KR20180038802A - Method of Preparing Heteroatom-Doped Carbon Materials Using Spent Coffee Grounds and Application of Electrode Materials Thereof - Google Patents

Abstract

The present invention relates to a method for preparing heteroatom-doped carbon materials using spent coffee grounds, which can be used as an electrode material of a fuel cell, a super capacitor or a redox flow battery by preparing nitrogen-doped carbon materials by activating a variety of spent coffee grounds from general coffee wastes, which are daily wastes, to coffee grounds, which extracted biodiesel, or by preparing a carbon material which is doped with boron and nitrogen simultaneously and has high specific surface area by being doped with a boron precursor.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a hetero-element-doped carbon material,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing carbon material doped with boron or nitrogen hetero-element using spent coffee grounds, and more particularly to a method for producing carbon material doped with boron or nitrogen from brewer's wastes, It can be used as an electrode material by synthesizing a carbon material having a high specific surface area and being doped with nitrogen or doped with boron and nitrogen at the same time through activation treatment of various waste coffee raw materials The present invention relates to a method for producing carbon materials using spent coffee grounds.

Coffee is the most abundant food ingredient in Korea, as Koreans' eating habits gradually become more westernized. Coffee beans, which account for 99.8% of coffee beans, have increased exponentially. According to the Ministry of Environment's press release (distributed on April 12, 2016), the amount of coffee waste produced annually in Korea is about 103,000 tons. Conventional disposal methods are to mix landfills with standard wastes in landfills. In this process, economic and social costs are incurred, such as the waste of landfills and landfill saturation.

The most widely used method to solve this problem is to use it as compost. Composting livestock manure has the disadvantage of producing odors, but composting recycled coffee waste is free from this problem. In addition, it has components such as nitrogen, phosphorus and potassium, making it suitable as an environmentally friendly compost.

In addition, the coffee grounds contain about 15% lipid, which is sufficient to obtain biomass fuel. The biodiesel can be produced by a extraction method using a solvent, and it can also be used as a bio pellet.

However, both of these methods have common limitations. But still remain in waste form after being used as fertilizer and biomass, respectively. We have tried to minimize the cost of landfilling, but there is a problem that can not be a fundamental solution to the complete treatment of coffee grounds.

The present inventors have made extensive efforts to find an economical method for recycling waste coffee. As a result, when the activator is added to a variety of waste coffee raw materials ranging from common coffee grounds, which are municipal wastes, to coffee grounds extracted from lipids and biodiesel, It was confirmed that a carbon material doped with hetero atoms of boron and nitrogen having a high specific surface area can be prepared and used as an electrode material for an electrode, a supercapacitor and a redox flow cell of a fuel cell, thereby completing the present invention .

Korean Registered Patent No. 10-1176969 (registered on August 20, 2012) Korean Registered Patent No. 10-0259546 (registered on March 23, 2000) Japanese Patent Laid-Open No. 2005-075686 (published on September 1, 2003)

It is an object of the present invention to provide a method and apparatus for semi-permanent utilization of coffee grounds using a variety of waste coffee materials, from ordinary coffee grounds to coffee grounds extracted from lipids and biodiesel, And a method of manufacturing a carbon material doped with a hetero-element such as carbon.

Another object of the present invention is to provide a carbonaceous material doped with nitrogen or doped with boron and nitrogen simultaneously produced by the above production method as an electrode material for a fuel cell, a super capacitor and a redox flow cell having excellent performance I have to.

In order to achieve the above object, the present invention is (a) the waste coffee grounds potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄₎ and one member selected from the group consisting of zinc chloride (ZnCl ₂₎ Mixing the above activator aqueous solution to obtain a slurry; (b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; And (c) purifying and drying the activated carbon of (b). The present invention also provides a method for producing a hetero-element-doped carbon material using waste coffee.

