WO2018052179A1

WO2018052179A1 - Electrode material and electrochemical device using same

Info

Publication number: WO2018052179A1
Application number: PCT/KR2017/006149
Authority: WO
Inventors: 박정욱; 강석민; 황민영; 조인희
Original assignee: 엘지이노텍 주식회사
Priority date: 2016-09-13
Filing date: 2017-06-13
Publication date: 2018-03-22
Also published as: KR20180029794A; KR102519740B1; CN211208258U

Abstract

An embodiment relates to an electrode material and an electrochemical device using the same and, more specifically, to: an electrode material, which can implement an electrochemical device and has a high capacitance by comprising a carbon source, comprising a crystalline structure and an amorphous structure, wherein the crystalline structure comprises a crystal lattice, the amorphous structure comprises pores, the interlayer distance of the crystalline structure is 0.37-0.40 nm, and the ratio of the crystalline structure to the unit weight (g) of the electrode material is 0.4-0.91; and an electrochemical device using the same.

Description

Electrode Materials and Electrochemical Devices Using the Same

The embodiment relates to an electrode material and an electrochemical device using the same, and more particularly, to an electrode material capable of realizing an electrochemical device having a high capacitance and an electrochemical device using the same.

Recently, interest in energy storage technology is increasing.

As the field of application extends to the energy of mobile phones, camcorders and notebook PCs, and even electric vehicles, efforts for research and development of electrochemical devices are becoming more concrete.

The electrochemical device enables conversion between electrical energy and chemical energy, and specific examples thereof include a supercapacitor (electric double layer capacitor, EDLC), a lithium ion secondary battery, a hybrid capacitor, and the like.

Electrochemical devices are attracting attention in terms of charge / discharge and high energy density, and high capacitance and energy density are required as the application fields are expanded.

As an example of a supercapacitor, a unit cell is formed including an anode and a cathode impregnated with an electrolyte, a separator provided between two electrodes, a gasket for preventing leakage of the electrolyte and preventing insulation and short circuit, and a metal case. Cells are laminated and configured by combining terminals of a positive electrode and a negative electrode. A composition for forming an electrode may include a binder and a conductive material in addition to an electrode active material, and each component may be applied to a supercapacitor in a slurry form after mixing.

At this time, the performance of the electrochemical device is determined in particular by the electrode active material, and activated carbon is mainly used as the electrode active material.

However, the commercialized electrode active material has a limitation in increasing the capacity of the electrochemical device, a solution for this situation is required.

The embodiment aims to provide an electrode material capable of implementing an electrochemical device having a high capacitance.

In addition, it is an object of the embodiment to provide an electrochemical device using an electrode material capable of realizing an electrochemical device with significantly improved capacitance.

The electrode material of the present invention comprises a carbon source, the carbon source comprises crystalline and amorphous, the crystalline comprises a crystal lattice, the amorphous comprises pores, the interlayer distance of the crystalline is between 0.37 nm and 0.40 nm and the electrode The ratio of said crystalline to the unit weight (g) of material is 0.4 to 0.91.

In one embodiment of the electrode material, the ratio of the crystalline to the unit weight (g) may satisfy the following equation (1) and (2).

Equation 1 20x + 2000y = k

[Equation 2] x + y = 1

(Wherein x is a crystalline ratio, y is an amorphous ratio and k is 200 to 1200).

In one embodiment of the electrode material, the volume of the pores having a diameter of more than 0 nm and 1 nm or less in the pores may be 60% to 85% of the total volume of the amorphous.

In one embodiment of the electrode material, the volume of the pores having a diameter of 0.6 nm to 0.9 nm in the pores may be 45% to 75% of the total volume of the amorphous.

In one embodiment of the electrode material, the volume of the pores having a diameter of 0.75 nm to 0.85 nm in the pores may be 15% to 23% of the total volume of the amorphous.

In one embodiment of the electrode material, the specific surface area may be 200 m ² / g to 1200 m ² / g.

In one embodiment of the electrode material, the apparent density is 0.7 g / cm ³ To 1.5 g / cm ³ .

The electrochemical device of the present invention includes a first electrode, a second electrode and a separator disposed between the first electrode and the second electrode, and forms at least one of the first electrode and the second electrode. The electrode material comprises a carbon source, the carbon source comprises crystalline and amorphous, the crystalline comprises a crystalline lattice, the amorphous comprises pores, the crystalline interlayer distance is between 0.37 nm and 0.40 nm and the The ratio of the crystalline to the unit weight (g) is 0.4 to 0.91.

In one embodiment of the electrochemical device, the ratio of the crystalline to the unit weight (g) may satisfy the following equation (1) and (2).

