Preparation method for applying metal antimony hard carbon composite material to negative electrode of sodium-ion battery

Abstract

The invention relates to the technical field of sodium ion battery manufacturing, in particular to a preparation method for applying a metal antimony hard carbon composite material to a sodium ion battery negative electrode, which comprises the following steps: (1) taking a corncob as a carbon source, ultrasonically cleaning the corncob, drying in a drying box for three days, and crushing for later use; (2) carrying out low-temperature carbonization on the crushed corncob, and grinding for later use; (3) dispersing a small amount of corncobs subjected to low-temperature carbonization in an ethanol solution, and performing ultrasonic oscillation to obtain a solution a; (4) dissolving antimony chloride in an ethanol solution, and magnetically stirring at room temperature to obtain a solution b; (5) slowly adding the solution b into the solution a, and continuously magnetically stirring at room temperature; and (6) dropwise adding an ammonia water solution into the mixed solution to neutralize the acidity of the solution to cause precipitation. According to the technical scheme, the metal antimony and the hard carbon material are effectively combined together, and the electrochemical performance of the sodium ion battery is improved under the mutual synergistic effect.

Description

Technical Field

[0001] The present invention relates to the technical field of sodium ion battery manufacturing, and in particular to a method for preparing a metal antimony hard carbon composite material applied to a negative electrode of a sodium ion battery. Background Art

[0002] Sodium-ion batteries are essentially rechargeable batteries that use sodium ions as carriers. Their working principle is similar to that of lithium-ion batteries, and they belong to the same main group elements in the periodic table. Due to the scarcity of lithium resources, their development is limited, so sodium-ion batteries came into being as a supplementary alternative product. Sodium-ion batteries are mainly composed of four parts: positive electrode materials, negative electrode materials, separators, and electrolytes. Among them, the negative electrode material largely determines the electrochemical performance of the rechargeable battery.

[0003] At present, hard carbon materials are recognized as the negative electrode materials with the most development potential, but the capacity of hard carbon materials is relatively low and cannot meet market demand. Therefore, metal materials have attracted the attention of scholars due to their high theoretical capacity. However, metals have disadvantages such as easy expansion and deformation, which can cause the material structure to break and pulverize, resulting in a sharp drop in capacity and affecting electrochemical stability. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a metal antimony hard carbon composite material for use in a negative electrode of a sodium ion battery, which has the advantages of effectively combining metal antimony and hard carbon materials together, and improving the electrochemical performance of the sodium ion battery under the synergistic effect of each other, and solves the problem that the shortcomings of metals such as easy expansion and deformation will cause the material structure to break and pulverize, resulting in a sharp drop in capacity and affecting the electrochemical stability.

[0005] To achieve the above object, the present invention provides the following technical solution: a method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, comprising the following steps:

[0006] 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, ultrasonicate for 1-3 hours, dry at 80-100°C overnight, and crush the corn cobs with a grinder for later use;

[0007] 2) taking 1-10 g of crushed corn cobs for low temperature carbonization, heating from 25° C. to 500-700° C. for 1-3 h and keeping the temperature for 1-3 h, and grinding for later use;

[0008] 3) 1-5 g of low-temperature carbonized corn cobs were dispersed in 100-500 ml of ethanol solution and subjected to ultrasonic oscillation, which was named solution a;

[0009] 4) Dissolve 1-5 g of antimony chloride in 10-100 ml of ethanol solution and stir magnetically at room temperature for 1-2 h, named solution B;

[0010] 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 10 to 30 hours;

[0011] 6) Take 1-20 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation;

[0012] 7) Filter, wash and dry after magnetic stirring at room temperature for 10 to 30 hours;

[0013] 8) Take the sample for further high-temperature carbonization, heating from 25°C room temperature to 700-1500°C for 100-500 min and keeping it at that temperature for 1-3 h;