The invention also, (a) for the waste coffee grounds potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄₎ and zinc chloride (ZnCl ₂₎ with at least one active selected from the group consisting of the aqueous solution Mixing to obtain a slurry; (b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; (c) purifying and drying the activated carbon of (b), and then adding and mixing a boron precursor to obtain a slurry; (d) drying the slurry of (c) and heat-treating the slurry in the heating furnace to obtain activated carbon; And (e) purifying the activated carbon of (d). The present invention provides a method for producing a hetero-element-doped carbon material using waste coffee.

The present invention also provides a 1) nitrogen-doped porous carbon material produced by the above process and 2) a hetero-element-doped carbon material of boron and nitrogen co-doped porous carbon material.

The present invention also provides an electrode material comprising 1) a nitrogen doped porous carbon material and / or 2) a boron and nitrogen co-doped porous carbon material.

The manufacturing method according to the present invention uses a variety of waste coffee raw materials ranging from general coffee grounds, which are municipal wastes to coffee grounds extracted from lipids and biodiesel, as a high-performance battery electrode material, And biomass can be processed semi-permanently beyond the one-time, and at the same time, economic value can be created. In addition, when carbon dioxide is used for doping boron, it can contribute to reduction of carbon dioxide due to the carbon material conversion by the carbon dioxide reducing agent.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view schematically showing a manufacturing process for carrying out Examples 1 and 2 of the present invention. FIG.
Fig. 2 is a photograph showing a process for producing activated carbon in Example 1. Fig.
FIG. 3 is a graph showing a nitrogen adsorption isotherm during the specific surface area analysis of activated carbon according to Example 1. FIG.
FIG. 4 is a view showing a micropore distribution in the specific surface area analysis of activated carbon according to Example 1. FIG.
5 is a scanning electron microscope photograph of activated carbons according to Example 1. Fig.
FIG. 6 is a graph showing CV graphs of activated carbons according to Examples 1 and 2. FIG.
7 is a graph showing the performance and durability of activated carbons according to Examples 1 and 2. FIG.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, the carbon material produced through the activation treatment and the doping of boron or nitrogen from various kinds of waste coffee raw materials ranging from common coffee grounds, which are municipal wastes, to coffee grounds extracted from lipids and biodiesel is used as an electrode, a supercapacitor, It was confirmed that the electrode can be used as an electrode of a toxic flow cell.

Therefore, the invention in one aspect (a) the waste coffee grounds potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄₎ and zinc chloride (ZnCl ₂₎ to activate at least one selected from the group consisting of Mixing the aqueous solution to obtain a slurry; (b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; And (c) purifying and drying the activated carbon of (b). BACKGROUND OF THE INVENTION

In the present invention of (a) the waste coffee grounds potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO _4), and aqueous zinc chloride solution (ZnCl ₂₎ by at least one member selected from the group consisting of activator To obtain a slurry; (b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; (c) purifying and drying the activated carbon of (b), and then adding and mixing a boron precursor to obtain a slurry; (d) drying the slurry of (c) and heat-treating the slurry in the heating furnace to obtain activated carbon; And (e) purifying the activated carbon of (d). BACKGROUND OF THE INVENTION

The present invention relates to a process for producing a carbon material using spent coffee grounds as a raw material and a case where the carbon material produced through the process is applied as a battery electrode material. According to one preferred embodiment of the present invention, activated carbon is produced by applying potassium hydroxide activation method (KOH activation) to a variety of waste coffee raw materials ranging from general coffee grounds as municipal wastes to coffee grounds extracted from lipids and biodiesel . The activated carbon produced by the present invention has a high specific surface area and a structure doped with nitrogen and boron, and thus can be used as a high-quality electrode material for a battery.

Due to the nature of coffee waste, organic waste, there is a possibility of corruption, such as the formation of molds, depending on the storage method. It is possible to produce activated carbon of a constant quality irrespective of the spoilage state of the raw material. Ultimately, coffee waste can be used to produce high-performance electrode materials to create economic value.

The present invention introduces potassium hydroxide activation method to produce high quality activated carbon from coffee grounds. The potassium hydroxide activation method is a kind of chemical activation method and is a very effective treatment method for inducing the porous structure.

