KR20210084153A - METHOD FOR SYNTHESIZING Cu1.81S WHICH ONE KIND OF COPPER SULFIDE - Google Patents

Abstract

The present invention relates to a method for synthesizing Cu_1.81S compound as one kind of copper sulfide compounds. The method includes the steps of: (a) mixing powdery copper (Cu) with powdery sulfur (S) at a predetermined ratio to provide a copper-sulfur mixture as a first precursor for synthesizing the Cu_1.81S compound; (b) subjecting the copper-sulfur mixture as the first precursor to a predetermined ball milling process to provide Cu_1.96S as a second precursor for synthesizing the Cu_1.81S compound; and (c) subjecting the Cu_1.96S as the second precursor or a third precursor derived therefrom to a predetermined wet milling process to provide a Cu_1.81S compound.

Description

Method for synthesizing Cu1.81S copper sulfide compound {METHOD FOR SYNTHESIZING Cu1.81S WHICH ONE KIND OF COPPER SULFIDE}

The present invention relates to a method for synthesizing a _{Cu 1.81} S compound, which is a type of copper sulfide compound.

_{In recent decades, Cu 2-x} S, a copper sulfide compound, has been the subject of much interest and research due to its rich phase, complex structure, and excellent tunability. It is being used or expected to be used in a wide range of fields such as batteries, electrodes, catalysts, super-ion materials, etc.

Among them, Cu _1.81 S has excellent electrochemical performance while being stable, and when it has a tetragonal phase, advantages such as better thermoelectric properties and electrical conductivity are known.

However, a _{relatively small number of methods for synthesizing the Cu 1.81} S compound are known due to technical difficulties. In the prior literature (Applied Surface Science, 2014, Vol.315, pp.235-240, "Controlled synthesis of novel rod-like Cu _1.81 S nanostructures and field emission properties"), _{a method for synthesizing Cu 1.81} S compound at high temperature Although the synthesis method based on the heat treatment process is disclosed, this method has a disadvantage in that the efficiency may be _{lowered in synthesizing the Cu 1.81 S compound as a separate heat treatment process must be performed.}

Therefore, there is still a need for a method capable of efficiently synthesizing _{Cu 1.81 S compound.}

Accordingly, an object of the present invention is to provide a method capable of efficiently synthesizing a _{Cu 1.81} S compound from a copper and sulfur mixture by performing a predetermined ball milling process at room temperature.

In addition, the present invention provides a method for efficiently synthesizing _{Cu 1.81} S compound from a copper and sulfur mixture by performing a predetermined ball milling process and a wet milling process at room temperature for other purposes.

Another object of the present invention is to provide a method capable of efficiently synthesizing a _{Cu 1.81} S compound from a copper and sulfur mixture by performing a predetermined ball milling process, a heat treatment process, and a Ÿ‡ milling process.

Another object of the present invention is to provide a method capable of producing a _{Cu 1.81} S compound having a tetragonal phase by changing the phase of a specific copper sulfide compound by performing a predetermined Ÿ‡ milling process at room temperature. do.

In order to achieve the object of the present invention as described above and to realize the characteristic effects of the present invention to be described later, the characteristic configuration of the present invention is as follows.

According to one aspect of the present invention, in the method of synthesizing _{Cu 1.81 S compound among copper sulfide compounds, (a) as a first precursor for synthesizing the Cu 1.81} S compound, copper (Cu) in powder form and powder form producing a copper-sulfur mixture in which sulfur (S) is mixed in a predetermined ratio; (b) performing a predetermined ball milling process on the copper-sulfur mixture as the first precursor to generate _{Cu 1.96} S as a second precursor for synthesizing _{the Cu 1.81 S compound;} and (c) performing a predetermined wet milling process on _{the Cu 1.96} S as the generated second precursor _{or a third precursor calculated therefrom to generate the Cu 1.81} S compound. A method for synthesizing a Cu _1.81 S compound is provided.

As an example, in the predetermined ball milling process, the copper-sulfur mixture as the first precursor corresponding to a first mass, and a plurality of first milling balls for predetermined ball milling in an atmosphere of a predetermined inert gas There is provided a method for synthesizing _{Cu 1.81} S compound, characterized in that it is put into a container and performed for a predetermined first ball milling time at a predetermined first ball milling revolutions per minute.

As an example, the predetermined ratio to the copper-sulfur mixture is a mole percent ratio of [Cu]:[S]=2:1, wherein the first mass is 5 g, There is provided a method for synthesizing _{Cu 1.81} S compound, characterized in that the first ball milling revolutions per minute is 500 rpm, and the predetermined first ball milling time is 2 hours.

As an example, the predetermined Ÿ‡ milling process includes a Cu _1.96 S compound as the second precursor corresponding to the second mass, a plurality of second milling balls, and a predetermined solvent - the predetermined solvent is isopropyl alcohol ( IPA), including at least one of heptane, and tetrahydrofuran (THF) - is put into a predetermined Ÿ‡ milling vessel, and the predetermined first Ÿ‡ milling revolutions per minute _{A method for synthesizing a Cu 1.81} S compound is provided, characterized in that the first Ÿ‡ milling time is performed.

As an example, the second mass is 2 g, the predetermined first Ÿ‡ milling revolutions per minute is 200 rpm, and the predetermined first Ÿ‡ milling time is at least 12 hours or longer and 24 There is provided a method characterized in that less than or equal to time.

As an example, before step (c), (c0) performing a heat treatment on the _{Cu 1.96 S compound as the generated second precursor under a predetermined heat treatment condition to synthesize the Cu 1.81} S compound. 3 producing a heat-treated Cu _{2 S compound as a precursor;} Cu characterized in that in the step (c), the predetermined Ÿ‡ milling process is performed on the _{heat-treated Cu 2} S compound as the third precursor to generate _{the Cu 1.81 S compound 1.81} Methods for synthesizing S compounds are provided.

As an example, the predetermined ratio to the copper-sulfur mixture is a mole percent ratio of [Cu]:[S]=2:1, wherein the first mass is 5 g, The first ball milling revolutions per minute is characterized in that 500rpm, the predetermined first ball milling time is characterized in that 2 hours, the predetermined heat treatment conditions, heat treatment at a temperature of 400 degrees Celsius for 2 hours There is provided a method for synthesizing _{Cu 1.81} S compound, characterized in that it is carried out.

