CN110752353B - Flexible self-supporting tin diselenide/carbon nano tube composite film electrode material and preparation method and application thereof - Google Patents
Flexible self-supporting tin diselenide/carbon nano tube composite film electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of sodium ion battery materials, and discloses a flexible self-supporting tin diselenide/carbon nano tube composite film electrode material, and a preparation method and application thereof. The flexible self-supporting tin diselenide/carbon nano tube composite film electrode material is prepared by ultrasonically mixing a carbon nano tube and ethylene glycol to obtain a mixed solution A; adding ethylenediamine, stirring and mixing to obtain a mixed solution B; and adding tin diselenide and selenium powder into the mixed solution B, stirring to obtain a mixed solution C, carrying out hydrothermal reaction on the mixed solution C at the temperature of 150-220 ℃, carrying out vacuum filtration and washing on a product, and drying at the temperature of 40-80 ℃ to obtain the product. The composite film electrode material has the characteristics of layered film structure, good flexibility, micro-nano morphology, rich pore structure, no conductive agent and binder, high specific capacity, high multiplying power and high cycling stability, and can be used for sodium ion battery electrodes.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a flexible self-supporting tin diselenide/carbon nano tube composite film electrode material and a preparation method and application thereof.
Background
Tin diselenide is a semiconductor material, has excellent optical and electrical properties, has a lamellar structure, has the advantages of safety, environmental protection, stable cycle performance and the like, and can be used as a cathode material of a sodium ion battery. At present, the method for preparing the cathode material of the tin diselenide sodium ion battery is mainly a liquid phase method. Pengherin et al discloses a preparation method of a nano tin diselenide powder material, which adopts sodium selenite as a selenium source, ethylene glycol as a solvent and ethylenediamine as an auxiliary solvent, and a hydrothermal reaction is carried out in a high-pressure reaction kettle to obtain the tin diselenide nanosheets. The preparation process mostly needs hydrazine hydrate as an auxiliary material, the hydrazine hydrate is a hypertoxic substance, is not friendly to human bodies and environment, and the preparation process is complex and has higher cost, thus not meeting the requirements of large-scale industrial production. And the pure tin diselenide material has poor electrochemical performance and severe attenuation of battery capacity.
Therefore, the pure tin diselenide material can be modified to slow down the volume expansion, slow down the capacity attenuation and improve the electrochemical performance. Meanwhile, the simplified process is considered, and toxic materials such as hydrazine hydrate and the like are replaced by environment-friendly and nontoxic medicines. The carbon nano tube is a common carbon material, has a fiber structure, is uniformly coated on the surface of the tin diselenide material, can improve the conductivity, and simultaneously slows down the volume expansion, so that the problem of capacity attenuation is overcome to a certain extent by pure tin diselenide. And the carbon nano tube material is non-toxic and harmless and is friendly to human and environment.
After the tin diselenide is compounded with the carbon nano tube, if the original process is used, namely the tin diselenide/carbon nano tube material is used in combination with a conductive agent and a bonding agent, the process is still complex, and the cost is higher. If the use of conductive agents and binders can be reduced or eliminated while maintaining good electrochemical performance, the cost can be greatly reduced and the requirements of industrial production can be met. The flexible self-supporting material can be used for mounting the battery without matching with a conductive agent and a binder, and has the advantages of simple process, low cost and good application prospect.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material.
The invention also aims to provide a preparation method of the flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material.
The invention also aims to provide application of the flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material.
The purpose of the invention is realized by the following technical scheme:
a flexible self-supporting tin diselenide/carbon nano tube composite film electrode material is prepared by ultrasonically mixing a carbon nano tube and ethylene glycol to obtain a mixed solution A; adding ethylenediamine, stirring and mixing to obtain a mixed solution B; and adding tin diselenide and selenium powder into the mixed solution B, stirring to obtain a mixed solution C, carrying out hydrothermal reaction on the mixed solution C at the temperature of 150-220 ℃, carrying out vacuum filtration and washing on a product, and drying at the temperature of 40-80 ℃ to obtain the product.
Preferably, the concentration of the mixed solution A is 0.4-1.5 mg/ml, and the concentration of the mixed solution B is 0.4-2 mg/ml.
