CN115347173A - Three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material and preparation method and application thereof - Google Patents
Three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material which comprises a double-layer carbon and tin oxide-based material, wherein the tin oxide-based material is coated on the surface of inner-layer carbon, and the outer-layer carbon is coated on the surface of the tin oxide-based material and mutually bridged to form a three-dimensional network structure. The carbon coating technology can effectively protect the volume structure stability of the tin oxide-based negative electrode material in the charge-discharge cycle process, the double carbon confinement can effectively relieve the volume change of the tin oxide-based material and improve the conductivity of the tin oxide-based material, and the problems of large volume change and poor electrode stability of the tin oxide-based material in the charge-discharge process are solved. Meanwhile, the three-dimensional bridging structure has a large specific surface area, so that the active material can be fully contacted with the electrolyte to promote capacity improvement. The three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material is applied to a potassium ion battery, has high rate capacity and good cycle performance, and is suitable for large-scale energy storage.
Description
Technical Field
The invention belongs to the technical field of novel ion battery cathode materials, and particularly relates to a three-dimensional bridged double-carbon-limited-domain tin oxide-based cathode material and a preparation method and application thereof.
Background
With the development of large energy storage systems such as electric cars and smart power grids, the disadvantages of lithium ion batteries are gradually obvious, the lithium resource reserves are limited, so that the cost is higher, the application of the lithium ion batteries in the large energy storage systems is limited, and the increasing energy requirements of people cannot be met, and potassium ion batteries are gradually an ideal substitute for the lithium ion batteries due to the characteristics of low cost, rich reserves and wide distribution.
The alloy cathode tin oxide-based material can be used as a cathode material of a potassium ion battery due to the characteristics of higher theoretical capacity, small polarization voltage and moderate working voltage. However, the volume change of the tin oxide-based material is large in the charging and discharging processes, the stability of the electrode is poor, particle pulverization is easy to cause, and the capacity is reduced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a three-dimensional bridged dual-carbon limited-domain tin oxide-based negative electrode material, and a preparation method and application thereof, so as to solve the problems of large volume change and poor electrode stability of the tin oxide-based material in the charging and discharging processes.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material which comprises a double-layer carbon and tin oxide-based material, wherein the tin oxide-based material is coated on the surface of inner-layer carbon, and the outer-layer carbon is coated on the surface of the tin oxide-based material and mutually linked to form a three-dimensional network structure;
the tin oxide-based material is a tin oxide material or a tin oxide/tin sulfide material.
Preferably, the mass fraction of the tin oxide base in the dual-carbon limited-area tin oxide-based negative electrode material is 60-90%, and the mass fraction of the dual-carbon is 10-40%.
The invention also discloses a preparation method of the three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material, and when the tin oxide-based material is a tin oxide material, the preparation method comprises the following steps:
s1, dissolving glucose in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A to obtain carbon spheres;
s3, dissolving the carbon spheres and the tin chloride in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, carrying out hydrothermal reaction on the precursor solution B to obtain tin oxide coated carbon spheres;
s5, dissolving the tin oxide coated carbon spheres and a carbon source in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, carrying out hydrothermal reaction on the precursor solution C to obtain a target product, namely the three-dimensional bridged double-carbon limited-range tin oxide cathode material.
Preferably, in step S1, the ratio of the glucose to the deionized water is 3g:30ml;
in the step S3, the dosage ratio of the carbon spheres, the stannic chloride and the deionized water is 0.12g: (0.26-0.78) g:30ml;
in step S5, the carbon source is glucose, dopamine hydrochloride or starch.
Preferably, in the step S2, the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 8h;
in the steps S4 and S6, the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 12h.
The invention discloses a preparation method of the three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material, which comprises the following steps of:
s1, dissolving glucose in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A to obtain carbon spheres;
s3, dissolving the carbon spheres and the tin chloride in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, carrying out hydrothermal reaction on the precursor solution B to obtain tin oxide coated carbon spheres;
s5, dissolving the tin oxide coated carbon spheres and the sulfur source in deionized water, and uniformly stirring to obtain a precursor solution D; carrying out hydrothermal reaction on the precursor solution D to obtain tin oxide/tin sulfide coated carbon spheres;
s6, dissolving the tin oxide/tin sulfide coated carbon spheres and a carbon source in deionized water, and uniformly stirring to obtain a precursor solution E;
s7, carrying out hydrothermal reaction on the precursor solution E to obtain the target product three-dimensional bridged double-carbon-confinement tin oxide/tin sulfide negative electrode material.