As an example, in the predetermined Ÿ‡ milling process, the heat-treated Cu ₂ S compound as the third precursor corresponding to a third mass, a plurality of third milling balls, and a predetermined solvent - the predetermined solvent is iso By adding at least one of propyl alcohol (IPA), heptane, and tetrahydrofuran (THF) into a predetermined Ÿ‡ milling vessel, a predetermined second Ÿ‡ milling revolutions per minute _{A method for synthesizing a Cu 1.81} S compound is provided, characterized in that it is carried out for a predetermined second Ÿ‡ milling time.

As an example, the third mass is 2 g, the predetermined second Ÿ‡ milling revolutions per minute is 200 rpm, and the predetermined second Ÿ‡ milling time is at least 24 hours or more and 72 hours. _{A method for synthesizing Cu 1.81} S compound is provided, characterized in that the time is less than or equal to the time.

As an example, there is provided a method characterized in that _{the produced Cu 1.81 S compound has a tetragonal phase.}

In addition, according to another aspect of the present invention, in the method of synthesizing _{Cu 1.81 S compound among copper sulfide compounds, (a) as a first precursor for synthesizing the Cu 1.81} S compound, copper (Cu) in powder form and producing a copper-sulfur mixture in which sulfur (S) in powder form is mixed in a predetermined ratio; and (b) performing a predetermined ball milling process on the copper-sulfur mixture as the first precursor _{to produce the Cu 1.81} S compound; A method for synthesizing a Cu _{1.81 S compound comprising a is provided.}

As an example, in the predetermined ball milling process, the copper-sulfur mixture as the first precursor corresponding to the fourth mass and a plurality of fourth milling balls are used in a predetermined inert gas atmosphere environment for a predetermined ball milling vessel. There is provided a method for synthesizing _{Cu 1.81} S compound, characterized in that the second ball milling is performed for a predetermined second ball milling time at a predetermined second ball milling revolutions per minute.

As an example, the predetermined ratio to the copper-sulfur mixture is a mole percent ratio of [Cu]:[S]=2:1, and the fourth mass is 5 g, 2 ball milling revolutions per minute is characterized in that 500rpm, the second ball milling time is _{provided a Cu 1.81} S compound synthesis method, characterized in that 36 hours.

As an example, there is provided a method characterized in that _{the produced Cu 1.81 S compound has a tetragonal phase.}

According to the present invention, the following effects are obtained.

The present invention may provide a method for efficiently synthesizing _{Cu 1.81} S compound from a copper and sulfur mixture by performing a predetermined ball milling process at room temperature.

In addition, the present invention can provide a method for efficiently synthesizing a _{Cu 1.81} S compound from a copper and sulfur mixture by performing a predetermined ball milling process and a wet milling process at room temperature. have.

In addition, the present invention can provide a method for efficiently synthesizing a _{Cu 1.81} S compound from a copper and sulfur mixture by performing a predetermined ball milling process, a heat treatment process, and a Ÿ‡ milling process.

In addition, the present invention can provide a method capable of producing a _{Cu 1.81} S compound having a tetragonal phase by changing the phase of a specific copper sulfide compound by performing a predetermined Ÿ‡ milling process at room temperature.

1 is a diagram schematically illustrating methods capable of synthesizing a _{Cu 1.81} S compound from a copper-sulfur mixture, according to an embodiment of the present invention.
2 is an XRD graph of each result generated by time by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention, Cu _1.96 S compound which is a result generated at a specific time, and It is a figure showing the SEM image of the _{Cu 1.81 S compound.}
Figure 3a, according to an embodiment of the present invention, a Cu _1.96 S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture, is produced by performing a predetermined heat treatment on the produced _{Cu 1.96 S compound} It is a view showing an XRD graph of each _{Cu 1.81} S compound produced by performing a predetermined Ÿ‡ milling process on the _{Cu 2} S compound and the produced Cu _{2 S .}
Figure 3b, a predetermined Ÿ ‡ milling process, the resultant Cu _1.81 S compound XRD graphs, the heat-treated Cu ₂ S compounds on the performed 24 hours with respect to, a heat-treated Cu ₂ S compounds in accordance with one embodiment of the present invention It is a diagram showing the XRD graph _{of the Cu 1.81} S compound, which is the result of performing a predetermined Ÿ‡ milling process for 72 hours.
3C is a view showing an XRD graph and an SEM image of a _{Cu 1.81} S compound, which is a result of performing a predetermined Ÿ‡ milling process on the _{heat-treated Cu 2} S compound for 72 hours, according to an embodiment of the present invention.
3D is an XRD graph and SEM showing that the result of performing a predetermined Ÿ‡ milling process on the _{heat-treated Cu 2 S compound for 12 hours is Cu 1.81} S, not Cu ₂ S, as an example for comparison with the present invention; It is a drawing representing an image.
Figure 4 is, as an example for comparison with the present invention, the copper-performing a given ball milling process with respect to the sulfur compounds to generate Cu _1.96 S compound, and performing a predetermined heat treatment to the resulting Cu _1.96 S compound and a diagram showing an XRD chart, and a SEM image showing that generates a Cu ₂ S compounds, performed 72 h Stirling predetermined process with respect to the generated Cu ₂ S resultant compound is Cu ₂ S.
5, as an example for comparison with the present invention, a predetermined ball milling process, a predetermined heat treatment, and a predetermined Ÿ‡ milling process are performed with a mixing ratio of the copper-sulfur mixture in a 1:1 mole percent ratio. It is a diagram showing an XRD graph, an HAADF analysis image, and an SEM image showing that the resulting product is CuS.
6 is, as an example for comparison with the present invention, copper - by performing a predetermined ball-milling process with respect to the sulfur compounds to generate Cu _1.96 S compound, and performing a heat treatment with respect to the resulting Cu _1.96 S compound Cu _It is a view showing each XRD graph of the result obtained by producing a ₂ S compound and performing a predetermined Ÿ‡ milling using different solvents for the produced Cu 2 S compound.
Figure 7a, according to an embodiment of the present invention, a predetermined Ÿ‡ milling process is performed on the Cu _1.96 S compound produced by performing a predetermined ball milling process on the copper-sulfur mixture and the Cu _{1.96 S compound produced} It is a figure showing the XRD graph of each _{Cu 1.81} S compound as a result.
_{7b is a Cu 1.96} S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention, a predetermined Ÿ‡ milling process for 12 hours and 24 hours It is a figure showing the XRD graph of each _{Cu 1.81 S compound as a result.
Figure 7c is a Cu 1.96} S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention, a result of performing a predetermined Ÿ‡ milling process for 24 hours; _It is a figure showing the XRD graph and the SEM image of the 1.81 S compound.
7d is a result of performing a predetermined Ÿ‡ milling process for 72 hours on _{a Cu 1.96} S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture as an example for comparison with the present invention; It is a figure showing an XRD graph and an SEM image showing _{Cu 1.75} S rather than _{Cu 1.81 S.}
Figure 8 is, as an example for comparison with the present invention, the copper-performing a given ball milling process with respect to the sulfur compounds to a desired Stirling process with respect to Cu _1.96 S compounds produced a Cu _1.96 S compound, and the resulting It is a diagram showing an XRD graph and an SEM image showing that the result of 72 hours is Cu _{2 S.}
9 is a view showing an XRD graph of a _{Cu 1.81} S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0010] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0010] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0023] Reference is made to the accompanying drawings, which show by way of illustration specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the present invention. It should be understood that the various embodiments of the present invention are different but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein with respect to one embodiment may be embodied in other embodiments without departing from the spirit and scope of the invention.