Equation 1 20x + 2000y = k

[Equation 2] x + y = 1

In one embodiment of the electrochemical device, the volume of the pores having a diameter of more than 0 nm and 1 nm or less in the pores may be 60% to 85% of the total volume of the amorphous.

The electrochemical device formed by including the electrode material of the embodiment is capable of realizing high capacitance, and thus has excellent electrical characteristics.

The electrode material of the embodiment can be used in electrochemical devices with significantly improved capacitance.

1 is a view schematically showing an enlarged shape of an electrode material according to an embodiment of the present invention.

2 is a view schematically showing an electrochemical device according to an embodiment of the present invention.

3 is a manufacturing process chart of the electrode material according to an embodiment of the present invention.

4 is a view schematically showing a change in carbon source according to heat treatment and activation treatment.

5 is an X-ray diffraction analysis pattern of the electrode material according to an embodiment of the present invention

6 is a graph showing the distribution of pores according to the pore diameter of Example 1 and Comparative Example 8. FIG.

In the description of the embodiments, it is described that each layer, film, electrode, plate or substrate, etc., is formed on or under the "on" of each layer, film, electrode, plate or substrate, etc. In the case, “on” and “under” include both being formed “directly” or “indirectly” through other components.

In addition, the criteria for the top, side or bottom of each component will be described with reference to the drawings. The size of each component in the drawings may be exaggerated for description, and does not mean a size that is actually applied.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view schematically showing an enlarged shape of an electrode material according to an embodiment of the present invention. A description with reference to FIG. 1 is as follows.

The electrode material comprises a carbon source 100, and the carbon source 100 comprises a crystalline 21 and an amorphous 11 comprising a crystal lattice. That is, the crystalline 21 and the amorphous 11 are mixed in the carbon source 100 included in the electrode material.

The carbon source 100 may include, for example, a material such as petroleum or coal-based pitch, green coke (green coke), calcination (calcination) coke, or the like. However, as long as it does not depart from the object of the present invention, it is not necessarily limited thereto.

The amorphous 11 included in the carbon source 100 includes pores 12.

The pores 12 impart porosity to the electrode material, and electrolyte ions 13 may be inserted into the pores 12 included in the amorphous 11.

The presence or absence of pores 12 and / or the diameter length of the pores 12 in the amorphous 11 is a factor influencing the specific surface area of the electrode material. Accordingly, the capacitance of the electrode material may be improved by adjusting the presence or absence of the pores 12 and / or the diameter length of the pores 12.

The electrode material may include at least one pore 12 in the amorphous 11. That is, the electrode material may include a plurality of pores 12 in the amorphous 11.

When the electrode material comprises a plurality of pores 12, the length of the diameter may be the same or different for each pore 12. Specifically, the electrode material may include pores 12 having the same length diameter. In addition, the electrode material may include pores 12 having different length diameters. In addition, the electrode material may include both pores 12 having the same diameter in length and pores 12 having different diameters in length.

Crystalline 21 included in the carbon source 100 is formed as the partial crystallization in the process of heat treatment at a temperature of 650 ℃ to 900 ℃ as described later.

Whether the carbon source 100 includes the crystalline 21 can be confirmed by X-ray diffraction (XRD). Some of the diffraction occurs when X-rays are irradiated to the crystals. The diffraction angles and intensities are inherent in each material structure, and the diffraction X-rays can be used to obtain information related to the type and amount of crystalline material contained in the sample. That is, according to the X-ray diffraction analysis, information about the structure of the crystalline substance can be known.

The electrode material includes a crystalline 21 in addition to the pores 12 of the amorphous 11 in the carbon source 100. Accordingly, the crystalline 21 may serve to move the electrolyte ions 13 so that the electrolyte ions 13 easily flow, thereby lowering the resistance to improve electrical conductivity. In addition, the capacitance can be significantly improved.

The crystalline interlayer distance d is 0.37 nm to 0.40 nm.

The crystalline interlayer distance d may be controlled by an activation temperature and / or a content ratio of a carbon source and an activator, which will be described later.

If the crystalline interlayer distance d is less than 0.37 nm, electrolyte ions 13 cannot be inserted between adjacent crystal lattice layers. In addition, when the crystalline interlayer distance (d) exceeds 0.40 nm, the distance between adjacent crystal layers becomes farther, and van der Waals forces existing between the respective crystal layers cannot act, thereby losing crystallinity. Accordingly, there is a problem that the capacitance F / cc is lowered when the crystalline interlayer distance d is out of the above range.

The crystalline interlayer distance d may be measured by a method well known in the art, and may be, for example, X-ray diffraction analysis or TEM photograph, but is not necessarily limited thereto.

