CN114551891A - Tin disulfide/titanium dioxide/carbon composite material and preparation method and application thereof - Google Patents
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Abstract
The invention provides a tin disulfide/titanium dioxide/carbon composite material, and a preparation method and application thereof. The invention utilizes the surface limited domain in-situ growth mechanism to prepare the tin disulfide/titanium dioxide/carbon composite material, and in the composite material, the nano-scale tin disulfide and titanium dioxide are sealed in a porous carbon skeleton. The porous carbon skeleton not only improves the conductivity of the tin disulfide, but also increases the contact area of the active material and the electrolyte, and shortens the transmission path of ions/electrons. The nano-scale titanium dioxide has certain elasticity and polar adsorption, provides a buffer effect for volume expansion of the tin disulfide caused by sodium ion removal/insertion, and can adsorb sodium polysulfide products generated in the process of sodium ion removal/insertion of the tin disulfide. The combination of the porous carbon skeleton and the titanium dioxide improves the cycling stability and rate capability of the tin disulfide. The composite material has excellent cycling stability and rate capability as a cathode material of a sodium ion battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a tin disulfide/titanium dioxide/carbon composite material and a preparation method and application thereof.
Background
With the rapid development and wide application of lithium ion battery technology, the demand of lithium source is increasing continuously, so that the cost of lithium ion battery is continuously increased, which is difficult to meet the use demand of smart grid requiring low price and large-scale chemical energy conversion electric energy of renewable energy, and the reserve of lithium source becomes the primary problem hindering the wide application of lithium ion battery. In contrast, the earth crust has abundant sodium resources, and the sodium ion battery has an electrochemical reaction mechanism similar to that of the lithium ion battery, and has recently attracted great attention as an important substitute of the lithium ion battery.
Among the numerous sodium ion negative electrode materials, transition metal sulfides such as tin disulfide are one of the best candidates for sodium ion battery negative electrode materials due to their high theoretical capacity. However, the tin disulfide sodium ion battery cathode materials prepared in the prior art all have poor cycle stability due to large volume expansion caused in the process of sodium ion removal/insertion. In addition, tin disulfide can generate sodium polysulfide product during the process of sodium ion extraction, and the sodium polysulfide product is easy to generate shuttle effect in electrolyte, and the cycle performance of tin disulfide can also be rapidly reduced. The tin disulfide has low electronic conductivity, so that the tin disulfide has serious polarization phenomenon under the condition of heavy current charge and discharge, and further has the problems of low rate performance and the like. These problems have severely hampered the continued use of tin disulfide in sodium ion batteries. Therefore, a tin disulfide material capable of meeting the use requirement of the cathode material of the sodium-ion battery is needed in the prior art.
Disclosure of Invention
In order to effectively solve the defects of tin disulfide as a negative electrode material of a sodium ion battery, the invention provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, and the prepared nano-scale tin disulfide and titanium dioxide are sealed in a porous carbon skeleton. The porous carbon skeleton not only improves the conductivity of the tin disulfide, but also increases the contact area of the active material and the electrolyte, and shortens the transmission path of ions/electrons. The nanometer titanium dioxide has certain elasticity and polar adsorption, and the function not only provides a buffer function for the volume expansion of the tin disulfide caused by sodium ion removal/insertion, but also can adsorb sodium polysulfide products generated in the process of sodium ion removal/insertion of the tin disulfide. The combination of the porous carbon skeleton and the titanium dioxide improves the cycling stability and rate capability of the tin disulfide.
In a first aspect, the invention provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following steps:
s1, adding the tin source into absolute ethyl alcohol, stirring until the tin source is completely dissolved, and then sequentially adding phenol and formaldehyde, and continuously stirring until the tin source is completely dissolved; wherein the tin source is one of stannic chloride pentahydrate, stannous chloride dihydrate, anhydrous stannic chloride and anhydrous stannous chloride;
s2, adding a titanium source into the step S1, then quickly adding ammonia water, hydrolyzing the titanium source and the tin source to generate titanium dioxide and tin dioxide precursors under the action of the ammonia water, reacting the phenol and the formaldehyde to generate phenolic resin, continuously stirring for 2 hours after the dropwise addition is finished, and cleaning and drying the obtained precipitate; wherein the titanium source is one of titanium tetrachloride, tetrabutyl titanate and titanium isopropoxide;
s3, mixing the product obtained in the step S2 with sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment under a protective atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
The phenol and formaldehyde react to form a phenolic resin which is carbonized after heat treatment, from which the carbon in the present application originates.