Preferably, the volume ratio of ethylene glycol to ethylene diamine is 1: (10-20).
Preferably, the carbon nanotube is one or more of an aminated single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube.
Preferably, the concentration of tin diselenide in the solution C is 2.5-4 mg/ml, and the molar ratio of the selenium powder to the tin diselenide is (1.5-2.7): 1.
preferably, the time of the hydrothermal reaction is 18-30 h; the drying time is 5-8 h.
Preferably, the power of the ultrasound is 400-900W, the frequency of the ultrasound is 10-25 kHz, and the time of the ultrasound is 30-60 min.
Preferably, the reagents for suction filtration and washing are deionized water and absolute ethyl alcohol.
The preparation method of the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material comprises the following specific steps:
s1, ultrasonically mixing a carbon nano tube and ethylene glycol to obtain a mixed solution A;
s2, adding ethylenediamine into the mixed solution A, and stirring and mixing to obtain a mixed solution B;
s3, adding tin diselenide and selenium powder into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
and S4, carrying out hydrothermal reaction on the mixed solution C at the temperature of 150-220 ℃, carrying out vacuum filtration and washing on a product, and drying at the temperature of 40-80 ℃ to obtain the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material.
The flexible self-supporting tin diselenide/carbon nano tube composite film electrode material is applied to the field of sodium ion batteries or energy storage.
Compared with the prior art, the invention has the following beneficial effects:
1. the tin diselenide/carbon tube composite film material has a film-shaped structure, is good in flexibility, can be bent for multiple times, has a small-diameter and uniformly-distributed tin diselenide laminated structure, and the carbon tube is uniformly coated on the surface of the tin diselenide material. The characteristics of nano size, lamellar structure and thin film structure effectively improve the reaction area of ions, and the carbon tube is coated to ensure that the capacity is not attenuated or is attenuated little during charging and discharging; the addition of the carbon tube further improves the surface conductivity of the material, and obviously improves the rate capability and the cycle performance of the material.
2. The reaction raw materials of the carbon nano tube, the tin diselenide, the ethylene glycol, the ethylenediamine and the selenium powder used in the invention have the characteristics of low price, low risk and wide sources, and are obviously superior to the hazardous chemical materials which are easy to poison or explode and are used in the prior similar technology.
3. The invention can obtain the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material by controlling the reaction conditions, the obtained film composite material has small thickness of lamina, larger surface area and two-dimensional lamina-shaped structure, can effectively improve the transmission rate of ions, ensures that the charge and discharge capacity is not attenuated, and the material capacity is attenuated slowly by adding the carbon tube.
4. The flexible self-supporting tin diselenide/carbon nano tube composite film electrode material can be directly used as a sodium ion battery electrode, and does not need to use a binder and a conductive agent, so that the experimental cost is reduced, the production period is shortened, and the application range of the material in other fields is enlarged.
5. In the process of the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material, the reaction conditions are mild, the control is convenient, the operation is simple, the production cost is low, and the industrial production is easy to realize.
Drawings
Fig. 1 is an XRD pattern of tin diselenide/carbon nanotube thin film composite material prepared in examples 1-3.
Fig. 2 is an SEM photograph of tin diselenide/carbon nanotube thin film composites obtained in examples 1-3 and pure tin diselenide.
FIG. 3 is a constant current cycle diagram of the tin diselenide/carbon nanotube thin film composite material prepared in examples 1 to 3 at a current density of 0.1A/g.
Fig. 4 is a rate performance curve of tin diselenide/carbon nanotube thin film composite materials prepared in examples 1-3.