The ratio of the crystalline 21 to the unit weight g of the electrode material is 0.4 to 0.91.

Depending on the type of the carbon source 100 included in the electrode material, the specific surface area of the carbon source 100 including only the crystalline 21 and only the amorphous 11 may be different. Therefore, in order to implement an electrode material capable of improving the capacitance value, the ratio of the crystalline 21 and the amorphous 11 per unit weight (g) of the electrode material may be specified.

The ratio of the crystalline 21 to the unit weight (g) of the electrode material may be derived by

Equations

1 and 2 below.

Equation 1 20x + 2000y = k

[Equation 2] x + y = 1

Wherein x is the proportion of crystalline, y is the proportion of amorphous, and k is 200 to 1200 for the specific surface area value.

In addition, the ratio of the crystalline 21 to the unit weight (g) of the electrode material may be controlled by the heat treatment temperature of the carbon source 100 as described below.

The carbon source 100 includes both the amorphous 11 and the crystalline 21, and thus the capacitance may be improved by considering all the factors related to the capacitance in the amorphous 11 and the crystalline 21.

In one embodiment, by adjusting the ratio of the pores 12 having a constant diameter of the amorphous 11 can be implemented a high capacitance.

The ratio of the pores 12 and the diameter of the pores 12 having a specific range of diameters can be measured by the BET measurement method, but is not necessarily limited thereto.

The pores 12 may be composed of pores 12 having various diameters.

Specifically, the pores 12 may include pores 12 having a diameter greater than 0 nm and 1 nm or less. The volume of the pores 12 having a diameter in the above range may be 60% to 85% of the total volume of the amorphous (11).

If the volume of pores 12 having a diameter in this range is less than 60% or more than 85% relative to the total volume of amorphous 11, the capacitance of the electrode material is significantly reduced. Accordingly, there is a problem in that the electrical properties of the electrode material and the electrochemical device 10 including the same are lowered.

In one embodiment, the volume of pores 12 with a diameter of 0.6 nm to 0.9 nm may be 45% to 75% of the total volume of the amorphous 11. When the volume of the pores 12 having a diameter of 0.6 nm to 0.9 nm is within the above range, the effect of improving capacitance can be improved, which is preferable.

In another embodiment, the volume of pores 12 with a diameter of 0.75 nm to 0.85 nm may be 15% to 23% of the total volume of the amorphous 11. When the volume of the pores 12 having a diameter of 0.75 nm to 0.85 nm is in the above-described range, the effect of improving capacitance can be significantly improved, which is very preferable.

In addition, in one embodiment, the specific surface area of the electrode material is also a factor influencing the capacitance. Specifically, when the specific surface area is large, energy storage characteristics are generally improved, but when the specific surface area is too large, the electrode density may be lowered, and thus the capacitance F / cc may be reduced.

In the present invention, the lower the heat treatment temperature of the carbon source 100, the higher the ratio of amorphous 11 can increase the specific surface area of the electrode material, the higher the heat treatment temperature of the carbon source 100, the higher the crystalline 21 of The ratio may be high to reduce the specific surface area of the electrode material.

The specific surface area of the electrode material may vary depending on the carbon source 100 included in the electrode material.

In addition, the specific surface area of the electrode material may also vary depending on the ratio of the crystalline 21 and the amorphous 11 included in the carbon source 100.

If the ratio of the crystalline 21 is less than 0.4, there is a problem that the specific surface area of the electrode material is small and the electrostatic capacity is significantly lowered. In addition, when the ratio of the crystalline 21 is more than 0.91, there is a problem that the specific surface area of the electrode material is excessively increased and the capacitance is rather reduced.

In one embodiment, the specific surface area of the electrode material may be 200 m ² / g to 1200 m ² / g. When the specific surface area of the electrode material is within the above-described range, the electrolyte ions are easily introduced between the crystal lattice or the amorphous pores 12, and thus the electrostatic capacity is remarkably improved.

The specific surface area may be measured by BET measurement, but is not necessarily limited thereto.

In the present specification, the apparent density means mass per unit volume, and the apparent density may also affect the capacitance. Specifically, if the apparent density is too large, there is a problem that the capacitance decreases, and if the apparent density is too small, energy storage characteristics may be degraded.

In one embodiment, the apparent density of the electrode material is 0.7 g / cm ³ To 1.5 g / cm ³ . It is preferable that the apparent density is a value within the above-mentioned range because the capacitance of the electrode material increases.

In another embodiment, the apparent density of the electrode material may be between 0.9 g / cm ³ and 1.3 g / cm ³ . If the apparent density is a value within the above-mentioned range, the effect of improving the capacitance of the electrode material is more preferable.