In addition, it should be understood that the location or arrangement of individual components within each disclosed embodiment may be changed without departing from the spirit and scope of the present invention. Accordingly, the detailed description set forth below is not intended to be taken in a limiting sense, and the scope of the invention, if properly described, is limited only by the appended claims, along with all scope equivalents to those claimed. Like reference numerals in the drawings refer to the same or similar functions throughout the various aspects.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to enable those of ordinary skill in the art to easily practice the present invention.

1 is a diagram schematically illustrating methods capable of synthesizing a _{Cu 1.81} S compound from a copper-sulfur mixture, according to an embodiment of the present invention.

Referring to FIG. 1 , _{the method for synthesizing Cu 1.81} S compound in the present invention is basically a part of a predetermined ball milling process, a predetermined heat treatment, and a predetermined Ÿ‡ milling (wet milling) process. Or it can be done by performing a process including all.

Specifically, in one embodiment of the present invention, a method for the synthesis of Cu _1.81 S compounds, first, a copper (Cu) powder and sulfur (S) powder as the first first precursor for the synthesis of Cu _1.81 S compound It can begin by producing a copper-sulfur mixture mixed in a predetermined mole percent ratio as the first precursor.

Then, with respect to the produced copper-sulfur mixture as a first precursor, a predetermined ball milling process may be performed, and according to the time for performing the predetermined ball milling, a method _{for synthesizing the Cu 1.81} S compound is performed. _{A Cu 1.96} S compound as the second precursor may be generated, or a Cu _1.81 S compound may be directly generated.

In this case, the ball milling process is a milling process in contrast to the Ÿ‡ milling process to be described later, and dry ball milling in which a separate solvent is not used may be performed.

As such, the data of the actual experimental example related to the time for performing a predetermined ball milling on the copper-sulfur mixture as the first precursor is shown in FIG.

2 is an XRD graph of each result generated by time by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention, Cu _1.96 S compound which is a result generated at a specific time, and It is a figure showing the SEM image of the _{Cu 1.81 S compound.}

Referring to FIG. 2 , the predetermined ball milling is performed on the copper-sulfur compound as the first precursor for up to 36 hours, and XRD (X-Ray Diffraction) analysis is performed on the results generated for each specific time in the process. Data presented graphically are shown. Based on each pattern of these XRD graphs, it can be seen that _{a compound of Cu 1.96} S is produced when a predetermined ball milling is performed for 2 hours, whereas a compound of _{Cu 1.81} S is produced when a predetermined ball milling is performed for 36 hours. can In addition, in FIG. 2, _{SEM images of the produced Cu 1.96} S and Cu _1.81 S are shown together at the same magnification (10,000 times on the left, 5,000 times on the right), through which a predetermined ball milling of Cu _{1.96 was performed for 2 hours.} It can be seen that the particle size of _{Cu 1.81} S after a predetermined ball milling for 36 hours was smaller than that of S.

_{Then, when the Cu 1.96} S compound as the second precursor is generated as described above, the Cu 1.96 S compound as the generated second precursor or a third precursor calculated by performing a separate treatment on the _{Cu 1.96 S compound as a result of a predetermined Ÿ‡} A wet milling process may be performed to _{produce a Cu 1.81} S compound. At this time, according to detailed implementation conditions of the invention, the Cu _1.81 S compound finally produced may have a tetragonal phase.

_{As such, the method of synthesizing the Cu 1.81} S compound based on the predetermined ball milling and Ÿ‡ milling can be largely composed of three methods as shown in FIG. 1 , and each method is described in a specific example and a separate method. It will be described in more detail below with reference to the drawings.

[Cu _1.81 S compound synthesis method 1]

A specific embodiment of the present invention for synthesizing the Cu _1.81 S compound will be described with reference to FIGS. 3A to 3D as follows.

Figure 3a, according to an embodiment of the present invention, a Cu _1.96 S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture, is produced by performing a predetermined heat treatment on the produced _{Cu 1.96 S compound} It is a view showing an XRD graph of each _{Cu 1.81} S compound produced by performing a predetermined Ÿ‡ milling process on the _{Cu 2} S compound and the produced Cu _{2 S .}

First, _{as the first precursor for synthesizing the Cu 1.81} S compound, a copper-sulfur mixture in which copper (Cu) powder and sulfur (S) powder are mixed in a predetermined molar ratio may be generated as the first precursor. At this time, as an experimental condition as a specific example, the molar ratio of copper powder and sulfur powder may be set to [Cu]:[S]=2:1, and each atomic weight ratio is [Cu]:[S]=2 Since it is :1, the mass ratio of the copper powder and the sulfur powder that is finally added to produce the first precursor may be 4:1, but is not limited thereto, and the mole percent ratio and input amount, etc. are may vary.

In an actual experimental example for the present invention, 3.993 g of copper powder (Alfa Aesar, 99.9%) and 1.007 g of sulfur powder (Sigma-Aldrich, 99.98%) were added to generate 5 g of a copper-sulfur mixture as a first precursor and used and no additional additive input or purification process was performed.