Preferably, the molar ratio of the tin source in the step S1 to the titanium source in the step S2 is 5:1-1: 3.
Preferably, the phenol in the step S1 is one of 3-aminophenol, hydroquinone and resorcinol.
Preferably, the heating rate of the heat treatment in the step S3 is 2-10 ℃/min; the temperature of the heat treatment in the step S3 is 400-800 ℃.
In a second aspect, the present invention also provides a tin disulfide/titanium dioxide/carbon composite material prepared by the above preparation method, the tin disulfide/titanium dioxide/carbon composite material comprising tin disulfide as an active site for sodium desorption/intercalation, titanium dioxide as a means for alleviating volume expansion of tin disulfide during sodium desorption/intercalation and adsorbing sodium polysulfide, and carbon as a conductive network.
Preferably, the particle size of the tin disulfide is 5-30 nm; the particle size of the titanium dioxide is 3-20 nm; the carbon exhibits a porous skeletal structure; the tin disulfide and titanium dioxide are encapsulated in carbon at the same time.
In a third aspect, the invention also provides an application of the tin disulfide/titanium dioxide/carbon composite material in a sodium ion negative electrode material.
The invention prepares the sodium ion battery cathode material from the prepared tin disulfide/titanium dioxide/carbon composite material. The preparation method comprises the following steps:
adding a tin disulfide/titanium dioxide/carbon composite material (active substance), acetylene black (conductive agent) and sodium carboxymethylcellulose (binder) into deionized water according to the mass ratio of 8:1:1, uniformly stirring, coating on a copper foil with the thickness of 25 micrometers, then placing the copper foil into a vacuum drying oven with the temperature of 80 ℃, drying for 12 hours, taking out, and cutting the copper foil into a wafer with the diameter of 16 millimeters by using a cutting machine, namely a negative pole piece.
Compared with the prior art, the invention achieves the following beneficial effects:
1. the preparation method is simple to operate, easy to control and short in preparation period, and is beneficial to realizing commercial large-scale production;
2. according to the tin disulfide/titanium dioxide/carbon composite material prepared by the invention, the carbon skeleton has a porous structure, so that the conductivity of the composite material can be improved, the contact area of an active material and an electrolyte is greatly increased, the diffusion path of ions/electrons is shortened, and the rate capability of the composite material serving as a cathode material of a sodium ion battery is improved;
3. according to the tin disulfide/titanium dioxide/carbon composite material prepared by the invention, the titanium dioxide nanoparticles have elasticity and an adsorption effect, so that the volume expansion of tin disulfide in a sodium removal/insertion process can be relieved, a sodium polysulfide product generated in the sodium removal/insertion process of tin disulfide can be adsorbed, and the circulation stability performance when the tin disulfide/titanium dioxide/carbon composite material is used as a sodium ion battery cathode material is improved;
4. according to the tin disulfide/titanium dioxide/carbon composite material prepared by the invention, the tin disulfide serving as a sodium storage main body has a very small particle size, so that the volume expansion of the tin disulfide in a sodium removal/insertion process can be relieved, the diffusion path of ions/electrons is shortened, and the cycle and rate performance when the tin disulfide/titanium dioxide/carbon composite material is used as a sodium ion battery cathode material are improved;
5. according to the tin disulfide/titanium dioxide/carbon composite material prepared by the invention, due to the mutual interaction of the porous property of the carbon skeleton, the elasticity and the adsorption property of titanium dioxide and the ultra-small particle size of tin disulfide, when the composite material is used as a negative electrode material of a sodium ion battery, the composite material shows excellent sodium storage property, and when the charge-discharge current density is 0.2A/g, the capacity is kept at 692.5mAh/g after 100 cycles; when the charging and discharging current is increased to 10A/g, the high capacity of 328.7mAh/g is still maintained.
Drawings
In order to clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly described below, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a scanning electron microscope image of the tin disulfide/titanium dioxide/carbon composite material prepared in example 1 of the present invention.