The electrode material of the present invention comprises a carbon source 100, the carbon source 100 comprises a crystalline 21 comprising a crystal lattice and an amorphous 11 comprising pores 12, the crystalline interlayer distance (d) is 0.37 nm to 0.40 nm, and the ratio of the crystalline to the unit weight (g) of the electrode material is 0.4 to 0.91. Accordingly, the electrode material may have a high capacitance.

2 schematically illustrates an electrochemical device 10 of one embodiment.

The electrochemical device 10 is not particularly limited as long as it is within the scope of the present invention without departing from the object of the electrical energy and chemical energy conversion. For example, the electrochemical device 10 may be a supercapacitor, a secondary battery, or the like. Hereinafter, a description will be given with reference to FIG. 2, in which a supercapacitor is used as the electrochemical device 10.

The electrochemical device 10 of the present invention is formed including the electrode material described above.

The electrochemical device 10 includes a first electrode 2, a second electrode 4, and a separator 3 disposed between the first electrode 2 and the second electrode 4.

At least one of the first electrode 2 and the second electrode 4 included in the electrochemical element 10 is formed by including the electrode material described above, and thus overlaps with the foregoing description with respect to the electrode material. The detailed description thereof will be omitted within the scope.

The electrode material forming at least one of the first electrode 2 and the second electrode 4 includes a carbon source 100 and the carbon source 100 includes a crystalline 21 and pores (including a crystal lattice). Interlayer distance (d) of the crystalline is from 0.37 to 0.40 nm, and the ratio of the crystalline to the unit weight (g) of the electrode material is 0.4 to 0.91.

Accordingly, the electrode material may be included as an electrode forming composition for at least one of the first electrode 2 and the second electrode 4 so that the electrode material may function as an electrode active material.

In the electrochemical device 10, the ratio of the crystalline to the unit weight (g) may satisfy the following equations (1) and (2).

Equation 1 20x + 2000y = k

[Equation 2] x + y = 1

Wherein x is a crystalline ratio, y is an amorphous ratio, and k is 200 to 1200.

In one embodiment, the volume of the pores 12 having a diameter greater than 0 nm and 1 nm or less in the pores 12 included in the electrochemical device 10 may be 60% to 85% of the total volume of the amorphous 11. Can be.

In another embodiment, the volume of the pores 12 having a diameter of 0.6 nm to 0.9 nm among the pores 12 included in the electrochemical device 10 may be 45% to 75% of the total volume of the amorphous 11. Can be.

In another embodiment, the volume of the pores 12 having a diameter of 0.75 nm to 0.85 nm in the pores 12 may be 15% to 23% of the total volume of the amorphous 11.

In the electrochemical device 10, the specific surface area of the electrode material may be 200 m ² / g to 1200 m ² / g.

In addition, in the electrochemical device 10, the apparent density of the electrode material may be 0.7 g / cm ³ to 1.5 g / cm ³ .

The first electrode 2 may be an anode, and the second electrode 4 may be a cathode.

The separator 3 is disposed between the first electrode 2 and the second electrode 4. Specifically, the separator 3 may be disposed in contact with the first electrode 2 and the second electrode 4. One side and the other side of the separator 3 may be disposed in direct contact with the first electrode 2 and the second electrode 4.

The first electrode 2, the second electrode 4, and the separator 3 may be impregnated with an electrolyte.

In one embodiment, the electrolyte may be a non-aqueous electrolyte.

More specifically, when a non-aqueous electrolyte is used, the electrolyte cation may be TEA ⁺ , TEMA ⁺ , Li ⁺ , EMIM ⁺ , Na ^+, etc., and the electrolyte anion may be BF ₄ ⁻ , PF ₆ ⁻ , TFSI ⁻ , FSI ^−, or the like. have. The electrolyte solvent may also be an organic electrolyte, more specifically ACN, PC, GBL, DMK, or the like.

The concentration of the electrolyte may be different for each kind of the solvent and the electrolyte ions 13.

If necessary, the electrochemical device 10 may include two or more separators.

In an embodiment, when the electrochemical device 10 includes a plurality of separators, the separators 1 other than the separator 3 disposed between the first electrode 2 and the second electrode 4 may be formed. It may be disposed above the first electrode 2.

In an embodiment, at least one electrode of the first electrode 2 and the second electrode 4 may be a rolling composition of an electrode forming composition including the electrode material described above on a base substrate.

In an embodiment, the first electrode 2 and / or the second electrode 4 may be coated with a composition for forming an electrode including the electrode material on a base substrate.