Preferably, in step S5, the sulfur source is thiourea or thioacetamide; the mass ratio of the tin oxide coated carbon spheres to the sulfur source is 1:1 to 10:1;
in the step S6, the usage ratio of the tin oxide/tin sulfide coated carbon spheres, the carbon source and the deionized water is 0.5g:0.12g:30ml.
Preferably, the temperature of the hydrothermal reaction of the precursor solution D is 180-200 ℃ and the time is 6-12 h.
The invention also discloses an application of the three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material in preparation of a potassium ion battery.
Preferably, the tin oxide-based negative electrode material, PVDF and acetylene black are mixed in a ratio of 7:2:1 into slurry, uniformly coating the slurry on a copper foil, drying to obtain a working electrode, and matching the working electrode with a counter electrode metal sodium to assemble a battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a three-dimensional bridged double-carbon-confinement tin oxide-based negative electrode material which comprises a double-layer carbon and a tin oxide-based material, wherein the tin oxide-based material is coated on the surface of an inner layer carbon, and the outer layer carbon is coated on the surface of the tin oxide-based material and mutually linked to form a three-dimensional network structure. The internal and external double-carbon-limited-domain carbon coating technology can effectively protect the volume structure stability of the tin oxide-based negative electrode material in the charge-discharge cycle process, the double-carbon limited domain can effectively relieve the volume change of the tin oxide-based material and improve the conductivity of the tin oxide-based material, and the problems of large volume change and poor electrode stability of the tin oxide-based material in the charge-discharge process are solved. Meanwhile, the three-dimensional bridging structure has a large specific surface area, so that the active material can be fully contacted with the electrolyte to promote capacity improvement. The three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material disclosed by the invention is high in rate capacity and good in cycle performance, and is suitable for large-scale energy storage.
The invention also discloses a preparation method of the three-dimensional bridged double-carbon-confinement tin oxide-based negative electrode material, wherein a structure with inner-layer carbon as tin oxide-coated carbon spheres is formed through hydrothermal reaction of carbon spheres and tin chloride, and a structure with outer-layer carbon coated on the surface layer of the tin oxide-coated carbon is further formed through hydrothermal reaction of the tin oxide-coated carbon spheres and a carbon source, so that the three-dimensional bridged double-carbon-confinement tin oxide-based negative electrode material is obtained. The invention has simple preparation process and low cost, and is suitable for large-scale use.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a three-dimensional bridged dual-carbon-limited-domain tin oxide cathode material according to the present invention;
FIG. 2 is a schematic diagram of a process for preparing a three-dimensional bridged dual-carbon-limited-domain tin oxide/tin sulfide negative electrode material of the present invention;
FIG. 3 is a cycle performance test chart of the three-dimensional bridged dual-carbon-limited-domain tin oxide cathode material of the present invention;
fig. 4 is a cycle performance test chart of the three-dimensional bridged dual-carbon-limited-domain tin oxide/tin sulfide negative electrode material.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Moreover, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material comprises double-layer carbon and tin oxide-based materials, wherein the tin oxide-based materials are coated on the surface of inner-layer carbon, and the outer-layer carbon is coated on the surface of the tin oxide-based materials and mutually bridged to form a three-dimensional network structure. The three-dimensional bridged double-carbon-limited-domain tin oxide-based cathode material comprises a double-carbon-limited-domain tin oxide cathode material and a double-carbon-limited-domain tin oxide/tin sulfide cathode material, wherein the double-carbon-limited-domain tin oxide and the double-carbon-limited-domain tin oxide/tin sulfide are used as basic units and are bridged to form a material with a three-dimensional porous network structure; the size of the basic unit is 50-500 nm, and the size of the three-dimensional porous network pore is 0.1-5 μm.