The recipe proposed by the present invention may comprise the following steps:

(a) drying the waste coffee grounds, and potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄₎ and zinc chloride (ZnCl ₂₎ as a slurry by mixing one or activator solution or more selected from the group consisting of ; (b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; (c) purifying and drying the activated carbon of (b), and then adding and mixing a boron precursor to obtain a slurry; (d) drying the slurry of (c) and heat-treating the slurry in the heating furnace to obtain activated carbon; And (e) purifying the activated carbon of (d).

Can be the recipe for invention presented is applicable to a case that does not dry the coffee grounds: (a) potassium hydroxide that contains the water waste coffee grounds (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO _4), and Mixing at least one activator aqueous solution selected from the group consisting of zinc chloride (ZnCl ₂ ) to obtain a slurry; (b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; (c) purifying and drying the activated carbon of (b), and then adding and mixing a boron precursor to obtain a slurry; (d) drying the slurry of (c) and heat-treating the slurry in the heating furnace to obtain activated carbon; And (e) purifying the activated carbon of (d).

A preparation method according to a preferred embodiment of the present invention is as follows:

(a) drying the coffee grounds as raw materials, mixing the dried coffee grounds with an aqueous solution of potassium hydroxide to obtain a slurry; (b) heat treating the partially or fully dried slurry in a furnace in which nitrogen flows; (c) purifying the generated activated carbon with hydrochloric acid, water, ethanol or the like; (d) drying the purified activated carbon; (e) Completion of nitrogen-doped activated carbon.

or

(a) mixing a coffee grounds containing water with an aqueous potassium hydroxide solution; (b) heat treating the slurry mixed in (a) and partially or wholly drying the slurry in a nitrogen furnace furnace; (c) purifying the generated activated carbon with hydrochloric acid, water, ethanol, and the like, and drying the activated carbon; (d) Completion of nitrogen-doped activated carbon.

This recipe is applicable not only to general coffee grounds but also to coffee grounds after lipid or biodiesel extraction. The production step of the activated carbon with this raw material is the same as the above step.

Due to the nature of coffee waste, organic waste, it is possible to produce spoiled raw materials such as fungi. The above manufacturing process is applicable even in the case of the raw materials.

The coffee grounds used in the step (a) of the present invention can be recovered from common waste coffee grounds or waste coffee grounds generated after the production of coffee beverages in the group consisting of benzene, xylene, chloroform, hexane, ethyl acetate, methanol, ethanol and cyclohexane It may be a waste coffee residue generated after extracting lipids or extracting biodiesel through a transfer reaction using one or more selected organic solvents or steam. That is, it includes coffee grounds that have been subjected to lipid or biodiesel extraction as well as ordinary coffee grounds in a conventional sense. It can also be used as a raw material in the manufacturing process, regardless of whether it is corruptible due to the characteristics of the organic waste.

In the step (a), it is possible to proceed to the next step without drying the coffee grounds.

The coffee grounds extracted from the biodiesel in step (a) can be classified according to the extraction method as follows: (1) Organic solvent (benzene, xylene, chloroform, hexane, ethyl acetate, methanol, ethanol, cyclohexane Etc.); (2) coffee grounds through in-situ transesterification; (3) steam residue and coffee grounds extracted with acid and base water vapor.

The aqueous solution of the activator is preferably used in a concentration of 6 mol or less, preferably 0.5 to 6M. At the time of mixing, the mass ratio of the coffee ground raw material and the activating agent is preferably 1: 0.1 to 1: 3.

The purpose of the step (a) is to secure the porosity through the chemical activation method. Therefore, the following activating agents may be used in addition to the potassium hydroxide but are not limited thereto: sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄ ) Zinc (ZnCl ₂ ).

The mixing of the steps (a) and (c) can be performed by a mixing method using an agitator and a sonication method, and the mixing time may vary depending on the amount of the raw material. Generally, 30 minutes to 1 hour is suitable.

In the step (a), the activator may be mixed with the coffee grounds in powder form in addition to mixing the activator such as potassium hydroxide in an aqueous solution.