Fig. 5 is a diagram of a tin diselenide/carbon nanotube thin film composite material prepared in example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated. Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
1. Uniformly dispersing 27 mg of aminated carbon nanotubes (purchased from Jiangsu Xiancheng nano material science and technology Co., Ltd., purity of more than 95% and diameter of 1-2 nm) into 64 ml of ethylene glycol by using an ultrasonic cell crusher for 60 minutes to obtain an ethylene glycol/aminated carbon nanotube solution;
2. adding ethylenediamine (the volume ratio of the ethylene glycol/aminated carbon nanotube solution to the ethylenediamine is 16:1) into the ethylene glycol/aminated carbon nanotube solution obtained in the step 1, and stirring for 20 minutes to obtain an ethylene glycol/aminated carbon nanotube/ethylenediamine mixed solution;
3. pouring 56.4 mg of stannous chloride dihydrate into 16 ml of ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution, and stirring for 20 minutes until the stannous chloride dihydrate is dissolved in the ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution;
4. pouring selenium powder (the molar ratio of the selenium powder to stannous chloride dihydrate is 2:1) into the ethylene glycol/aminated carbon nanotube/ethylenediamine mixed solution, and stirring for 30 minutes until the selenium powder is dissolved in the ethylene glycol/aminated carbon nanotube/ethylenediamine mixed solution;
5. transferring the mixed solution obtained in the step (4) into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven, reacting for 30 hours at 150 ℃, stopping the reaction, naturally cooling to room temperature, and taking out;
6. and (3) carrying out suction filtration on the sample obtained in the step (5) by using a suction filtration device, wherein the used filter membrane is a water-system filter membrane, washing the water-system filter membrane by using a large amount of deionized water, carrying out forced air drying at the temperature of 60 ℃ for 8 hours, and separating the material from the filter membrane to obtain the tin diselenide/carbon nanotube film composite material.
The obtained tin diselenide/carbon nano tube composite film material is directly cut into a wafer, a conductive agent and a bonding agent are not used, and the button sodium ion battery is directly installed in the glove box. Fig. 5 is a diagram of a tin diselenide/carbon nanotube thin film composite material prepared in example 1. Wherein, the left side is the picture of the obtained film unfolding, and the right side is the picture of the film bending. The film can be completely torn off from the filter membrane without cracking, which shows that the film forming effect is good and the suction filtration method is more suitable; the film on the right side still keeps good toughness after being bent by 180 degrees, does not crack or break and has good flexibility.
Example 2
1. Uniformly dispersing 27 mg of aminated carbon nanotubes (purchased from Jiangsu Xiancheng nano material science and technology limited, the purity is more than 95 percent, and the diameter is 1-2 nm) into 64 ml of ethylene glycol by using an ultrasonic cell crusher for 60 minutes to obtain an ethylene glycol/aminated carbon nanotube solution;
2. adding ethylene diamine (the volume ratio of the ethylene glycol/carbon nanotube solution to the ethylene diamine is 16:1) into the ethylene glycol/aminated carbon nanotube solution obtained in the step 1, and stirring for 20 minutes to obtain an ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution for later use;
3. pouring 56.4 mg of stannous chloride dihydrate into the ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution, and stirring for 20 minutes until the stannous chloride dihydrate is dissolved in the ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution;
4. and the molar ratio of the selenium powder to the stannous chloride dihydrate is 2:1) pouring the mixture into a mixed solution of ethylene glycol/aminated carbon nano tube/ethylene diamine, and stirring for 30 minutes until selenium powder is dissolved in the mixed solution of ethylene glycol/aminated carbon nano tube/ethylene diamine;
5. transferring the mixed solution obtained in the step (4) into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven, reacting for 18 hours at 220 ℃, stopping the reaction, naturally cooling to room temperature, and taking out;
6. and (3) performing suction filtration on the sample obtained in the step (5) by using a suction filtration device, wherein the filter membrane is a water-system filter membrane, washing the water-system filter membrane by using a large amount of deionized water, performing forced air drying at the temperature of 60 ℃ for 8 hours, and separating the material from the filter membrane to obtain the tin diselenide/carbon nanotube film composite material.
The obtained tin diselenide/carbon nano tube composite film material is directly cut into a wafer, a conductive agent and a bonding agent are not used, and the button sodium ion battery is directly installed in the glove box.