Figure 2 is an XRD pattern of the tin disulfide/titanium dioxide/carbon composite prepared in example 1 of the present invention.
Figure 3 is an elemental distribution plot of a tin disulfide/titanium dioxide/carbon composite prepared in example 1 of the present invention.
Figure 4 is a graph showing electrochemical cycle life measurements of the tin disulfide/titanium dioxide/carbon composite prepared in example 1 of the present invention.
Fig. 5 is a test chart of electrochemical rate capability of the tin disulfide/titanium dioxide/carbon composite material prepared in the embodiment 1 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 2mol of stannous chloride dihydrate into 60mL of anhydrous ethanol, stirring until the stannous chloride dihydrate is completely dissolved, and then sequentially adding 0.2g of 3-aminophenol and 0.2mL of formaldehyde, and continuously stirring until the stannous chloride dihydrate is completely dissolved;
s2, adding 2mol of tetrabutyl titanate into the step S1, then quickly adding 1mL of ammonia water, hydrolyzing tetrabutyl titanate and stannous chloride dihydrate to generate titanium dioxide and stannic oxide precursors under the action of the ammonia water, reacting 3-aminophenol with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after dropwise adding, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment at 600 ℃ at a heating rate of 5 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
The embodiment also provides a tin disulfide/titanium dioxide/carbon composite material prepared by the method, the composite material comprises tin disulfide serving as a sodium removal/insertion active site, titanium dioxide serving as a conductive network and carbon (in the embodiment, 3-aminophenol and formaldehyde react to generate phenolic resin, and the phenolic resin is carbonized after heat treatment, and the carbon in the embodiment is derived from the carbon in the embodiment). Other embodiments of the present application also include embodiments of products obtained by method embodiments, which are not described in detail in the following embodiments.
Example 2
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 2mol of stannous chloride dihydrate into 60mL of anhydrous ethanol, stirring until the stannous chloride dihydrate is completely dissolved, and then sequentially adding 0.2g of 3-aminophenol and 0.2mL of formaldehyde, and continuously stirring until the stannous chloride dihydrate is completely dissolved;
s2, adding 1mol of tetrabutyl titanate into the step S1, then quickly adding 1mL of ammonia water, hydrolyzing tetrabutyl titanate and stannous chloride dihydrate to generate titanium dioxide and stannic oxide precursors under the action of the ammonia water, reacting 3-aminophenol with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after dropwise adding, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment at 600 ℃ at a heating rate of 10 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Example 3
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 2mol of stannic chloride pentahydrate into 60mL of absolute ethyl alcohol, stirring until the stannic chloride pentahydrate is completely dissolved, and then sequentially adding 0.2g of 3-aminophenol and 0.2mL of formaldehyde, and continuously stirring until the stannic chloride pentahydrate is completely dissolved;
s2, adding 2mol of tetrabutyl titanate into the step S1, then quickly adding 0.5mL of ammonia water, hydrolyzing tetrabutyl titanate and stannic chloride pentahydrate to generate titanium dioxide and stannic oxide precursors under the action of the ammonia water, reacting 3-aminophenol with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after the dropwise addition is finished, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment at 800 ℃ at a heating rate of 10 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Example 4
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 2mol of stannic chloride pentahydrate into 60mL of absolute ethyl alcohol, stirring until the stannic chloride pentahydrate is completely dissolved, and then sequentially adding 0.2g of hydroquinone and 0.2mL of formaldehyde, and continuously stirring until the hydroquinone and the formaldehyde are completely dissolved;
s2, adding 1mol of titanium tetrachloride into the step S1, then quickly adding 0.5mL of ammonia water, hydrolyzing the titanium tetrachloride and tin tetrachloride pentahydrate to generate titanium dioxide and tin dioxide precursors under the action of the ammonia water, reacting hydroquinone with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after dropwise addition is finished, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment at 800 ℃ at a heating rate of 10 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Example 5
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 2mol of anhydrous tin tetrachloride into 60mL of anhydrous ethanol, stirring until the anhydrous tin tetrachloride is completely dissolved, and then sequentially adding 0.2g of 3-aminophenol and 0.2mL of formaldehyde, and continuously stirring until the anhydrous tin tetrachloride is completely dissolved;