Next, a predetermined ball milling process may be performed on the produced copper-sulfur mixture as the first precursor. Specifically, a copper-sulfur mixture as a first precursor corresponding to the first mass, and a plurality of first milling balls are put into a predetermined ball milling container in an atmosphere environment of a predetermined inert gas to perform a predetermined first ball milling A dry ball milling process may be performed for a predetermined first ball milling time at the number of revolutions per minute. At this time, as an experimental condition as a specific example, the first mass of the copper-sulfur mixture as the first precursor to be input may be 5 g. In addition, the plurality of first milling balls _{may be made of a ceramic material such as zirconia (ZrO 2} ), and milling balls of different specifications may be mixed and used. In addition, in the present invention, the predetermined inert gas for creating an inert gas atmosphere environment may be argon (Ar), and the predetermined ball milling container may be a stainless steel container, The predetermined ball milling process may be performed at 500 rpm for one ball milling revolutions per minute, and for 2 hours for a predetermined first ball milling time. However, the first mass of the first precursor used in the predetermined ball milling process, the number and configuration of the first milling balls, the type of inert gas used to create an inert gas atmosphere, The type, the predetermined number of revolutions per minute for the first ball milling, etc. _{may be differently determined within the range in which Cu 1.81} S, which is the object of the present invention, can be synthesized according to the implementation conditions of the invention, and the predetermined first ball milling time is 2 hours It may be determined differently within the range in which the _{Cu 1.96} S compound as the second precursor, which is the result of the corresponding ball milling process, is generated based on the . In addition, it will be natural that the predetermined first ball milling revolutions per minute may be used in a speed unit other than revolutions per minute when the corresponding ball milling process performs milling in a manner other than rotation.

In an actual experimental example for the present invention, 5 g of a copper-sulfur mixture as a first precursor, _{two types of milling balls made of zirconia (ZrO 2} ) material (diameter 5 mm 25 g, diameter 10 mm 25 g) were put in a total of 50 g, which is an inert gas It is put into a first container (jar) having a capacity of 80ml made of stainless steel inside a glove box in an argon (Ar) atmosphere and sealed, and it is then sealed with a planetary ball mill machine (Fritsch GmBH, Pulverisette 5 classic). line) at a predetermined first revolutions per minute of 500 rpm and a predetermined first ball milling time of 2 hours, and as a result, _{5 g of Cu 1.96} S compound as a second precursor was produced and obtained. For reference, in the above experimental example, pure copper and sulfur powder are used without additional additives, and thus, the Cu _1.96 S compound produced has a high purity and does not contain impurities.

_{3A, an XRD graph of the Cu 1.96} S compound as a second precursor produced by dry ball milling for 2 hours under the experimental conditions in the actual experimental example as above is shown. ('1. After dry ball milling')

Then, a heat treatment may be performed on the generated Cu _1.96 S compound as a second precursor under a predetermined heat treatment condition. _{Specifically, with respect to the Cu 1.96} S compound as the second precursor, heat treatment can be performed at a temperature of 400 degrees for 2 hours, and the predetermined heat treatment conditions, such as temperature and time, are Cu _{1.81, which is the object of the present invention, according to the operating conditions of the present invention.} S may be determined differently within a range in which it can be synthesized.

As an actual experimental example for the present invention, 5 g of Cu _1.96 S compound produced through the dry ball milling process as described above is put into a cylindrical furnace, and argon (Ar) gas is flowed at a flow rate of 200 sccm to argon Heat treatment was performed for 2 hours by creating a temperature environment of 400 degrees Celsius at a temperature increase rate of 5 degrees Celsius per minute in (Ar) atmosphere, and as a result, _{5 g of Cu 2} S compound (hereinafter, heat-treated Cu ₂ S compound) powder as a third precursor was produced. has been obtained

3a, an XRD graph of _{the Cu 2} S compound produced by performing heat treatment for 2 hours on the _{Cu 1.96} S compound as the second precursor under the experimental conditions in the actual experimental example as above is shown. ('2. After heat treatment')

Next, a predetermined Ÿ‡ milling process may be performed on the heat-treated Cu _{2 S compound as a third precursor. Specifically, the heat-treated Cu 2} S compound as a third precursor corresponding to the third mass, a plurality of third milling balls, and a predetermined solvent are put into a predetermined Ÿ‡ milling container to perform a predetermined second Ÿ‡ milling. The predetermined Ÿ‡ milling process may be performed for a predetermined second Ÿ‡ milling time at the number of revolutions per minute. At this time, as an experimental condition as a specific example, the preparation of the heat-treated Cu ₂ S compound as a third precursor to be input 3 The mass may be 2 g, and the material of the plurality of third milling balls _{may be a ceramic material such as zirconia (ZrO 2} ), and a mixture of milling balls of different specifications may be used. In addition, the predetermined solvent used in the Ÿ‡ milling process may include at least one of isopropyl alcohol (IPA), heptane, and tetrahydrofuran (THF), The container for Ÿ‡ milling may be a Nalgene bottle, the predetermined second Ÿ‡ milling revolutions per minute is 200 rpm, the predetermined second Ÿ‡ milling time is at least 24 hours, and the predetermined Ÿ‡ milling process is performed. can However, the third mass of the third precursor used in the predetermined Ÿ‡ milling process, the number and configuration of the third milling balls, the predetermined solvent type, the predetermined Ÿ‡ milling vessel type, the predetermined second Ÿ‡ milling revolutions per minute, and the predetermined second Ÿ‡ milling time may be differently determined within a range in which _{Cu 1.81 S, the object of the present invention, can be synthesized according to the conditions of the present invention.} In addition, as for the predetermined second Ÿ‡ milling revolutions per minute, it is natural that a speed unit other than the revolutions per minute may be used when the corresponding Ÿ‡ milling process performs milling in a manner other than rotation.

In an actual experimental example for the present invention, ₂ g of heat-treated Cu 2 S compound as a third precursor, 8 ml of isopropyl alcohol (IPA, Daejung, 99.5%) as a predetermined solvent, zirconia (ZrO ₂ ) For milling of material Put a total of 45g of two types of balls (diameter 5mm 15g, diameter 1mm 30g) into a 125ml Nalgene (HDPE) bottle, and perform Ÿ‡ milling for 24 hours or 72 hours at 200rpm revolutions per minute on a horizontal ball milling equipment. As a result, a Cu _1.81 S compound in a colloidal state was produced and obtained.

In Figure 3a, the XRD graph of _{the Cu 1.81} S compound produced by performing a predetermined Ÿ‡ milling for a predetermined time on the _{heat-treated Cu 2} S compound as the third precursor under the experimental conditions in the actual experimental example as above is shown. . ('3. After Ÿ‡ Milling') At this time, in the actual experimental example, predetermined Ÿ‡ milling was performed for 24 hours or 72 hours, which is shown in more detail in FIG. 3B , which is a separate drawing.