Example 3
1. Uniformly dispersing 27 mg of aminated carbon nanotubes (purchased from Jiangsu Xiancheng nano material science and technology Co., Ltd., purity of more than 95% and diameter of 1-2 nm) into 64 ml of ethylene glycol by using an ultrasonic cell crusher for 60 minutes to obtain an ethylene glycol/aminated carbon nanotube solution;
2. adding ethylene diamine (the volume ratio is 16:1) into the ethylene glycol/aminated carbon nanotube solution obtained in the step 1, and stirring for 20 minutes to obtain an ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution;
3. pouring 56.4 mg of stannous chloride dihydrate into the ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution, and stirring for 20 minutes until the stannous chloride dihydrate is dissolved in the ethylene glycol/aminated carbon nanotube/ethylene diamine mixed solution;
4. pouring selenium powder (the molar ratio of the selenium powder to stannous chloride dihydrate is 2:1) into the ethylene glycol/aminated carbon nanotube/ethylenediamine mixed solution, and stirring for 30 minutes until the selenium powder is dissolved in the ethylene glycol/aminated carbon nanotube/ethylenediamine mixed solution;
5. transferring the mixed solution obtained in the step (4) into a polytetrafluoroethylene reaction kettle, sealing the reaction kettle, placing the reaction kettle in a forced air drying oven, reacting for 25 hours at 180 ℃, stopping the reaction, naturally cooling to room temperature, and taking out;
6. and (3) carrying out suction filtration on the sample obtained in the step (5) by using a suction filtration device, wherein the used filter membrane is a water-system filter membrane, washing the water-system filter membrane by using a large amount of deionized water, carrying out forced air drying at the temperature of 60 ℃ for 8 hours, and separating the material from the filter membrane to obtain the tin diselenide/carbon nanotube film composite material.
7. The obtained tin diselenide/carbon nano tube composite film material is directly cut into a wafer, a conductive agent and a bonding agent are not used, and the button sodium ion battery is directly installed in the glove box.
Fig. 1 is an XRD pattern of tin diselenide/carbon nanotube thin film composite material prepared in examples 1-3. From bottom to top, XRD diffraction peaks of the tin diselenide/carbon nanotube thin film composite material obtained by the standard card 23-0602 and the examples 1, 2 and 3 are sequentially arranged. As can be seen from fig. 1, the X-ray diffraction peak values of the prepared three tin diselenide/carbon nanotube thin film composites are completely consistent with the PDF standard cards 23-0602, which shows that after the carbon nanotubes are added, the material components of the composites are still the same as those of pure tin diselenide, the peak angle of X-ray diffraction is the same, and the peak intensity is equivalent, thus proving that the main body structure of the prepared tin diselenide/carbon nanotube thin film composites is still tin diselenide (SnSe)2) The crystal structure and the components are not changed,the addition of the carbon nano tube does not influence the component structure of the substance, and the addition of the carbon nano tube plays a supporting role and assists in forming a film structure. The three reaction conditions used all gave pure substances, free of impurities.
Fig. 2 is an SEM photograph of the tin diselenide/carbon nanotube thin film composite obtained in examples 1 to 3 and pure tin diselenide. (a) Tin diselenide, (b-d) tin diselenide/carbon nanotube thin film composite material, wherein the test multiple of (b) is × 20K, the test multiple of (c) is × 80K, and the test multiple of (d) is × 120K. As can be seen from fig. 2, the prepared tin diselenide and tin diselenide/carbon nanotube film composite are both of a nanosheet structure, the surface of the tin diselenide/carbon nanotube film composite is coated with carbon nanotubes, and the carbon nanotubes are not uniformly distributed on the surface of the tin diselenide nanosheet. The pure tin diselenide material is uniformly dispersed into a lamellar structure, the thickness of each lamellar is about 100nm, the lamellar structures are mutually staggered, the surface area is enlarged due to the lamellar structure, the reaction contact area is increased, and the sodium insertion and sodium removal process is facilitated. The pure tin diselenide is of a leaf-shaped structure, the appearance of a reaction product is a nano thin sheet with irregular ports and smooth leaf surface, the thickness of the sheet layer is about 80nm, and the top of the sheet layer has a growth trend. The addition of carbon nanotubes results in increased flexibility and thus may be used in making bendable film, i.e. from powder to film as compared with pure tin diselenide. The tin diselenide/carbon nano tube film composite material does not need to be added with a conductive agent and an adhesive, can be directly cut into pieces to install the battery, saves time, simplifies the process and reduces the cost.
