Preparation method and application of micro-flower-shaped Cu3SbS4 material

Abstract

The invention discloses a preparation method and application of a micro-flower-shaped Cu3SbS4 material, and the preparation method comprises the following steps: step 1, adding CuC l2 and SbCl 3 into an ethylene glycol solution, and stirring to form a uniform mixed solution; 2, adding thiourea into the mixed solution, stirring, and transferring into a high-pressure kettle; 3, sealing the autoclave at high temperature, and naturally cooling to room temperature until a black solid product is generated; and 4, centrifuging the black solid product, washing, and carrying out vacuum drying. The Cu3SbS4 material prepared by the preparation method disclosed by the invention is synthesized by a simple hydrothermal method; as the negative electrode of the lithium ion battery, after 200 cycles, the material has high specific capacity and high stability under the current of 100mA / g; and after 100 times of circulation, the reversible specific capacity can reach up to 392.9 mAh / g under the current of 50mA / g as the negative electrode of the sodium-ion battery. A new gate is opened for exploring the design of the antimony-based negative electrode material for the lithium ion and sodium ion battery with excellent performance, and the antimony-based negative electrode material has wide application potential.

Description

Technical Field

[0001] The invention belongs to the field of material preparation, and in particular relates to a method for preparing a micro-flower-shaped Cu3SbS4 material. Background Art

[0002] High-performance batteries are increasingly required for many applications such as portable electronics, electric vehicles or stationary storage systems used in conjunction with renewable electrical energy sources due to their high energy density. Lithium-ion batteries (LIBs) are generally considered the storage system of choice for such applications. However, given the limited abundance of lithium salts and the resulting increasing cost, there is growing interest in developing conceptually identical sodium-ion (Na-ion) batteries (SIBs) as potential inexpensive alternatives for large-scale applications. Importantly, the technological transition from LIBs to Na-ion batteries requires not only the replacement of lithium ions with sodium ions but also the selection of electrode materials composed entirely of relatively abundant elements. Cu3SbS4 stands out as a promising low-cost, non-toxic rechargeable electrode material that can be used as both a LIB electrode and a Na-ion battery electrode material. Cu3SbS4 has a high theoretical specific capacity of 669 mAh / g, assuming full lithiation / sodiumation to form Li2S+Li3Sb+Cu (or Na2S+Na3Sb+Cu). However, the poor reversibility of Cu3SbS4 as an electrode material for LIBs at room temperature has hampered its development. Here, we present a simple solvothermal synthesis route to prepare microflower-like Cu3SbS4 materials and investigate their electrochemical performance as anode materials for lithium-ion and sodium-ion batteries using button cells. Summary of the invention

[0003] The purpose of the present invention is to overcome the above problems existing in the prior art and provide a method for preparing a micro-flower-shaped Cu3SbS4 material.

[0004] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions:

[0005] A method for preparing a micro-flower-shaped Cu3SbS4 material, the preparation method is as follows:

[0006] Step 1: Add CuCl2 and SbCl3 into ethylene glycol solution and stir to form a uniform mixed solution;

[0007] Step 2: adding thiourea to the above mixed solution, stirring and transferring to an autoclave;

[0008] Step 3: After sealing the autoclave at high temperature, cool it naturally to room temperature until a black solid product is produced;

[0009] Step 4: The black solid product is centrifuged, washed, and vacuum dried.

[0010] Further, CuCl2 is 2.5-3.5mmol, SbCl3 is 0.5-1.5mmol, and the ethylene glycol solution is 35-45mL.

[0011] Furthermore, CuCl2 and SbCl3 are added into the ethylene glycol solution and stirred by a magnetic stirrer.

[0012] Further, the thiourea is 3.0-3.5 mmol.

[0013] Furthermore, after thiourea is added to the mixed solution, the stirring time is 0.5-1.5 hours.

[0014] Furthermore, the autoclave is a stainless steel autoclave lined with polytetrafluoroethylene.

[0015] Furthermore, the temperature of the high temperature sealing of the autoclave is 130-170° C. and the time is 12-36 hours.

[0016] Furthermore, distilled water and ethanol are used for washing.

[0017] Furthermore, the vacuum drying temperature is 30-70° C., and the time is 5-15 hours.

[0018] The present invention also provides an application of the micro-flower-shaped Cu3SbS4 material prepared by the above preparation method in lithium ion or sodium ion batteries.

[0019] The beneficial effects of the present invention are:

[0020] The Cu3SbS4 material prepared by the present invention is synthesized by a simple hydrothermal method; as a negative electrode of a lithium-ion battery, after 200 cycles, it has a high specific capacity and high stability (477.6 mAh / g) at a current of 100 mA / g; as a negative electrode of a sodium-ion battery, after 100 cycles, at a current of 50 mA / g, the reversible specific capacity is as high as 392.9 mAh / g. This opens a new door for exploring the design of antimony-based negative electrode materials for lithium-ion and sodium-ion batteries with excellent performance, and has broad application potential. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of this application. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0022] Figure 1 It is the XRD diffraction pattern of the Cu3SbS4 material prepared by the preparation method of the present invention;

[0023] Figure 2is a SEM image of the Cu3SbS4 material prepared by the preparation method of the present invention;