Figure 3b, a predetermined Ÿ ‡ milling process, the resultant Cu _1.81 S compound XRD graphs, the heat-treated Cu ₂ S compounds on the performed 24 hours with respect to, a heat-treated Cu ₂ S compounds in accordance with one embodiment of the present invention It is a diagram showing the XRD graph _{of the Cu 1.81} S compound, which is the result of performing a predetermined Ÿ‡ milling process for 72 hours.

Referring to FIG. 3b, it can be confirmed through the XRD graph as shown in FIG. 3b that _{the Cu 1.81} S compound can be synthesized when a predetermined Ÿ‡ milling process is performed on the _{heat-treated Cu 2 S compound for at least 24 hours.} As more detailed experimental data, in FIG. 3c, _{an XRD graph and SEM image of the Cu 1.81} S compound, which is the result of performing a predetermined Ÿ‡ milling process on the _{heat-treated Cu 2} S compound for 72 hours (clockwise from the top left) , 2,000 times, 5,000 times, 30,000 times, and 10,000 times magnifications) are shown.

In addition, in FIG. 3d, an XRD graph and SEM image showing that the result of performing a predetermined Ÿ‡ milling process on the _{heat-treated Cu 2 S compound for 12 hours is Cu 2} S rather than Cu _{1.81 S (clockwise from the top left,} 2,000 times, 5,000 times, 30,000 times, and 10,000 times) are shown. Referring to FIG. 3d, _{in order to synthesize the Cu 1.81} S compound, which is the object of the present invention, the time for performing a predetermined Ÿ‡ milling process is an important variable. can be checked

In addition, comparative experimental examples additionally performed for comparison with _{[Cu 1.81} S compound synthesis method 1] as described above will be described below.

[Comparative Experiment 1: Performing a predetermined stirring process instead of a predetermined Ÿ‡ milling process]

In [Cu _1.81 S compound synthesis method 1] as described above, a comparative experiment was performed in which a predetermined Stirling process was performed instead of a predetermined Ÿ‡ milling process, which will be described with reference to FIG. 4, a separate drawing as follows. .

Figure 4 is, as an example for comparison with the present invention, the copper-performing a given ball milling process with respect to the sulfur compounds to generate Cu _1.96 S compound, and performing a predetermined heat treatment to the resulting Cu _1.96 S compound in the clockwise direction from to generate a Cu ₂ S compounds, performed 72 h predetermined Stirling process with respect to the generated Cu ₂ S compounds results showing that Cu ₂ S XRD graph and a SEM image (upper left, two thousand times, 5 It is a diagram showing magnifications of 1,000 times, 40,000 times, and 10,000 times).

Referring to FIG. 4 , the basic experimental conditions and experimental procedures of [Comparative Experiment 1] are similar to those of [Cu _1.81 S compound synthesis method 1] as described above, but instead of the predetermined Ÿ‡ milling process, a predetermined Stirring process was performed. Time was carried out, and the specific experimental conditions were that ₂ g of the heat-treated Cu 2 S compound and isopropyl alcohol (IPA) were put into a 20 ml vial container, and stirring was performed at 1000 rpm revolutions per minute for 72 hours, and the result was It was confirmed by XRD etc. As a result, it was confirmed that the result was _{Cu 2 S, not Cu 1.81} S, which is the object of the present invention, and it was confirmed that a predetermined Ÿ‡ milling process may be required to synthesize _{Cu 1.81 S.} In addition, as shown in FIG. 3c , it was confirmed that the particle size was relatively larger when compared with the SEM image in which a predetermined Ÿ‡ milling process was performed for the same 72 hours.

Next, another comparative experimental example additionally performed for comparison with _{[Cu 1.81} S compound synthesis method 1] as described above will be described below.

[Comparative Experiment 2: Change in mole percent ratio of copper-sulfur mixture as the first precursor]

In [Cu _1.81 S compound synthesis method 1] as described above, the ratio of the copper-sulfur mixture used as the first precursor is [Cu]:[S] = [Cu]:[S] in a 2:1 mole percent ratio. = 1:1 mol% ratio was changed to perform a comparative experiment, which will be described with reference to FIG. 5, which is a separate drawing.

5, as an example for comparison with the present invention, a predetermined ball milling process, a predetermined heat treatment, and a predetermined Ÿ‡ milling process are performed with a mixing ratio of the copper-sulfur mixture in a 1:1 mole percent ratio. XRD graph, HAADF analysis image, and SEM image (clockwise from upper left, magnifications of 2,000, 5,000, and 10,000) showing that the resulting product is CuS.

Referring to FIG. 5 , the basic experimental conditions and experimental procedures of the [Comparative Experiment 2] are similar to those of [Cu _1.81 S compound synthesis method 1] as described above, but the ratio of the copper-sulfur mixture used as the first precursor is A comparative experiment was performed at a ratio of 1:1 mole percent, and the specific experimental conditions were that a predetermined ball milling process was performed for 2 hours using a mixture of 3.323 g of copper powder and 1.677 g of sulfur powder to obtain 5 g of CuS powder. 5 g of heat-treated CuS powder was generated by performing a predetermined heat treatment thereon, and a predetermined Ÿ‡ milling process was performed on 2 g of heat-treated CuS powder for 72 hours, and the resulting result was confirmed by XRD or the like.

As a result, it was confirmed that the result was _{CuS, not Cu 1.81} S, which is the object of the present invention. From that, in [Cu _1.81 S compound synthesis method 1] of the present invention, copper melts during a predetermined Ÿ‡ milling process, but , it can be confirmed that copper melting did not occur in the predetermined Ÿ‡ milling process for the heat-treated CuS in [Comparative Experiment 2] as described above, so that the mixing ratio of the copper-sulfur mixture as the first precursor It was found that the pattern could be different depending on the

Next, another comparative experimental example additionally performed for comparison with _{[Cu 1.81} S compound synthesis method 1] as described above will be described below.

[Comparative experiment 3: Change the solvent used in the predetermined Ÿ‡ milling process]

In [Cu _1.81 S compound synthesis method 1] as described above, a comparative experiment was performed by varying a predetermined solvent used in a predetermined Ÿ‡ milling process, and this is described with reference to FIG. 6, a separate drawing, as follows. same.