In another embodiment, the first electrode 2 and / or the second electrode 4 may be formed by making the electrode-forming material into a sheet state and attaching it to a base substrate, followed by drying, but the present invention is necessarily implemented. It is not limited to the examples.

The base substrate may be formed including a conductive material. Specific examples of the conductive material may be metals and the like. More specifically, the metal may be copper, aluminum, or the like, but the present invention is not necessarily limited to the embodiments.

The base substrate may have a thin film shape.

The electrode forming composition may include a binder and a conductive material in addition to the electrode material, and may further include a solvent. In addition, each component may be applied to the electrochemical device 10 as a slurry after mixing.

The binder imparts adhesion to the composition for forming an electrode. Specific examples of the binder include carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), polyethylene (PE), polypropylene (PP) And polyvinyl alcohol (PVA). The binder may be used including at least one of the above examples, but the embodiment is not necessarily limited thereto.

In one embodiment, the binder may be included in 1 to 45% by weight based on the total composition for forming the electrode.

The conductive material imparts conductivity to the composition for forming an electrode. Specific examples of the conductive material may include carbon black, graphene, carbon nanotubes (CNT), carbon nanofibers (CNF), and the like. The conductive material may be used including at least one of the above examples, but the embodiment is not necessarily limited thereto.

In one embodiment, the conductive material may be included in an amount of 1 to 45% by weight based on the entire composition for forming an electrode.

If necessary, the electrode forming composition may further include a solvent. Specific examples of the solvent may include water or an organic solvent, but embodiments are not necessarily limited thereto.

In one embodiment, the solvent may be included in 10 to 97% by weight based on the total composition for forming the electrode.

In one embodiment,

lead wires

6 and 7 may be attached to each of the first electrode 2 and the second electrode 4. In addition, the first electrode 2, the second electrode 4, and the separator 3 disposed therebetween may have a structure disposed in the cover 5.

In one embodiment, the cover 5 may be formed including a conductive material. The conductive material may include a metal and the like. Specific examples of the metal may be aluminum and the like.

3 is a manufacturing process chart of the electrode material according to an embodiment of the present invention, Figure 4 is a view showing a change in the carbon source according to the activation process. Hereinafter, the manufacturing method of an electrode material is demonstrated with reference to FIG. 3 and FIG.

First, the carbon source 100 is heat treated at a temperature of 650 ℃ to 900 ℃.

If the temperature of the heat treatment is less than 650 ° C., the crystalline 21 is not formed in the carbon source 100. In addition, when the heat treatment temperature exceeds 900 ℃ there is a problem that can not implement a high capacitance because only the crystalline 21 is present in the carbon source 100 without the amorphous (11). That is, the carbon source 100 is heat-treated at a temperature of 650 ° C. to 900 ° C. to form amorphous 11 and crystalline 21 in the carbon source 100.

In one embodiment, the heat treatment temperature may be 650 ℃ to 850 ℃.

The ratio of the crystalline 21 to the unit weight (g) of the electrode material may be controlled by the heat treatment temperature of the carbon source 100.

The ratio of the crystalline 21 to the unit weight (g) of the electrode material varies according to the heat treatment temperature of the carbon source 100, and the ratio of the crystalline 21 affects the specific surface area of the electrode material and thus the electrostatic The dose value can be changed.

The lower the heat treatment temperature of the carbon source 100 is, the higher the proportion of amorphous 11 increases the specific surface area of the electrode material. The higher the heat treatment temperature of the carbon source 100, the higher the ratio of crystalline 21 is increased. The specific surface area can be reduced.

In an embodiment, the electrode material may include the crystalline 21 as the heat treatment of the carbon source 100 within a temperature range of 650 ° C. to 900 ° C., as well as an optimal crystalline to improve the capacitance value. The ratio of 21) may be implemented in the range of 0.4 to 0.91 based on the unit weight (g) of the electrode material.

The time for which the heat treatment process is performed may vary depending on the size of the reactor.

The heat treatment may be performed in an inert gas atmosphere. Specific examples of the inert gas may be helium, argon, nitrogen, and the like. The inert gas may be used including at least one of the above examples, but the embodiment is not necessarily limited thereto.

Subsequently, the heat treated carbon source 100 is activated with a material containing alkali at a temperature of 800 ° C to 1000 ° C.

In the activation process step, the amorphous 11 is broken to form pores 12, or the crystalline 21 has a crystalline interlayer distance (see FIG. 4), thereby increasing the specific surface area of the carbon source.

If the activation treatment temperature is less than 800 ℃ or more than 1000 ℃, the crystalline interlayer distance of the crystalline 21 in the crystalline 21 of the carbon source 100 is out of 0.37 nm to 0.40 nm there is a problem that can not secure a high capacitance .