[0024] Figure 3 is a SEM image of the Cu3SbS4 material prepared by the preparation method of the present invention;

[0025] Figure 4 It is a SEM picture of the Cu3SbS4 material prepared by the preparation method of the present invention. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] like Figure 1 A preparation method of a micro-flower-shaped Cu3SbS4 material is shown, and the preparation method is as follows:

[0029] Step 1: Add 3 mmol CuCl2 and 1 mmol SbCl3 into 40 mL ethylene glycol solution and stir with a magnetic stirrer to form a uniform mixed solution;

[0030] Step 2: 3.2 mmol of thiourea was added to the above mixed solution, stirred for 1 hour and then transferred to a stainless steel autoclave (60 ml capacity) lined with polytetrafluoroethylene;

[0031] Step 3: The autoclave was sealed and maintained at 150°C for 24 hours, and then cooled naturally to room temperature until a black solid product was produced;

[0032] Step 4: After centrifugation, the black solid product is washed with distilled water and ethanol, and vacuum dried at 50° C. for 10 hours.

[0033] Example 2

[0034] like Figure 1 A preparation method of a micro-flower-shaped Cu3SbS4 material is shown, and the preparation method is as follows:

[0035] Step 1: Add 2.5mmolCuCl2 and 0.5mmolSbCl3 into 35mL ethylene glycol solution and stir with a magnetic stirrer to form a uniform mixed solution;

[0036] Step 2: 3.0 mmol of thiourea was added to the above mixed solution, and after stirring for 0.5 hour, it was transferred to a stainless steel autoclave (capacity of 60 ml) lined with polytetrafluoroethylene;

[0037] Step 3: The autoclave was sealed and maintained at a temperature of 130° C. for 12 hours, and then cooled naturally to room temperature until a black solid product was produced;

[0038] Step 4: After centrifugation, the black solid product is washed with distilled water and ethanol, and vacuum dried at 30° C. for 5 hours.

[0039] Example 3

[0040] like Figure 1 A preparation method of a micro-flower-shaped Cu3SbS4 material is shown, and the preparation method is as follows:

[0041] Step 1: Add 3.5mmolCuCl2 and 1.5mmolSbCl3 into 45mL ethylene glycol solution and stir with a magnetic stirrer to form a uniform mixed solution;

[0042] Step 2: 3.5 mmol of thiourea was added to the above mixed solution, and after stirring for 1.5 hours, it was transferred to a stainless steel autoclave (capacity of 60 ml) lined with polytetrafluoroethylene;

[0043] Step 3: The autoclave was sealed and maintained at a temperature of 170°C for 36 hours, and then cooled naturally to room temperature until a black solid product was produced;

[0044] Step 4: After centrifugation, the black solid product is washed with distilled water and ethanol, and vacuum dried at 70° C. for 15 hours.

[0045] The present invention also provides an application of the micro-flower-shaped Cu3SbS4 material prepared by the above preparation method in lithium ion or sodium ion batteries.

[0046] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0047] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A method for preparing a micro-flower-shaped Cu3SbS4 material, characterized in that: The preparation method is as follows: Step 1: Add CuCl2 and SbCl3 into ethylene glycol solution and stir to form a uniform mixed solution; Step 2: adding thiourea to the above mixed solution, stirring and transferring to an autoclave; Step 3: After sealing the autoclave at high temperature, cool it naturally to room temperature until a black solid product is produced; Step 4: The black solid product is centrifuged, washed, and vacuum dried.

2. The method for preparing a micro-flower-shaped Cu3SbS4 material according to claim 1, characterized in that: CuCl2 is 2.5-3.5mmol, SbCl3 is 0.5-1.5mmol, and ethylene glycol solution is 35-45mL.

3. The method for preparing a micro-flower-shaped Cu3SbS4 material according to claim 2, characterized in that: CuCl2 and SbCl3 were added to the ethylene glycol solution and stirred by a magnetic stirrer.

4. The method for preparing a micro-flower-shaped Cu3SbS4 material according to claim 3, characterized in that: Thiourea is 3.0-3.5 mmol.

5. The method for preparing a micro-flower-shaped Cu3SbS4 material according to claim 4, characterized in that: After adding thiourea to the above mixed solution, the stirring time is 0.5-1.5 hours.

6. A method for preparing a micro-flower-shaped Cu3SbS4 material according to any one of claims 1 to 5, characterized in that: The autoclave is a stainless steel autoclave lined with polytetrafluoroethylene.

7. The method for preparing the micro-flower-shaped Cu3SbS4 material according to claim 6, characterized in that: The temperature of the high temperature sealing of the autoclave is 130-170°C and the time is 12-36 hours.

8. The method for preparing the micro-flower-shaped Cu3SbS4 material according to claim 7, characterized in that: Wash with distilled water and ethanol.

9. The method for preparing the micro-flower-shaped Cu3SbS4 material according to claim 8, characterized in that: The vacuum drying temperature is 30-70°C and the time is 5-15 hours.

10. Use of the micro-flower-shaped Cu3SbS4 material prepared by the preparation method according to any one of claims 1 to 9 in lithium-ion or sodium-ion batteries.

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