s2, adding 2mol of titanium tetrachloride into the step S1, then quickly adding 2mL of ammonia water, hydrolyzing the titanium tetrachloride and anhydrous tin tetrachloride to generate titanium dioxide and tin dioxide precursors under the action of the ammonia water, reacting 3-aminophenol with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after dropwise addition is finished, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment at 600 ℃ at a heating rate of 10 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Example 6
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 2mol of anhydrous tin tetrachloride into 60mL of anhydrous ethanol, stirring until the anhydrous tin tetrachloride is completely dissolved, and then sequentially adding 0.2g of 3-aminophenol and 0.2mL of formaldehyde, and continuously stirring until the anhydrous tin tetrachloride is completely dissolved;
s2, adding 3mol of titanium isopropoxide into the step S1, then quickly adding 3mL of ammonia water, hydrolyzing the titanium isopropoxide and anhydrous tin tetrachloride to generate titanium dioxide and a tin dioxide precursor under the action of the ammonia water, reacting 3-aminophenol with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after dropwise adding is finished, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out 700 ℃ heat treatment at a heating rate of 10 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Example 7
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 5mol of anhydrous stannous chloride into 60mL of anhydrous ethanol, stirring until the anhydrous stannous chloride is completely dissolved, and then sequentially adding 0.2g of resorcinol and 0.2mL of formaldehyde, and continuously stirring until the resorcinol and the formaldehyde are completely dissolved;
s2, adding 1mol of titanium isopropoxide into the step S1, then quickly adding 3mL of ammonia water, hydrolyzing the titanium isopropoxide and anhydrous stannous chloride to generate titanium dioxide and stannic oxide precursors under the action of the ammonia water, reacting resorcinol and formaldehyde to generate phenolic resin, continuously stirring for 2h after dropwise adding is finished, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out 400 ℃ heat treatment at a heating rate of 2 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Example 8
The embodiment provides a preparation method of a tin disulfide/titanium dioxide/carbon composite material, which comprises the following specific steps:
s1, adding 1mol of anhydrous stannous chloride into 60mL of anhydrous ethanol, stirring until the anhydrous stannous chloride is completely dissolved, and then sequentially adding 0.2g of 3-aminophenol and 0.2mL of formaldehyde, and continuously stirring until the anhydrous stannous chloride is completely dissolved;
s2, adding 3mol of tetrabutyl titanate into the step S1, then quickly adding 1mL of ammonia water, hydrolyzing tetrabutyl titanate and anhydrous stannous chloride to generate titanium dioxide and stannic oxide precursors under the action of the ammonia water, reacting 3-aminophenol with formaldehyde to generate phenolic resin, continuously stirring for 2 hours after dropwise adding, and cleaning and drying the obtained precipitate;
s3, mixing 0.2g of the product obtained in the step S2 with 1g of sublimed sulfur, placing the mixture in a tube furnace, and carrying out 700 ℃ heat treatment at a heating rate of 5 ℃/min under an argon atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
Scanning electron microscopy, X-ray diffraction and elemental analysis characterization are carried out on the tin disulfide/titanium dioxide/carbon composite material prepared in the embodiment 1, the tin disulfide/titanium dioxide/carbon composite material prepared in the embodiment 1 is assembled into a battery, the electrochemical cycling stability and rate capability of the battery are tested, the charging and discharging current density of the cycling stability test is 0.2A/g, and the operation is carried out until the charging and discharging current density is 0.2A/gThe discharge voltage is 0.01-3V; the current density of charge and discharge is 0.2, 0.5, 1, 2, 5, 10 and 0.2A/g in sequence in the multiplying power performance test, and the voltage is cut off to be 0.01-3V. In the process of assembling the battery, the tin disulfide/titanium dioxide/carbon composite material (active substance), the acetylene black (conductive agent) and the sodium carboxymethylcellulose (binder) are added into deionized water according to the mass ratio of 8:1:1, are uniformly stirred, are coated on a copper foil with the thickness of 25 micrometers, are placed into a vacuum drying oven at the temperature of 80 ℃ to be dried for 12 hours, are taken out, and are cut into a wafer with the diameter of 16 millimeters by a cutting machine, namely a negative pole piece. Assembling a negative pole piece and a metal sodium as a counter electrode to form a button cell for measuring the electrochemical performance of the button cell, wherein the electrolyte is NaClO4EC (1: 1, volume ratio).