In addition, when the activation treatment temperature is outside the range of 800 ℃ to 1000 ℃ it is difficult to control the proportion of pores 12 having a specific range of diameter, the volume of the pores 12 having a diameter greater than 0 and less than 1 nm is amorphous ( 11) Electrode materials can be produced which deviate from 60 to 85% of the total volume. In this case, there is a problem that the electrode material and the electrochemical device 10 including the same cannot implement high capacitance.

Specific examples of the alkali may be lithium, sodium, potassium metal, and the like, but are not necessarily limited thereto.

The activation treatment may be performed in an inert gas atmosphere.

Specific examples of the inert gas may be helium, argon, nitrogen, and the like. The inert gas may be used including at least one of the above examples, but the embodiment is not necessarily limited thereto.

The activation treatment may be performed in an inert gas atmosphere.

In the activation treatment step, the carbon source 100 and the activator are mixed in a weight ratio of 1: 0.8 to 1: 5.5.

If the weight ratio of the carbon source and the activator is less than 1: 0.8, the carbon source may not be sufficiently activated. Accordingly, even if the crystalline 21 is present in the electrode material, there is a problem that the interlayer distance of the crystalline 21 sufficient to insert the electrolyte ions cannot be secured.

On the other hand, when the weight ratio of the carbon source and the activator exceeds 1: 5.5, the distance between adjacent crystal layers becomes far. As a result, van der Waals forces between the crystal layers cannot act and the electrode material loses crystallinity.

In addition, when the weight ratio of the carbon source and the activator is outside the above-described range, it may be difficult to adjust the proportion of the pores 12 having a specific range of diameters. Accordingly, it is difficult to implement the volume of the pores 12 greater than 0 nm and less than 1 nm in diameter to 60 to 85% of the total volume of the amorphous 11, so that the capacitance may be significantly reduced.

After the activation treatment is neutralized to remove the alkali-containing material, for example, hydrochloric acid, nitric acid, etc. may be used as a neutralizing agent.

After neutralization, the resultant is washed, and distilled water may be used as an example in the washing process.

After the cleaning may further comprise a drying process. The time and temperature of the drying process may vary depending on the size of the reactor.

The manufacturing method of the electrode material is well known in the art and may further include the process, if it is within the scope without departing from the object of the present invention.

The electrode material produced by the above-described method comprises a crystalline 21 comprising a crystal lattice and an amorphous 11 comprising pores 12 and the crystalline interlayer distance d is between 0.37 nm and 0.40 nm. 100) and the ratio of the crystalline to the unit weight (g) of the electrode material is 0.4 to 0.91. That is, according to the method of manufacturing the electrode material, the above-described electrode material is manufactured, and thus, the above-described contents may be applied in the same range to overlap with the description of the electrode material.

Example One

Preparation of materials for forming electrodes

The residue oil from the Naphta Cracking Center (NCC) process was heat treated at a temperature of 350 ° C. to produce a solid state pitch ranging from 1000 to 2500 molecular weight, and used as the carbon source of the electrode material.

The carbon source prepared by the above method was heat-treated in a hot spot of 60 Φ * 120 cm for 1 hour at a temperature of 750 ° C. under argon atmosphere.

Subsequently, an electrode material was prepared by activating a content ratio of a carbon source and a KOH activator 1: 4 at 900 ° C. for 1 hour in an argon atmosphere, and then a material for forming an electrode was prepared using the ingredients and contents shown in Table 1 below.

구분(중량%)Division (weight%)	바인더bookbinder	도전재Conductive material	본 발명에 따른 전극 재료Electrode material according to the invention
실시예 1Example 1	55	55	9090

Fabrication of Electrochemical Devices

The composition for forming an electrode was pressed on a copper base substrate with a roller to make a sheet, and then dried to prepare a first electrode and a second electrode, and a lead wire was attached to each electrode.

The first separator, the first electrode, the second separator and the second electrode were laminated and wound up, and the sealing rubber was attached thereto and then inserted into the aluminum cover. Subsequently, an electrolyte solution (1M TEABF4 in ACN) was injected and then sealed to impregnate the winding device to prepare an electrochemical device (super capacitor) (see FIG. 2).

실험예Experimental Example 1: 결정질 존재 유무 1: presence of crystalline

The presence or absence of a crystalline part in the electrode material formed according to Example 1 was confirmed by X-ray diffraction analysis.

5 is an X-ray diffraction analysis pattern of the electrode material according to Example 1 of the present invention

Referring to FIG. 5, a peak at a point where 2θ is 25.5 ° appears to be high, which corresponds to crystalline. Therefore, it was confirmed through the X-ray diffraction analysis pattern that the electrode material of Example 1 includes both amorphous and crystalline.