[0014] 9) Finally, the sample was collected and named sbc-1300.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The method of the present invention adopts a hard carbon and metal composite method to prepare a negative electrode material for a sodium ion battery, and uses cheap corn cobs as a biomass carbon source. The raw material source is abundant, and the development and utilization of corn cobs can improve economic and social benefits, while reducing pollution to the environment. The theoretical capacity of metal materials is much higher than that of hard carbon materials, and the preparation process is simple. However, metals are prone to expansion during the charging and discharging process, causing the structure to deform. Therefore, using hard carbon as a skeleton to limit metal expansion is an ideal solution. While increasing the capacity of rechargeable batteries, it maintains good cycle stability, and at the same time proposes new ideas and thoughts for the preparation of other sodium ion battery electrode materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the SEM image of sbc-1300 of the present invention;

[0018] Figure 2 is the XRD pattern of sbc-1300 of the present invention;

[0019] Figure 3 This is the cycle diagram of the sbc-1300 of the present invention at a current density of 0.1C. DETAILED DESCRIPTION

[0020] Example 1

[0021] A method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, the specific steps of which are as follows:

[0022] 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, perform ultrasonic treatment for 2 hours, dry at 80°C overnight, and crush the corn cobs with a grinder for later use;

[0023] 2) Take 10g of crushed corn cobs for low-temperature carbonization, raise the temperature from 25°C for 2h to 600°C and keep it at that temperature for 2h, grind and set aside;

[0024] 3) Take 1g of low-temperature carbonized corn cob and disperse it in 150ml of ethanol solution, and ultrasonically vibrate for 40min, named solution a;

[0025] 4) Dissolve 1 g of antimony chloride in 30 ml of ethanol solution and stir magnetically at room temperature for 1 h. This is called solution B.

[0026] 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 18 hours;

[0027] 6) Take 5 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation;

[0028] 7) Filter, wash and dry after magnetic stirring at room temperature for 24 hours;

[0029] 8) Take the sample for further high-temperature carbonization, heating from 25°C room temperature to 700°C for 140 min and keeping it at that temperature for 2 h;

[0030] 9) Finally, the sample was collected and named sbc-700.

[0031] Example 2

[0032] A method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, the specific steps of which are as follows:

[0033] 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, perform ultrasonic treatment for 2 hours, dry at 80°C overnight, and crush the corn cobs with a grinder for later use;

[0034] 2) Take 10g of crushed corn cobs for low-temperature carbonization, raise the temperature from 25°C for 2h to 600°C and keep it at that temperature for 2h, grind and set aside;

[0035] 3) Take 1g of low-temperature carbonized corn cob and disperse it in 150ml of ethanol solution, and ultrasonically vibrate for 40min, named solution a;

[0036] 4) Dissolve 1 g of antimony chloride in 30 ml of ethanol solution and stir magnetically at room temperature for 1 h. This is called solution B.

[0037] 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 18 hours;

[0038] 6) Take 5 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation;

[0039] 7) Filter, wash and dry after magnetic stirring at room temperature for 24 hours;

[0040] 8) Take the sample for further high-temperature carbonization, heating from 25°C room temperature to 900°C for 180 min and keeping it at that temperature for 2 h;

[0041] 9) Finally, the sample was collected and named sbc-900.

[0042] Example 3

[0043] A method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, the specific steps of which are as follows:

[0044] 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, perform ultrasonic treatment for 2 hours, dry at 80°C overnight, and crush the corn cobs with a grinder for later use;

[0045] 2) Take 10g of crushed corn cobs for low-temperature carbonization, raise the temperature from 25°C for 2h to 600°C and keep it at that temperature for 2h, grind and set aside;

[0046] 3) Take 1g of low-temperature carbonized corn cob and disperse it in 150ml of ethanol solution, and ultrasonically vibrate for 40min, named solution a;

[0047] 4) Dissolve 1 g of antimony chloride in 30 ml of ethanol solution and stir magnetically at room temperature for 1 h. This is called solution B.