It is preferable to dry at a temperature of 150 ° C. or lower, preferably 50 ° C. to 150 ° C. in the step (b), (c) or (d).

The gas of step (b) may be an exhaust gas containing nitrogen or nitrogen, or an inert gas such as argon.

When the above step (d) the heat treatment, the gas flow rate was increased to 400 ~ 1000 ℃ at a heating rate of 10 ~ 3000㎖min ^-1 are suitable, and 1 ~ 10 ℃ min ^-1 2 hours or less, preferably 1 It is possible to increase the temperature to 400 ~ 1000 ° C at a heating rate of ~ 5 ° C min ^-1 and then heat-treat for 0.5 ~ 2 hours.

The heat treatment of step (d) the flow during the conversion of carbon dioxide to carbon can be maintained to 10 ~ 3000㎖min ^-1 is 0.5 ~ 2 hours at 500-1000 ℃ at a heating rate of 1 ~ 5 ℃ min ^-1.

If the carbon dioxide is not converted to carbon, the flow rate of the exhaust gas containing nitrogen, argon gas or nitrogen is 10 to 3000 mlmin ^-1 , and the temperature of 1 to 5 ° C min ^-1 It can be maintained at 500 to 1000 ° C for 0.5 to 2 hours.

The tablets of (c) and (e) can be carried out by adding hydrochloric acid, water and ethanol. Particularly, in the purification of step (e), the main purpose is to remove the salts remaining on the activated carbon after the heat treatment. In this case, hydrochloric acid, distilled water and ethanol can be used sequentially.

The boron precursor may be boron oxide (B ₂ O ₃ ), boric acid (H ₂ BO ₃ ), lithium borohydride (LiBH ₄ ), potassium borohydride (KBH ₄ ), Magnesium borohydride (Mg (BH ₄ ) ₂ ), calcium boron hydride (Ca (BH ₄ ) ₂ ), strontium boron hydride (Sr (BH ₄ ) ₂ ) or ammonia borane (NH ₃ BH ₃ ) .

When the boron precursor solution is prepared, organic solvents such as dimethyl sulfoxide, dimethylformamide and the like can be used as the solvent, and they do not react with sodium borohydride. Solutions can be made using water, alcohols or organic solvents to the extent that other boron precursors mentioned above do not react either.

The concentration of the boron precursor solution may vary depending on the solubility depending on the solvent. In general, the use of a 0.5 to 6 molar solution is preferred.

The present invention also includes a method for producing high-quality carbon materials by adding a post-treatment process to the above-described method for producing carbon materials. (I) mixing a boron precursor solution such as a nitrogen-doped activated carbon and a sodium borohydride (NaBH ₄ ) solution with a coffee ground as a raw material; (ii) drying the mixed slurry; (iii) heat treating the dried slurry in a furnace through which carbon dioxide flows; (iv) purifying the generated activated carbon with hydrochloric acid, water, ethanol or the like; (v) drying the purified activated carbon; And (vi) completion of boron and nitrogen-doped activated carbon.

The step (i) may be performed by a mixing method using an agitator and a sonication method, and the mixing time may vary depending on the amount of the raw material. Generally, 30 minutes to 1 hour is suitable.

In addition to the method of mixing the boron precursor in the aqueous solution state in the step (i), it may be mixed with the activated carbon doped with nitrogen in powder form.

The step (ii) is preferably carried out at a temperature of 150 ° C or less, preferably 50 to 150 ° C.

And the carbon dioxide is converted through the boron precursor in the step (iii). In this process, boron is doped in the carbon structure of the activated carbon. Therefore, the flow rate and the heat treatment condition for carbon dioxide are important, and the flow rate is preferably 10 to 3000 mlmin ^-1 . In the case of heat treatment, it is preferable to maintain the maximum temperature at 500-1000 ° C for 2 hours at a heating rate of 1 to 5 ° C min ^-1 .

If carbon dioxide is not converted into carbon in the step (iii), an inert gas other than carbon dioxide or an exhaust gas containing nitrogen and nitrogen may be used. The flow rate and the heat treatment conditions are important, and the flow rate is preferably 10 to 3000 mlmin ^-1 . In the case of heat treatment, it is preferable to maintain the maximum temperature at 500-1000 ° C for 2 hours at a heating rate of 1 to 5 ° C min ^-1 .