A method for preparing a three-dimensional bridged dual-carbon-limited-domain tin oxide negative electrode material, as shown in fig. 1, comprises the following steps:
s1, dissolving glucose in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and carrying out hydrothermal preparation to obtain carbon spheres;
s3, dissolving the carbon spheres and the tin chloride in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and carrying out hydrothermal preparation to obtain tin oxide coated carbon spheres;
s5, dissolving the tin oxide coated carbon spheres and glucose in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and carrying out hydrothermal preparation to obtain the target product, namely the three-dimensional network double-carbon-confinement tin oxide cathode material.
A method for preparing a three-dimensional bridged dual-carbon-limited-domain tin oxide/tin sulfide negative electrode material, as shown in fig. 2, comprises the following steps:
s1, dissolving glucose in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and carrying out hydrothermal preparation to obtain carbon spheres;
s3, dissolving the carbon spheres and the tin chloride in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and carrying out hydrothermal preparation to obtain tin oxide coated carbon spheres;
s5, dissolving the tin oxide coated carbon spheres and thiourea in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and carrying out hydrothermal preparation to obtain tin oxide and tin sulfide heterojunction-coated carbon spheres;
s7, dissolving tin oxide and tin sulfide heterojunction-coated carbon spheres and glucose in deionized water, and uniformly stirring to obtain a precursor solution D;
and S8, transferring the precursor solution D into a reaction kettle, and carrying out hydrothermal preparation to obtain the target product three-dimensional bridged double-carbon-limited-domain tin oxide/tin sulfide cathode material.
In the preparation process, the molar weight of the stannic chloride is 0.001-0.003 mol; the thiourea can be replaced by a sulfur source such as thioacetamide; glucose can be substituted by dopamine hydrochloride, starch and other carbon sources.
Example 1
S1, dissolving 3g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and reacting at 160 ℃ for 8h to prepare carbon spheres;
s3, dissolving 0.12g of carbon spheres and 0.001mol of stannic chloride in 30ml of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and reacting at 160 ℃ for 12 hours to prepare tin oxide coated carbon spheres;
s5, dissolving 0.5g of tin oxide coated carbon spheres and 0.12g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and reacting at 160 ℃ for 12h for hydrothermal reaction to obtain the target product, namely the three-dimensional bridged double-carbon-limited-domain tin oxide cathode material.
Example 2
S1, dissolving 3g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and reacting at 180 ℃ for 8 hours to prepare carbon spheres;
s3, dissolving 0.12g of carbon spheres and 0.002mol of tin chloride in 30ml of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and reacting at 180 ℃ for 12 hours to prepare tin oxide coated carbon spheres;
s5, dissolving 0.5g of tin oxide coated carbon spheres and 0.12g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and reacting at 180 ℃ for 12 hours for hydrothermal preparation to obtain the target product, namely the three-dimensional network double-carbon-limited-area tin oxide nanostructure.
The electrochemical test method of the three-dimensional bridged double-carbon-limited-domain tin oxide negative electrode material obtained in the embodiment is as follows:
a button cell is adopted to research the electrochemical performance of a negative electrode material, DMF is adopted as a solvent for a negative electrode, and the formula of a pole piece is as follows according to active substances: PVDF: acetylene black =7:2: preparing slurry according to the proportion of 1, uniformly coating the slurry on a copper foil, drying the copper foil in a vacuum drying oven at 80 ℃ for 12 hours, and punching to obtain the pole piece for the experimental battery. The charge-discharge cycling test is carried out on the button cell, wherein the charge-discharge cutoff voltage is 0.01-2.6V, and the charge-discharge current is 500mA/g, and the result shows that the capacity retention rate of the three-dimensional bridged double-carbon-limited-domain tin oxide negative electrode material is 70%, and the cycling performance is good.
Example 3
S1, dissolving 3g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and reacting at 200 ℃ for 8h to prepare carbon spheres;
s3, dissolving 0.12g of carbon spheres and 0.003mol of tin chloride in 30ml of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and reacting at 200 ℃ for 12 hours to prepare tin oxide coated carbon spheres;
s5, dissolving 0.5g of tin oxide coated carbon spheres and 0.12g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and reacting at 200 ℃ for 12h for hydrothermal preparation to obtain the target product, namely the three-dimensional network double-carbon-limited-domain tin oxide nano structure.