6 is, as an example for comparison with the present invention, copper - by performing a predetermined ball-milling process with respect to the sulfur compounds to generate Cu _1.96 S compound, and performing a heat treatment with respect to the resulting Cu _1.96 S compound Cu _It is a view showing each XRD graph of the result obtained by producing a ₂ S compound and performing a predetermined Ÿ‡ milling using different solvents for the produced Cu 2 S compound.

Referring to FIG. 6 , the basic experimental conditions and experimental procedures of [Comparative Experiment 3] are similar to those of [Cu _1.81 S compound synthesis method 1] as described above, but a predetermined solvent used in a predetermined Ÿ‡ milling process is used. In addition to isopropyl alcohol (IPA), copper chloride hydrate (CuCl ₂ H ₂ O), tetrahydrofuran (Tetrahydrofuran, THF), heptane, ethanol (Ethanol), deionized water (DI) A comparison experiment was performed with each change, and the XRD graph of the final result is shown in FIG. 6 , respectively. As a result, when the present invention is carried out using isopropyl alcohol (IPA), tetrahydrofuran (THF), and heptane as a solvent, a Cu _1.81 S compound can be obtained as a final product. was found to be At this time, the produced Cu _1.81 S compound had a tetragonal phase, and it is revealed that isopropyl alcohol (IPA) was used as a predetermined solvent in actual experiments for the present invention.

[Cu _1.81 S compound synthesis method 2]

Cu _1.81 specific embodiment of the present invention for synthesizing the S compound is a method of synthesizing Cu _1.81 S compound without carrying out the heat treatment in Cu _1.81 S Compound Synthesis Method 1 as described above, this Fig. 7a to Fig. It will be described with reference to 7d as follows.

Figure 7a, according to an embodiment of the present invention, a predetermined Ÿ‡ milling process is performed on the Cu _1.96 S compound produced by performing a predetermined ball milling process on the copper-sulfur mixture and the Cu _{1.96 S compound produced} It is a figure showing the XRD graph of each _{Cu 1.81} S compound as a result.

First, _{as a first precursor for synthesizing the Cu 1.81} S compound, a copper-sulfur mixture in which copper (Cu) powder and sulfur (S) powder are mixed in a predetermined molar ratio is produced, and for that, a predetermined ball milling process There to be done to obtain a Cu _1.96 S compounds as the second precursor, the copper - Cu _1.96 specific experimental condition and the physical experiment as an example information relating to the S compounds as sulfur mixture and the second precursor is [Cu _1.81 S compound synthesis method 1 ], so a detailed description will be omitted.

_{7a, an XRD graph of the Cu 1.96} S compound as a second precursor produced by dry ball milling for 2 hours under the experimental conditions in the actual experimental example as above is shown. ('1. After dry ball milling')

Next, a predetermined Ÿ‡ milling process may be performed on the produced Cu _{1.96 S compound as a second precursor. Specifically, the Cu 1.96} S compound as the second precursor corresponding to the second mass, a plurality of second milling balls, and a predetermined solvent are put into a predetermined Ÿ‡ milling container, and the predetermined first Ÿ‡ milling The predetermined Ÿ‡ milling process may be performed for a predetermined first Ÿ‡ milling time at revolutions per minute, at this time, as an experimental condition as a specific example, the second mass of the _{Cu 1.96 S compound as a second precursor to be input} Silver may be 2 g, and the material of the plurality of second milling balls _{may be a ceramic material such as zirconia (ZrO 2} ), and milling balls of different specifications may be mixed and used. In addition, the predetermined solvent used in the Ÿ‡ milling process may include at least one of isopropyl alcohol (IPA), heptane, and tetrahydrofuran (THF), The container for Ÿ‡ milling may be a Nalgene bottle, wherein the predetermined first Ÿ‡ milling revolutions per minute is 200 rpm, and the predetermined first Ÿ‡ milling time is at least 12 hours or more and less than 72 hours. A milling process may be performed. However, the second mass of the second precursor used in the predetermined Ÿ‡ milling process, the number and configuration of the second milling balls, the predetermined solvent type, the predetermined Ÿ‡ milling container type, the predetermined first Ÿ‡ milling revolutions per minute, and a predetermined first Ÿ‡ milling time may be differently determined within a range in which _{Cu 1.81 S, which is the object of the present invention, can be synthesized according to the operating conditions of the present invention.} In addition, as for the predetermined first Ÿ‡ milling revolutions per minute, when the corresponding Ÿ‡ milling process performs milling in a manner other than rotation, it will be natural that a speed unit other than the revolutions per minute may be used.

In an actual experimental example for the present invention, 2 _{g of Cu 1.96} S compound as a second precursor, 8 ml of isopropyl alcohol (IPA, Daejung, 99.5%) as a predetermined solvent, zirconia (ZrO ₂ ) Two milling balls made of material Type (diameter 5mm 15g, diameter 1mm 30g) 45g total is put into a 125ml Nalgene (HDPE) bottle, and Ÿ‡ milling is performed for 12 hours or 24 hours at 200rpm revolutions per minute in a horizontal ball milling equipment. , as a result, a Cu _1.81 S compound in a colloidal state was produced and obtained.

7a, an XRD graph of _{the Cu 1.81} S compound produced by performing a predetermined Ÿ‡ milling for a predetermined time on the _{Cu 1.96} S compound as the second precursor under the experimental conditions in the actual experimental example as above is shown. ('2. After Ÿ‡ Milling') At this time, in the actual experimental example, predetermined Ÿ‡ milling was performed for 12 hours or 24 hours, which is shown in more detail in FIG. 7B , which is a separate drawing.

_{7b is a Cu 1.96} S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention, a predetermined Ÿ‡ milling process for 12 hours and 24 hours It is a figure showing the XRD graph of each _{Cu 1.81 S compound as a result.}

_Referring to FIG. 7b , it is shown through the XRD graph as shown in FIG. 7b that the Cu 1.81 S compound can be synthesized when a predetermined Ÿ‡ milling process is performed for at least 12 hours on the _{Cu 1.96} S compound as the second precursor. As more detailed experimental data, in FIG. 7c , the XRD graph and SEM image _{of the Cu 1.81} S compound, which is the result of performing a predetermined Ÿ‡ milling process on the _{Cu 1.96 S compound as the second precursor for 24 hours (upper left)} From clockwise, 2,000 times, 5,000 times, and 10,000 times magnifications) are shown.