In the step (iv), the main purpose is to remove the salts remaining in the activated carbon after the heat treatment. In this case, hydrochloric acid, distilled water, and ethanol are sequentially used.

The step (v) is preferably carried out at a temperature of 150 ° C or less, preferably 50 to 150 ° C.

The product obtained in the step (vi) is activated carbon doped with boron and nitrogen, and this porous carbon material can be used as an electrode material of a secondary battery.

Thus, in another aspect of the present invention, the present invention relates to a 1) nitrogen-doped porous carbon material and 2) a hetero-element-doped carbon material of boron and nitrogen co-doped porous carbon material produced by the above production method and having a specific surface area of 500 to 3000 m ² / g. < / RTI >

Still another aspect of the invention relates to an electrode material comprising 1) a nitrogen doped porous carbonaceous material and / or 2) a boron and nitrogen co-doped porous carbonaceous material.

The carbon material is suitable for use as an electrode material for a supercapacitor or a fuel cell. In addition, since it is active on bromine oxidation / reduction (Br ₂ + 2e ^- ⇔ 2Br ^- ), it can be used as anode material in Zn-Br redox flow cell.

In addition, lipid or biodiesel can be obtained as an additional product by the method of producing a hetero-carbon material using waste coffee of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are for illustrative purposes only and that the scope of the present invention is not limited by these embodiments.

[Example]

Example  1: Nitrogen from various coffee grounds Doped  Preparation of activated carbon and its zinc-bromide Redox flow cell (Zinc-Bromine Redox  Flow Battery) Application to anode material

The overall manufacturing process follows the 'Production of nitrogen-doped activated carbon' part of FIG.

The coffee grounds were divided into two groups to produce activated carbon. The first group is regular waste coffee grounds, and the second group is waste coffee residue after extracting lipids or biodiesel. The coffee grounds extracted from lipids or biodiesel are divided into three types according to the extraction method used: 1) coffee grounds extracted with chloroform; 2) coffee residue through in-situ ester exchange; 3) Coffee grounds extracted with steam. Therefore, activated carbon was prepared for four types of coffee grounds, which were not extracted from waste coffee residue.

Two grams of the coffee grounds dried in one experiment were taken and mixed with an aqueous solution of potassium hydroxide. The concentration of the aqueous solution used was 6 molar, and the amount was adjusted so that the mass ratio to the coffee grounds was 1: 0.5. By sonication for about 30 minutes, potassium hydroxide ions were allowed to penetrate evenly into the coffee grounds.

After sonication, the mixture was in the form of a slurry, which was laid flat on a crucible (Fig. 2-1) and dried in a vacuum oven set at 100 ° C for one day (Fig. 2-2)

The crucible containing the dried slurry was placed in an electric furnace and purged for 30 minutes by flowing nitrogen at 50 mlmin ^-1 in order to remove the oxidizing gas inside the furnace. Thereafter, the mixture was heated to 750 ° C at a heating rate of 5 ° C min ^-1 , and then heat-treated for 1 hour to activate.

The heat-treated activated carbon was dried in a vacuum oven set at 100 ° C. for one day after two purification steps of hydrochloric acid (2 molar) treatment, two distilled water treatment and one ethanol treatment. After drying, finally activated carbon doped with nitrogen was obtained (Fig. 2-3)

The activated carbon produced by the present invention has a very high specific surface area value through BET analysis. FIG. 3 shows the N ₂ adsorption isotherms of the activated carbon, and FIG. 4 shows the distribution of micropores affecting the electrochemical activity. The results are summarized in Table 1.