[0048] 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 18 hours;

[0049] 6) Take 5 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation;

[0050] 7) Filter, wash and dry after magnetic stirring at room temperature for 24 hours;

[0051] 8) Take the sample for further high-temperature carbonization, heating from 25°C room temperature to 1100°C for 220 min and keeping it at that temperature for 2 h;

[0052] 9) Finally, the sample was collected and named sbc-1100.

[0053] Example 4

[0054] A method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, the specific steps of which are as follows:

[0055] 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, perform ultrasonic treatment for 2 hours, dry at 80°C overnight, and crush the corn cobs with a grinder for later use;

[0056] 2) Take 10 g of crushed corn cobs for low-temperature carbonization, heat from 25°C to 600°C and keep warm for 2 h, grind and set aside;

[0057] 3) Take 1g of low-temperature carbonized corn cob and disperse it in 150ml of ethanol solution, and ultrasonically vibrate for 40min, named solution a;

[0058] 4) Dissolve 1 g of antimony chloride in 30 ml of ethanol solution and stir magnetically at room temperature for 1 h. This is called solution B.

[0059] 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 18 hours;

[0060] 6) Take 5 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation;

[0061] 7) Filter, wash and dry after magnetic stirring at room temperature for 24 hours;

[0062] 8) The sample was further subjected to high temperature carbonization, with the temperature increased from 25°C to 1300°C for 260 min and kept at this temperature for 2 h;

[0063] 9) Finally, the sample was collected and named sbc-1300.

[0064] Example 5

[0065] A method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, the specific steps of which are as follows:

[0066] 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, perform ultrasonic treatment for 2 hours, dry at 80°C overnight, and crush the corn cobs with a grinder for later use;

[0067] 2) Take 10g of crushed corn cobs for low-temperature carbonization, raise the temperature from 25°C for 2h to 600°C and keep it at that temperature for 2h, grind and set aside;

[0068] 3) Take 1g of low-temperature carbonized corn cob and disperse it in 150ml of ethanol solution, and ultrasonically vibrate for 40min, named solution a;

[0069] 4) Dissolve 1 g of antimony chloride in 30 ml of ethanol solution and stir magnetically at room temperature for 1 h. This is called solution B.

[0070] 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 18 hours;

[0071] 6) Take 5 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation;

[0072] 7) Filter, wash and dry after magnetic stirring at room temperature for 24 hours;

[0073] 8) Take the sample for further high-temperature carbonization, heating from 25°C room temperature for 300 min to 1500°C and keeping it for 2 h;

[0074] 9) Finally, the sample was collected and named sbc-1500.

[0075] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a metal antimony hard carbon composite material for a negative electrode of a sodium ion battery, characterized in that: The following steps are involved: 1) Wash the corn cobs produced in Heilongjiang with deionized water three times, ultrasonicate for 1-3 hours, dry at 80-100°C overnight, and crush the corn cobs with a grinder for later use; 2) taking 1-10 g of crushed corn cobs for low temperature carbonization, heating from 25° C. to 500-700° C. for 1-3 h and keeping the temperature for 1-3 h, and grinding for later use; 3) 1-5 g of low-temperature carbonized corn cobs were dispersed in 100-500 ml of ethanol solution and subjected to ultrasonic oscillation, which was named solution a; 4) Dissolve 1-5 g of antimony chloride in 10-100 ml of ethanol solution and stir magnetically at room temperature for 1-2 h, named solution B; 5) Slowly add solution b into solution a and continue magnetic stirring at room temperature for 10 to 30 hours; 6) Take 1-20 ml of ammonia solution and add it dropwise into the mixed solution to neutralize the acidity of the solution and cause precipitation; 7) Filter, wash and dry after magnetic stirring at room temperature for 10 to 30 hours; 8) Take the sample for further high-temperature carbonization, heating from 25°C room temperature to 700-1500°C for 100-500 min and keeping it at that temperature for 1-3 h; 9) Finally, the sample was collected and named sbc-1300.

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