As can be seen from fig. 1, the tin disulfide/titanium dioxide/carbon composite material prepared in example 1 of the present invention has a porous structure in appearance, and the pores are formed by a plurality of nano-spheres formed by packing nano-tin disulfide and titanium dioxide in carbon. On one hand, the porous structure is beneficial to the electrolyte to permeate into the active material, so that the contact area between the active material and the electrolyte is increased, the diffusion path of ions/electrons is further shortened, and the rate capability of the composite material is improved; on the other hand, the elasticity and the adsorption of the titanium dioxide can relieve the volume expansion of the tin disulfide, and can also prevent the shuttle effect of a sodium polysulfide product between electrolytes, thereby being beneficial to improving the cycle stability of the composite material. As can be seen from fig. 2, the XRD pattern of the tin disulfide/titanium dioxide/carbon composite material prepared in example 1 of the present invention is consistent with that of the standard PDF card of tin disulfide (JCPDF No. 23-0677), and since the formation of tin disulfide greatly inhibits the crystal growth of titanium dioxide during the post-heat treatment vulcanization, titanium dioxide exhibits an amorphous structure, and further, since the degree of crystallization of the carbon material is low, the XRD diffraction peak of the carbon material is weak with respect to tin disulfide, the diffraction peaks of titanium dioxide and carbon are not observed in the XRD diffraction pattern of the tin disulfide/titanium dioxide/carbon composite material. As can be seen from fig. 3, five elements, i.e., carbon, oxygen, sulfur, titanium, and tin, are uniformly distributed in the composite material sample, which indicates that the titanium dioxide and the tin disulfide nanoparticles are uniformly sealed in the conductive carbon skeleton, and combined with the XRD detection result, the titanium dioxide nanoparticles exist in an amorphous structure, and mainly play a role in alleviating volume expansion of tin disulfide during sodium intercalation and polar adsorption of sodium polysulfide generated during sodium intercalation. As can be seen from fig. 4 and 5, the sodium ion negative electrode material obtained in example 1 of the present invention exhibits stable cycle performance and excellent rate performance, the reversible specific capacity after 100 cycles of cycle is maintained at 692.5mAh/g, and when the charge and discharge current is increased to 10A/g, the high reversible specific capacity of 328.7mAh/g is still maintained. In conclusion, the tin disulfide/titanium dioxide/carbon composite material prepared by the method provided by the invention has excellent cycling stability and rate capability when being used as a negative electrode material of a sodium ion battery.
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Claims (7)
1. A preparation method of a tin disulfide/titanium dioxide/carbon composite material is characterized by comprising the following steps:
s1, adding the tin source into absolute ethyl alcohol, stirring until the tin source is completely dissolved, and then sequentially adding phenol and formaldehyde, and continuously stirring until the tin source is completely dissolved; wherein the tin source is one of stannic chloride pentahydrate, stannous chloride dihydrate, anhydrous stannic chloride and anhydrous stannous chloride;
s2, adding a titanium source into the step S1, then quickly adding ammonia water, hydrolyzing the titanium source and the tin source to generate titanium dioxide and tin dioxide precursors under the action of the ammonia water, reacting the phenol and the formaldehyde to generate phenolic resin, continuously stirring for 2 hours after the dropwise addition is finished, and cleaning and drying the obtained precipitate; wherein the titanium source is one of titanium tetrachloride, tetrabutyl titanate and titanium isopropoxide;
s3, mixing the product obtained in the step S2 with sublimed sulfur, placing the mixture in a tube furnace, and carrying out heat treatment under a protective atmosphere to obtain the tin disulfide/titanium dioxide/carbon composite material.
2. The method of claim 1, wherein the molar ratio of the tin source in step S1 to the titanium source in step S2 is from 5:1 to 1: 3.
3. The method of claim 1, wherein the phenol in step S1 is one of 3-aminophenol, hydroquinone and resorcinol.
4. The method of claim 1, wherein the temperature increase rate of the heat treatment in step S3 is 2-10 ℃/min; the temperature of the heat treatment in the step S3 is 400-800 ℃.