Sample SBET
(m ² / g) Pore volume
(cm < ³ > / g) Micropore Mesopore Ratio One 21.89 0.0035 - - - 2 1501.68 0.60 0.57 (0.57) 0.02 28.5 3 2300.64 1.02 0.91 (0.90) 0.12 7.6

1: Comparative group without potassium hydroxide activation

2: Activated carbon from common coffee grounds

3: Activated carbon from biodiesel-extracted coffee grounds

As a result, it can be seen that the activated carbon synthesized from the coffee grounds has a high specific surface area and numerous micro pores. This will serve as a favorable part of the zinc-bromodeoxane flow cell positive reaction.

The porous structure of the activated carbon as identified in the specific surface area analysis was also confirmed by scanning electron microscopy (SEM) (FIG. 5). Fig. 5 (a) shows activated carbon made from common coffee grounds, and b is activated carbon with biodiesel extracted coffee grounds as a raw material.

In order to measure the electrochemical activity of the anode reaction (Br ₂ + e ^- ⇔ 2Br ^- ) of the zinc-bromideox flow cell, the activity test was performed in a three-electrode system using a quaternary ammonium bromide (QBr) solution as an electrolyte. The activity of each activated carbon is shown by a graph of a cyclic voltammetry (CV) method (FIG. 6). In FIG. 6, a is activated carbon made from common coffee grounds, b is activated carbon from biodiesel extracted coffee grounds , and c is the result of the activated carbon of Example 2. Here, the area is proportional to the activity. Thus, performance and durability were shown at the same time by arranging the variation of the cycle according to each activated carbon (Fig. 7)

Example  2: nitrogen and boron Doped  Preparation of activated carbon and its zinc-bromide Redox flow cell (Zinc-Bromine Redox  Flow Battery) Application to anode material

Example 2 is a post-treatment step of Example 1 for obtaining activated carbon of good quality and follows the part of 'Production of boron and nitrogen-doped activated carbon' of FIG. 1.

Example 2 was conducted on the activated carbon prepared in Example 1, and the activated carbon having the common coffee grounds as the raw material.

Approximately 1 g of activated carbon was taken and mixed with a 1 molar sodium borohydride solution. At this time, the solvent used was dimethylsulfoxide, and the mass ratio of activated carbon was 1: 0.5. By sonication for about 30 minutes, sodium borohydride ions were allowed to penetrate evenly into the activated carbon.

The slurry-formulated mixture was placed in a crucible and dried at 150 ° C for one day only.

The crucible containing the dried slurry was placed in an electric furnace and purged for 30 minutes by flowing nitrogen at 50 mlmin ^-1 in order to remove the oxidizing gas inside the furnace. Thereafter, the mixture was heated up to 500 DEG C at a heating rate of 5 DEG C min <" ^{1 &} gt ;, and then carbon dioxide gas was introduced to cause carbon dioxide conversion. The flow rate at this time was 75 ml min ^-1 . Then, heat treatment was performed for 2 hours.

The heat-treated activated carbon was dried in a vacuum oven set at 100 ° C. for one day after two purification steps of hydrochloric acid (2 molar) treatment, two distilled water treatment and one ethanol treatment. After drying, activated carbon doped with boron and nitrogen was finally obtained.

Since boron and nitrogen are doped, the zinc-bromide redox flow cell will be a favorable part of the anodic reaction. In order to grasp this, an activity test was carried out in the same manner as in Example 1. CV graphs related thereto and graphs showing performance and durability are shown (FIGS. 6 and 7).

From Examples 1 and 2, it was confirmed that nitrogen-doped activated carbon and nitrogen-boron-doped activated carbon were produced from coffee grounds, which can be used as a cathode material of Zinc-Bromine Redox Flow Battery .