In addition, in FIG. 7d, an XRD graph and SEM image showing that _{Cu 1.75 S, not Cu 1.81} S, is a result of performing a predetermined Ÿ‡ milling process for 72 hours on _{a Cu 1.96 S compound as a second precursor (clockwise from the top left)} , 2,000 times, 5,000 times, 30,000 times, and 10,000 times) are shown. Referring to FIG. 3d , _{in order to synthesize the Cu 1.81} S compound, which is the object of the present invention, the time for performing a predetermined Ÿ‡ milling process is important. It can be confirmed that this is a variable, and _{in order to use the method of [Cu 1.81} S compound synthesis method 2] as described above, it can be confirmed that the time for performing the predetermined Ÿ‡ milling process must be less than 72 hours.

In addition, _{comparing the results of [Cu 1.81} S compound synthesis method 1] and [Cu _1.81 S compound synthesis method 2], when a predetermined heat treatment is performed, the crystallinity of the resultant generated by the predetermined heat treatment is increased and thus a predetermined heat treatment is performed. It seems that it can suppress the phenomenon of copper melting during the milling process of Ÿ‡.

And, a comparative experimental example additionally performed for comparison with _{[Cu 1.81} S compound synthesis method 2] as described above will be described below.

[Comparative Experiment 4: Performing a predetermined stirring process instead of a predetermined Ÿ‡ milling process]

In [Cu _1.81 S compound synthesis method 2] as described above, a comparative experiment was performed in which a predetermined Stirling process was performed instead of a predetermined Ÿ‡ milling process, which will be described with reference to FIG. 8, a separate drawing as follows. .

Figure 8 is, as an example for comparison with the present invention, the copper-performing a given ball milling process with respect to the sulfur compounds to a desired Stirling process with respect to Cu _1.96 S compounds produced a Cu _1.96 S compound, and the resulting It is a diagram showing an XRD graph and an SEM image (clockwise from the upper left, 2,000 times, 5,000 times, 40,000 times, and 10,000 times magnifications) showing that the result of 72 hours is Cu _{2 S.}

Referring to FIG. 8 , the basic experimental conditions and experimental procedures of [Comparative Experiment 4] are similar to those of [Cu _1.81 S compound synthesis method 2] as described above, but instead of the predetermined Ÿ‡ milling process, a predetermined Stirring process was performed. Time was carried out, and the specific experimental conditions were as follows: 2 _{g of Cu 1.96} S compound as a second precursor and isopropyl alcohol (IPA) were put into a 20 ml vial container, and stirring was performed at 1000 rpm revolutions per minute for 72 hours, and the The result was confirmed by XRD or the like. As a result, it was confirmed that the result was _{Cu 2 S, not Cu 1.81} S, which is the object of the present invention, and it was confirmed that a predetermined Ÿ‡ milling process may be required to synthesize _{Cu 1.81 S.}

In addition, according to the results of [Comparative Experiment 4], it can be seen that, unlike copper melting in the predetermined Ÿ‡ milling process, sulfur melting occurs in the predetermined stirring process, and as a result, the ratio of sulfur _{It seems that Cu 1.96} S changes to the composition of _{Cu 2} S as this increases.

[Cu _1.81 S compound synthesis method 3]

Cu _1.81 S compound concrete another of the present invention for the synthesis of example, by differently controlling the time of a given ball milling process in Cu _1.81 S Compound Synthesis Method 2 as described above as a method of synthesizing Cu _1.81 S compound , which will be described with reference to FIG. 9 as follows.

9 is a view showing an XRD graph of a _{Cu 1.81} S compound produced by performing a predetermined ball milling process on a copper-sulfur mixture according to an embodiment of the present invention.

First, _{as a first precursor for synthesizing the Cu 1.81} S compound, a copper-sulfur mixture in which copper (Cu) powder and sulfur (S) powder are mixed in a predetermined molar ratio may be produced, and the copper-sulfur mixture Specific experimental conditions and actual experimental examples related to the generation of are _{similar to those in [Cu 1.81} S compound synthesis method 1], so a detailed description will be omitted.

Next, a predetermined ball milling process may be performed on the produced copper-sulfur mixture as the first precursor. Specifically, a copper-sulfur mixture as a first precursor corresponding to the fourth mass, and a plurality of fourth milling balls are put into a predetermined ball milling container in a predetermined inert gas atmosphere environment to perform a predetermined second ball milling per minute The dry ball milling process may be performed for a predetermined second ball milling time at the number of revolutions. At this time, as an experimental condition as a specific example, the fourth mass of the copper-sulfur mixture as the first precursor to be input may be 5 g and , the plurality of fourth milling balls _{may be made of a ceramic material such as zirconia (ZrO 2} ), and milling balls of different specifications may be mixed and used. In addition, the inert gas for creating an inert gas atmosphere environment in the present invention may be argon (Ar), the predetermined ball milling vessel may be a stainless steel (stainless-steel) material, the predetermined second ball The predetermined number of revolutions per minute for milling is 500 rpm, and the predetermined second ball milling time is 36 hours, and the predetermined ball milling process may be performed. However, the fourth mass of the first precursor used in the predetermined ball milling process, the number and configuration of the fourth milling balls, the type of inert gas used to create an inert gas atmosphere, and a predetermined container for ball milling The type, the predetermined second ball milling revolutions per minute, etc. _{may be differently determined within the range in which Cu 1.81} S, which is the object of the present invention, can be synthesized according to the implementation conditions of the present invention, and the predetermined second ball milling time is 36 hours. Based on , it may be determined differently within the range in _{which the Cu 1.81} S compound, which is the result of the corresponding ball milling process, is generated. In addition, as for the predetermined second ball milling revolutions per minute, it will be natural that a speed unit other than the revolutions per minute may be used when the corresponding ball milling process performs milling in a manner other than rotation.

In an actual experimental example for the present invention, 5 g of a copper-sulfur mixture as a first precursor, _{two types of milling balls made of zirconia (ZrO 2} ) material (diameter 5 mm 25 g, diameter 10 mm 25 g) were put in a total of 50 g, which is an inert gas It is put into a first container (jar) having a capacity of 80ml made of stainless steel inside a glove box in an argon (Ar) atmosphere and sealed, and it is then sealed with a planetary ball mill machine (Fritsch GmBH, Pulverisette 5 classic). line) at a predetermined first revolutions per minute of 500 rpm and a predetermined first ball milling time of 36 hours, and as a result, 5 g of Cu _1.81 S compound was produced and obtained. For reference, in the above experimental example, pure copper and sulfur powder are used without additional additives and the like, and thus the produced Cu _1.81 S compound has an advantage that it has high purity and does not contain impurities.