실험예Experimental Example 2: 결정질의 층간 거리에 따른 정전 용량 측정 2: Capacitance measurement according to crystalline interlayer distance

Example 2 to 4

An electrochemical device was manufactured in the same manner as in Example 1, except that the content ratio of the carbon source and the activator was different from Example 1 in the range of 1: 0.8 to 1: 5.5.

Comparative example One

An electrochemical device was manufactured in the same manner as in Example 1, except that the activating treatment was performed using a content ratio of a carbon source and an activator of 1: 0.5.

Comparative example 2

An electrochemical device was manufactured in the same manner as in Example 1, except that the activating treatment was performed using a content ratio of a carbon source and an activator of 1: 6.

The interlayer distance of crystalline in the electrode material according to the Examples and Comparative Examples was measured by X-ray diffraction analysis.

In addition, the capacitance was measured by a Hi-EDLC 16CH instrument (manufactured by Human Instrument, Inc.) at a unit volume of 0.565 mA, and the results are shown in Table 2 below.

구분division	결정질의 층간 거리 [nm]Crystalline interlayer distance [nm]	정전 용량 [F/cc]Capacitance [F / cc]
실시예 2Example 2	0.3920.392	26.026.0
실시예 3Example 3	0.3810.381	24.424.4
실시예 4Example 4	0.3730.373	24.324.3
비교예 1Comparative Example 1	0.3520.352	15.615.6
비교예 2Comparative Example 2	0.4090.409	1818

Referring to Table 2, it can be seen that the electrode materials prepared in Examples 2 to 4 belong to the scope of the present invention because the crystalline interlayer distance in the crystalline range is 0.37 nm to 0.4 nm.

In addition, since the embodiments have a higher capacitance value than Comparative Examples 1 and 2, it can be seen that the electrode material of the present invention exhibits excellent electrical properties.

실험예Experimental Example 3: 3: 탄소원의Carbon source 단위 unit 중량에 대한 결정질의 비율에In the ratio of crystalline to weight 따른 정전 용량 측정 Capacitance measurements

Example 5 to 11 and Comparative example 3 to 7

An electrochemical device was manufactured in the same manner as in Example 1, except that the carbon source was heat-treated at different temperatures within the temperature range of 650 ° C to 900 ° C.

Specifically, Comparative Examples 3 and 4 were heat-treated at a temperature close to 650 ℃ even within the temperature range, Comparative Examples 5 to 7 was heat-treated at a temperature close to 900 ℃ even within the temperature range.

The specific surface areas of the electrode materials according to Examples 5 to 11 and Comparative Examples 3 to 7 were determined by the BET measurement method, and the capacitance was measured by the same method as Experimental Example 2, and the results are shown in Table 3 below.

구분division	x(결정질 비율)x (crystalline ratio)	y(비정질 비율)y (amorphous ratio)	비표면적[m²/g]Specific surface area [m ² / g]	정전 용량[F/cc]Capacitance [F / cc]
실시예 5Example 5	0.8900.890	0.1100.110	238238	25.525.5
실시예 6Example 6	0.8660.866	0.1340.134	285285	2626
실시예 7Example 7	0.8540.854	0.1460.146	309309	25.325.3
실시예 8Example 8	0.8480.848	0.1520.152	320320	2424
실시예 9Example 9	0.8270.827	0.1730.173	363363	24.424.4
실시예 10Example 10	0.5210.521	0.4790.479	969969	24.924.9
실시예 11Example 11	0.4530.453	0.5470.547	11041104	2626
비교예 3Comparative Example 3	0.9770.977	0.0230.023	6666	1919
비교예 4Comparative Example 4	0.9470.947	0.0530.053	124124	1818
비교예 5Comparative Example 5	0.3430.343	0.6570.657	13201320	2020
비교예 6Comparative Example 6	0.2020.202	0.7980.798	16001600	1919
비교예 7Comparative Example 7	0.0200.020	0.9800.980	19601960	1717

Referring to Table 3, all of the examples include crystalline within the range of 0.4 to 0.91, Comparative Examples were able to confirm that the ratio of the crystalline is outside the scope of the present invention.

Specifically, the heat treatment was performed within a temperature range of 650 ° C. to 900 ° C. Examples and comparative examples included both crystalline and amorphous materials.

Meanwhile, Comparative Examples 3 and 4, which were heat-treated at a high temperature even in the above temperature range, had a relatively high ratio of crystalline and a small specific surface area, and Comparative Examples 5 to 7 that were heat-treated at a low temperature within the above temperature range had a crystalline ratio It is relatively low and accordingly, the specific surface area is large.