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (19)

A method for producing a hetero-element-doped carbonaceous material using waste coffee comprising the steps of:
(a) the waste coffee grounds potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄₎ and zinc chloride (ZnCl ₂₎ to obtain a slurry by mixing the selected one activator aqueous solution of at least one kind from the group consisting of ;
(b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon; And
(c) purifying and drying the activated carbon of (b).
A method for producing a hetero-element-doped carbonaceous material using waste coffee comprising the steps of:
(a) the waste coffee grounds potassium hydroxide (KOH), sodium hydroxide (NaOH), phosphoric acid (H ₃ PO ₄₎ and zinc chloride (ZnCl ₂₎ to obtain a slurry by mixing the selected one activator aqueous solution of at least one kind from the group consisting of ;
(b) drying the slurry of (a) and subjecting it to heat treatment in a furnace into which an inert gas is introduced to obtain activated carbon;
(c) purifying and drying the activated carbon of (b), and then adding and mixing a boron precursor to obtain a slurry;
(d) drying the slurry of (c) and heat-treating the slurry in the heating furnace to obtain activated carbon; And
(e) purifying the activated carbon of (d).
The method according to claim 1 or 2, wherein the waste coffee grounds are composed of common waste coffee grounds or waste coffee grounds generated after the production of coffee beverages, which are composed of benzene, xylene, chloroform, hexane, ethyl acetate, methanol, ethanol and cyclohexane Wherein at least one organic solvent or steam selected from the group consisting of bubbles is used to extract lipids or biodiesel from the biodiesel through a diffusion reaction.
The method according to claim 1 or 2, wherein the aqueous solution of the activator is mixed after drying the waste coffee grounds of step (a) at 50 to 150 ° C, and drying of step (b), (c) Wherein the drying step is performed at a temperature of 50 to 150 ° C.
The method of claim 1 or 2, wherein the purification of step (c) is performed by adding hydrochloric acid, water and ethanol.
The method of claim 1 or 2, wherein the activator aqueous solution is 0.5 to 6M, and the mass ratio of waste coffee grounds and activator is 1: 0.1 to 1: 3. ≪ / RTI >
The method of claim 1 or 2, wherein the mixing of steps (a) and (c) uses a stirrer or sonication in the solid or slurry state. Gt;
The method according to claim 1 or 2, wherein the heat treatment in step (b) is performed at a temperature of 1 to 10 占 폚 min- ¹ under an exhaust gas containing nitrogen or argon gas or nitrogen, Wherein the heat treatment is performed for a period of time.
The method of claim 2, wherein the heat treatment in step (d) when switching the carbon dioxide in the carbon flow rate is 10 ~ 3000㎖min ^-1 and 1 and at a heating rate of 5 min ^-1 ℃ at 500-1000 ℃ 0.5 ~ 2 sigan Wherein the carbonaceous material is maintained at a temperature of < RTI ID = 0.0 > 100 C < / RTI >
The method according to claim 2, wherein the heat treatment in step (d) is performed so that the flow rate of the exhaust gas containing nitrogen, argon gas or nitrogen is 10-3000 ml min ^-1 when the carbon dioxide is not converted to carbon, ^-1 > at 500 to 1000 DEG C for 0.5 to 2 hours.
The method of claim 2, wherein the boron precursor is sodium boron hydride (NaBH _4), boron oxide (B ₂ O _3), boric Acid (H ₂ BO _3), lithium-boron hydride (LiBH _4), potassium boron hydride (KBH _4), magnesium boron hydride _{(Mg (BH 4) 2)} , calcium boron hydride _{(Ca (BH 4) 2)} , strontium boron hydride (Sr (BH _{4) 2)} and ammonia borane (NH ₃ BH < / RTI >< RTI ID = 0.0 > ₃ ). ≪ / RTI >
The method of claim 1 or 2, wherein the lipid or biodiesel is obtained as a by-product.
A hetero-element-doped carbon material characterized in that the carbon material produced by the method of claim 1 is doped with nitrogen.
A hetero-element-doped carbon material characterized in that the carbon material produced by the method of claim 2 is doped with boron and nitrogen.
An electrode material comprising the hetero-element-doped carbon material of claim 13.
An electrode material comprising the hetero-element-doped carbon material of claim 14.
The electrode material according to claim 15 or 16, wherein the electrode material is a fuel cell, a supercapacitor, or a redox flow cell.
An electrode material comprising the hetero-element-doped carbon material of claim 13 and the hetero-element-doped carbon material of claim 13.
The electrode material according to claim 18, which is an electrode material of a fuel cell, a supercapacitor or a redox flow cell.

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