_{FIG. 9 shows an XRD graph of the Cu 1.81} S compound produced by performing dry ball milling for 36 hours under the experimental conditions in the actual experimental example as above. ('1. After dry ball milling')

In the above, the present invention has been described with specific matters such as specific components and limited embodiments and drawings, but these are provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments. , those of ordinary skill in the art to which the present invention pertains can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the above-described embodiments, and not only the claims described below, but also all modifications equivalently or equivalently to the claims described below belong to the scope of the spirit of the present invention. will do it

Claims (14)

In the method of synthesizing _{Cu 1.81} S compound among copper sulfide compounds,
(a) generating a copper-sulfur mixture in which copper (Cu) in powder form and sulfur (S) in powder form are mixed in a predetermined ratio as a first precursor for synthesizing _{the Cu 1.81 S compound;}
(b) performing a predetermined ball milling process on the copper-sulfur mixture as the first precursor to generate _{Cu 1.96} S as a second precursor for synthesizing _{the Cu 1.81 S compound;} and
(c) performing a predetermined wet milling process on _{the Cu 1.96} S as the generated second precursor _{or a third precursor calculated therefrom to generate the Cu 1.81} S compound;
A method of synthesizing a Cu _{1.81 S compound comprising a.} According to claim 1,
In the predetermined ball milling process, the copper-sulfur mixture as the first precursor corresponding to a first mass, and a plurality of first milling balls are put into a predetermined ball milling container in an atmosphere environment of a predetermined inert gas A method for synthesizing _{a Cu 1.81} S compound, characterized in that for a predetermined first ball milling time at a predetermined first ball milling revolutions per minute. 3. The method of claim 2,
The predetermined ratio to the copper-sulfur mixture is [Cu]:[S] = 2:1, characterized in that the mole percent ratio,
The first mass is characterized in that 5g,
The predetermined first ball milling revolutions per minute is characterized in that 500rpm,
The predetermined first ball milling time is Cu _1.81 S compound synthesis method, characterized in that 2 hours. 3. The method of claim 2,
The predetermined Ÿ‡ milling process includes a Cu _1.96 S compound as the second precursor corresponding to a second mass, a plurality of second milling balls, and a predetermined solvent - the predetermined solvent is isopropyl alcohol (IPA), Heptane, and Tetrahydrofuran, Including at least one of THF) - a predetermined Ÿ ‡ were charged into a container for milling, Cu _1.81 S compound, characterized in that formed for a predetermined period of Claim 1 Ÿ ‡ milling time to a predetermined claim 1 Ÿ ‡ be milled rpm synthesis method. 5. The method of claim 4,
The second mass is characterized in that 2 g,
The predetermined first Ÿ‡ milling revolutions per minute is characterized in that 200rpm,
The predetermined first Ÿ‡ milling time is at least 12 hours or more and 24 hours or less. 3. The method of claim 2,
Before step (c),
(c0) heat treatment is performed on the _{Cu 1.96} S compound as the generated second precursor under a predetermined heat treatment condition to produce _{a heat-treated Cu 2} S compound as the third precursor for synthesizing _{the Cu 1.81 S compound} to do;
further comprising,
In step (c),
Cu _1.81 S compound synthesis characterized in that for generating the Cu _1.81 S compound by performing the predetermined Ÿ ‡ milling process with respect to the heat-treated Cu ₂ S compounds as the third precursor. 7. The method of claim 6,
The predetermined ratio to the copper-sulfur mixture is [Cu]:[S] = 2:1, characterized in that the mole percent ratio,
The first mass is characterized in that 5g,
The predetermined first ball milling revolutions per minute is characterized in that 500rpm,
The predetermined first ball milling time is characterized in that 2 hours,
_{The predetermined heat treatment condition, Cu 1.81} S compound synthesis method, characterized in that the heat treatment is performed at a temperature of 400 degrees Celsius for 2 hours. 7. The method of claim 6,
The predetermined Ÿ‡ milling process includes the heat-treated Cu ₂ S compound as the third precursor corresponding to a third mass, a plurality of third milling balls, and a predetermined solvent - the predetermined solvent is isopropyl alcohol ( IPA), including at least one of heptane, and tetrahydrofuran (THF) - is put into a predetermined Ÿ‡ milling vessel, and a predetermined second Ÿ‡ milling revolutions per minute A method for synthesizing _{Cu 1.81} S compound, characterized in that it is performed during the second Ÿ‡ milling time. 9. The method of claim 8,
The third mass is characterized in that 2 g,
The predetermined second Ÿ‡ milling revolutions per minute is characterized in that 200rpm,
Wherein the predetermined claim 2 Ÿ ‡ milling time is how synthetic Cu _1.81 S compound, characterized in that at least less than 24 hours and 72 hours. According to claim 1,
The method, characterized in that the produced Cu _1.81 S compound has a tetragonal phase. In the method of synthesizing _{Cu 1.81} S compound among copper sulfide compounds,
(a) generating a copper-sulfur mixture in which copper (Cu) in powder form and sulfur (S) in powder form are mixed in a predetermined ratio as a first precursor for synthesizing _{the Cu 1.81 S compound;} and
(b) performing a predetermined ball milling process on the copper-sulfur mixture as the first precursor _{to produce the Cu 1.81} S compound;
A method of synthesizing a Cu _{1.81 S compound comprising a.} 12. The method of claim 11,
In the predetermined ball milling process, the copper-sulfur mixture as the first precursor corresponding to the fourth mass and a plurality of fourth milling balls are put into a predetermined ball milling container in an atmosphere environment of a predetermined inert gas. A method for synthesizing _{a Cu 1.81} S compound, characterized in that the second ball milling is performed for a predetermined second ball milling time at a predetermined second ball milling revolutions per minute. 13. The method of claim 12,
The predetermined ratio to the copper-sulfur mixture is [Cu]:[S] = 2:1, characterized in that the mole percent ratio,
The fourth mass is characterized in that 5 g,
The second ball milling revolutions per minute is characterized in that 500rpm,
The second ball milling time is Cu _1.81 S compound synthesis method, characterized in that 36 hours. 12. The method of claim 11,
The method, characterized in that the produced Cu _1.81 S compound has a tetragonal phase.

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