5. The tin disulfide/titanium dioxide/carbon composite material produced by the production method according to any one of claims 1 to 4, wherein the tin disulfide/titanium dioxide/carbon composite material comprises tin disulfide as an active site for sodium desorption/intercalation, titanium dioxide as a means for alleviating volume expansion of tin disulfide during sodium desorption/intercalation and adsorbing sodium polysulfide, and carbon as a conductive network.
6. The tin disulfide/titanium dioxide/carbon composite of claim 5, wherein the particle size of the tin disulfide is from 5 to 30 nm; the particle size of the titanium dioxide is 3-20 nm; the carbon exhibits a porous skeletal structure; the tin disulfide and titanium dioxide are encapsulated in carbon at the same time.
7. Use of a tin disulphide/titanium dioxide/carbon composite material according to any one of claims 5 to 6 in a sodium ion negative electrode material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282136A (en) * | 2023-05-25 | 2023-06-23 | 新乡学院 | Preparation method of in-situ vertically grown tin sulfide nanosheets |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585527A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | In a kind of being rich in, the charcoal preparation methods of macropore |
| WO2010030019A1 (en) * | 2008-09-10 | 2010-03-18 | 住友化学株式会社 | Non-aqueous electrolyte secondary cell |
| CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
| CN107175097A (en) * | 2017-06-22 | 2017-09-19 | 陕西科技大学 | A kind of stannic disulfide parcel titanium dioxide composite photocatalyst and preparation method thereof |
| CN108786849A (en) * | 2018-06-08 | 2018-11-13 | 西北师范大学 | A kind of preparation and application of artificial gold/composite titania material |
| CN109626423A (en) * | 2018-12-17 | 2019-04-16 | 上海应用技术大学 | A method of preparing poriferous titanium dioxide ball |
| CN110808368A (en) * | 2019-12-05 | 2020-02-18 | 中国石油大学(华东) | SnS/TiO for potassium ion battery cathode2rGO composite material, preparation method and electrolyte matched with same |
| CN111943256A (en) * | 2020-07-07 | 2020-11-17 | 厦门大学 | Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material |
| CN113421971A (en) * | 2021-06-28 | 2021-09-21 | 大连理工大学 | Method for preparing perovskite solar cell without charge transport layer through solvent pre-assistance |
-
2022
- 2022-04-27 CN CN202210447333.3A patent/CN114551891B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585527A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | In a kind of being rich in, the charcoal preparation methods of macropore |
| WO2010030019A1 (en) * | 2008-09-10 | 2010-03-18 | 住友化学株式会社 | Non-aqueous electrolyte secondary cell |
| CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
| CN107175097A (en) * | 2017-06-22 | 2017-09-19 | 陕西科技大学 | A kind of stannic disulfide parcel titanium dioxide composite photocatalyst and preparation method thereof |
| CN108786849A (en) * | 2018-06-08 | 2018-11-13 | 西北师范大学 | A kind of preparation and application of artificial gold/composite titania material |
| CN109626423A (en) * | 2018-12-17 | 2019-04-16 | 上海应用技术大学 | A method of preparing poriferous titanium dioxide ball |
| CN110808368A (en) * | 2019-12-05 | 2020-02-18 | 中国石油大学(华东) | SnS/TiO for potassium ion battery cathode2rGO composite material, preparation method and electrolyte matched with same |
| CN111943256A (en) * | 2020-07-07 | 2020-11-17 | 厦门大学 | Preparation method and application of flexible self-supporting tin-based sulfide-carbon composite material |
| CN113421971A (en) * | 2021-06-28 | 2021-09-21 | 大连理工大学 | Method for preparing perovskite solar cell without charge transport layer through solvent pre-assistance |
Non-Patent Citations (1)
| Title |
|---|
| WEINA REN等: "SnS2 nanosheets arrays sandwiched by N-doped carbon and TiO2 for high-performance Na-ion storage", 《GREEN ENERGY & ENVIRONMENT 》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282136A (en) * | 2023-05-25 | 2023-06-23 | 新乡学院 | Preparation method of in-situ vertically grown tin sulfide nanosheets |
| CN116282136B (en) * | 2023-05-25 | 2024-03-22 | 新乡学院 | Preparation method of in-situ vertically grown tin sulfide nanosheets |
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