FIG. 3 is a constant current cycle diagram of the tin diselenide/carbon nanotube thin film composite material prepared in examples 1 to 3 at a current density of 0.1A/g. Wherein the round solid dotted line, the round hollow dotted line and the square hollow dotted line are respectively the tin diselenide/carbon nanotube thin film composite material prepared in the embodiments 1, 2 and 3. As can be seen from fig. 3, the tin diselenide/carbon nanotube thin film composite material has a capacity slightly attenuated after 30 charge-discharge cycles, and still has 70% of the initial capacity. The tin diselenide/carbon nanotube film composite material obtained by adding the carbon nanotube is beneficial to improving the stability of the material, and further improving the rate capability and the cycle performance of the material. After 30 cycles, the product still has higher specific capacity of 200 milliampere per gram, and has larger application prospect.
Fig. 4 is a rate performance curve of tin diselenide/carbon nanotube thin film composite materials prepared in examples 1-3. Wherein the round solid dotted line, the round hollow dotted line and the pentagonal hollow dotted line are respectively the tin diselenide/carbon nanotube thin film composite materials prepared in the embodiments 1, 2 and 3. It can be seen that the initial specific capacity of the tin diselenide/carbon nanotube film composite material prepared in example 1 is about 320mAh/g, the specific capacity can be recovered to 220mAh/g after charge and discharge cycles of 0.1A/g → 0.2A/g → 0.3A/g → 0.5A/g → 1A/g → 0.1A/g, the specific discharge capacities of the tin diselenide/carbon nanotube film composite material from 0.1A/g to 1A/g are 328mAh/g, 178mAh/g, 182mAh/g, 169mAh/g and 165mAh/g in sequence, and the specific capacity is recovered to 228mAh/g when the current density is returned to 0.1A/g from 1A/g. The rate performance curves of the tin diselenide/carbon nanotube thin film composite materials prepared in the embodiments 2 and 3 are equivalent to those of the tin diselenide/carbon nanotube thin film composite material prepared in the embodiment 1, and the difference is small.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A flexible self-supporting tin diselenide/carbon nano tube composite film electrode material is characterized in that the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material is prepared by mixing carbon nano tubes and ethylene glycol in an ultrasonic mode to obtain a mixed solution A; the power of the ultrasonic wave is 400-900W, the frequency of the ultrasonic wave is 10-25 kHz, and the time of the ultrasonic wave is 30-60 min; adding ethylenediamine, stirring and mixing to obtain a mixed solution B; adding stannous chloride dihydrate and selenium powder into the mixed solution B, stirring to obtain a mixed solution C, carrying out hydrothermal reaction on the mixed solution C at 150-220 ℃ for 18-30 h, carrying out vacuum filtration and washing on a product, and drying at 40-80 ℃ to obtain the stannous chloride dihydrate and selenium powder; the concentration of the mixed solution A is 0.4-1.5 mg/mL, and the concentration of the mixed solution B is 0.4-2 mg/mL; the volume ratio of the ethylenediamine to the ethylene glycol is 1: (10-20); the concentration of the stannous chloride dihydrate in the solution C is 2.5-4 mg/mL, and the molar ratio of the selenium powder to the stannous chloride dihydrate is (1.5-2.7): 1; the tin diselenide in the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material is of a lamellar structure, and the carbon nano tubes are uniformly coated on the surface of the tin diselenide.
2. The flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material of claim 1, wherein the carbon nanotubes are one or more of aminated single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes.
3. The flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material as claimed in claim 1, wherein the drying time is 5-8 hours.
4. The flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material as claimed in claim 1, wherein the reagents for suction filtration and washing are deionized water and absolute ethyl alcohol.
5. The preparation method of the flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material according to any one of claims 1 to 4, which is characterized by comprising the following specific steps of:
s1, ultrasonically mixing the carbon nano tube and ethylene glycol to obtain a mixed solution A;
s2, adding ethylenediamine into the mixed solution A, and stirring and mixing to obtain a mixed solution B;
s3, adding the stannous chloride dihydrate and the selenium powder into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
and S4, carrying out hydrothermal reaction on the mixed solution C at the temperature of 150-220 ℃, carrying out vacuum filtration and washing on the product, and drying at the temperature of 40-80 ℃ to obtain the flexible self-supporting tin diselenide/carbon nano tube composite film electrode material.
6. The use of the flexible self-supporting tin diselenide/carbon nanotube composite thin film electrode material of any one of claims 1 to 4 in the field of energy storage.
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