In addition, it was confirmed that the capacitance value of the embodiments is significantly superior to the comparative examples.

Example 12 to 14 and Comparative example 8

An electrochemical device was manufactured in the same manner as in Example 1, except that the material for forming an electrode was manufactured using the ingredients and contents shown in Table 4 below.

실험예 4: 기공 분포도 측정Experimental Example 4: Measurement of Pore Distribution

In Example 1 and Comparative Example 8, the BET measurement method using N ₂ adsorption (device: SURFACE AREA ANALYZER (TRISTAR-3000), manufactured by MICROMERITICS) measured the distribution of pores having a specific pore diameter and a corresponding diameter.

The results are shown in Table 5 below and are shown in a graph of FIG. 6.

Referring to Table 5 and FIG. 6, the electrode material of Example 1 contained pores, and the volume of pores having a diameter of more than 0 nm and 1.0 nm or less was 74.61% of the total amorphous volume. It turns out that it belongs to the scope of the invention.

However, Comparative Example 8 was found to be out of the scope of the present invention because the volume of the pores having a diameter of more than 0 nm and 1.0 nm or less was 32.16% with respect to the total amorphous volume even if the pores were included.

실험예 5: 겉보기 밀도 및 정전 용량 측정Experimental Example 5: Measurement of apparent density and capacitance

The apparent density and capacitance of each of Examples 1, 12, 13 and Comparative Example 8 prepared by the above-described method were measured.

The apparent density was calculated by mass per unit volume, and the capacitance was measured by a Hi-EDLC 16CH instrument (manufactured by Human Instrument, Inc.) at 0.565 mA. The results are shown in Table 6 below.

Referring to Table 6, it was found that the apparent densities and capacitances were higher in Examples 1, 12, and 13 than in Comparative Example 8.

In addition, as a result of comparing the apparent density and the capacitance of the embodiments, the higher the electrode material content ratio was confirmed that the effect of improving the capacitance is maximized.

Although described above with reference to the embodiment is only an example and is not intended to limit the invention, those of ordinary skill in the art to which the present invention does not exemplify the above within the scope not departing from the essential characteristics of this embodiment It will be appreciated that many variations and applications are possible. For example, each component specifically shown in the embodiment can be modified. And differences relating to such modifications and applications will have to be construed as being included in the scope of the invention defined in the appended claims.

Claims

Including carbon sources

The carbon source includes crystalline and amorphous,

The crystalline comprises a crystal lattice,

The amorphous comprises pores,

The crystalline interlayer distance is 0.37 nm to 0.40 nm

The ratio of the crystalline to the unit weight (g) of the electrode material is 0.4 to 0.91.
The method according to claim 1,

Wherein the ratio of the crystalline to the unit weight (g) satisfies Equations 1 and 2 below:

Equation 1 20x + 2000y = k

[Equation 2] x + y = 1

(Wherein x is a crystalline ratio, y is an amorphous ratio and k is 200 to 1200).
The electrode material of claim 1, wherein the volume of pores having a diameter greater than 0 nm and less than or equal to 1 nm is 60% to 85% of the total volume of the amorphous material.
The electrode material of claim 1, wherein the volume of pores having a diameter of 0.6 nm to 0.9 nm in the pores is 45% to 75% of the total volume of the amorphous.
The electrode material of claim 1, wherein the volume of the pores with a diameter of 0.75 nm to 0.85 nm is 15% to 23% of the total volume of the amorphous.
The electrode material of claim 1, wherein the specific surface area of the electrode material is 200 m 2 / g to 1200 m 2 / g.
The apparent density of the electrode material is 0.7 g / cm 3 The electrode material being from 1.5 g / cm 3 .
A first electrode;

Second electrode; And

And a separator disposed between the first electrode and the second electrode.

An electrode material for forming at least one electrode of the first electrode and the second electrode,

Including carbon sources

The carbon source includes crystalline and amorphous,

The crystalline comprises a crystal lattice,

The amorphous comprises pores,

The crystalline interlayer distance is 0.37 nm to 0.40 nm

And the ratio of the crystalline to the unit weight (g) of the electrode material is 0.4 to 0.91.
The method according to claim 8,

Wherein the ratio of the crystalline to the unit weight (g) satisfies Equation 1 and Equation 2 below:

Equation 1 20x + 2000y = k

[Equation 2] x + y = 1

(Wherein x is a crystalline ratio, y is an amorphous ratio and k is 200 to 1200).
The electrochemical device of claim 8, wherein the volume of the pores having a diameter greater than 0 nm and less than or equal to 1 nm is 60% to 85% of the total amorphous volume.