is a method for producing a one-dimensional electrically conductive Ni-organic structure, characterized in that one selected from nickel nitrate, nickel acetylacetonate, nickel acetylacetate, nickel acetate, nickel halide, and nickel hydroxide. The method of claim 10,
The organic solvent is any one selected from dimethyl sulfoxide (DMSO), dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), and triethyl phosphate (TEP). Method for producing a one-dimensional electrically conductive Ni-organic structure, characterized in that. The method of claim 10,
The aryltetraamine is substituted or unsubstituted benzene-tetramine, substituted or unsubstituted naphthalene-tetramine, substituted or unsubstituted anthracene-tetramine, Substituted or unsubstituted tetracene-tetramine, substituted or unsubstituted pentacene-tetramine, substituted or unsubstituted phenanthrene-tetramine, substituted or Unsubstituted pyrene-tetramine, substituted or unsubstituted chrysene-tetramine, substituted or unsubstituted perylene-tetramine, substituted or unsubstituted Fluorene-tetramine, substituted or unsubstituted coronene-tetramine, and substituted or unsubstituted ovalene-tetramine. A method for producing a one-dimensional electrically conductive Ni-organic structure, characterized in that. The method of claim 10,
The aryltetraamine is a method for producing a one-dimensional electrically conductive Ni-organic structure, characterized in that any one selected from the following compounds 1 to 7.

The method of claim 10,
The heat treatment in step (c) is a method for producing a one-dimensional electrically conductive Ni-organic structure, characterized in that it is carried out at a temperature of 50 to 80°C. The method of claim 15,
The heat treatment in step (c) is a method for producing a one-dimensional electrically conductive Ni-organic structure, characterized in that it is carried out for 1 to 3 hours. A method of manufacturing a supercapacitor electrode comprising a method of manufacturing a one-dimensional electrically conductive Ni-organic structure according to any one of claims 10 to 16.

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