Example 4
S1, dissolving 3g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and reacting at 160 ℃ for 8h to prepare carbon spheres;
s3, dissolving 0.12g of carbon spheres and 0.001mol of stannic chloride in 30ml of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and reacting at 160 ℃ for 12 hours to prepare tin oxide coated carbon spheres;
s5, dissolving 0.5g of tin oxide coated carbon spheres and 0.001mol of thiourea in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and reacting at 180 ℃ for 6 hours to hydrothermally prepare tin oxide and tin sulfide heterojunction-coated carbon spheres;
s7, dissolving 0.5g of tin oxide and tin sulfide heterojunction-coated carbon spheres and 0.12g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution D;
and S8, transferring the precursor solution D into a reaction kettle, and reacting at 160 ℃ for 12 hours for hydrothermal preparation to obtain the target product, namely the three-dimensional bridged double-carbon-limited-range tin oxide/tin sulfide negative electrode material.
Example 5
S1, dissolving 3g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and reacting at 180 ℃ for 8h to prepare carbon spheres;
s3, dissolving 0.12g of carbon spheres and 0.002mol of stannic chloride in 30ml of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and reacting at 180 ℃ for 12 hours to prepare tin oxide coated carbon spheres;
s5, dissolving 0.5g of tin oxide coated carbon spheres and 0.002mol of thiourea in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and carrying out a hydrothermal reaction at 180 ℃ for 12 hours to obtain tin oxide and tin sulfide heterojunction-coated carbon spheres;
s7, dissolving 0.5g of tin oxide and tin sulfide heterojunction-coated carbon spheres and 0.12g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution D;
and S8, transferring the precursor solution D into a reaction kettle, and reacting at 180 ℃ for 12 hours for hydrothermal preparation to obtain the target product, namely the three-dimensional bridged double-carbon-limited-range tin oxide/tin sulfide negative electrode material.
Referring to fig. 4, the electrochemical test method of the three-dimensional bridged dual-carbon-limited-domain tin oxide/tin sulfide negative electrode material obtained in this example is the same as that of example 2. The result shows that the capacity retention rate of the three-dimensional bridged double-carbon-limited tin oxide/tin sulfide negative electrode material is 75%, and the excellent cycle performance is shown, so that the better electrochemical performance is shown.
Example 6
S1, dissolving 3g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution A;
s2, transferring the precursor solution A into a reaction kettle, and reacting at 200 ℃ for 8 hours to prepare carbon spheres;
s3, dissolving 0.12g of carbon spheres and 0.003mol of tin chloride in 30ml of deionized water, and uniformly stirring to obtain a precursor solution B;
s4, transferring the precursor solution B into a reaction kettle, and reacting at 200 ℃ for 12 hours to prepare tin oxide coated carbon spheres;
s5, dissolving 0.5g of tin oxide coated carbon spheres and 0.003mol of thiourea in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, transferring the precursor solution C into a reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 6 hours to obtain tin oxide and tin sulfide heterojunction-coated carbon spheres;
s7, dissolving 0.5g of tin oxide and tin sulfide heterojunction-coated carbon spheres and 0.12g of glucose in 30ml of deionized water, and uniformly stirring to obtain a precursor solution D;
and S8, transferring the precursor solution D into a reaction kettle, and reacting at 200 ℃ for 12 hours for hydrothermal preparation to obtain the target product, namely the three-dimensional bridged double-carbon-limited-range tin oxide/tin sulfide negative electrode material.
In conclusion, the three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material is simple in preparation process, mild in preparation conditions and suitable for large-scale production, the internal and external double-carbon-limited domains can effectively protect the volume structure stability of the tin oxide and tin oxide/tin sulfide negative electrode material in the charge-discharge cycle process, and the double-carbon-limited domains can effectively relieve the volume change of the tin oxide and tin oxide/tin sulfide material and improve the conductivity of the tin oxide and tin oxide/tin sulfide material, so that the potassium ion storage performance is improved; the three-dimensional bridging structure has a large specific surface area, can realize full contact between an active material and electrolyte to promote capacity improvement, and has certain advantages in application of potassium ion battery cathode materials.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A three-dimensional bridged double-carbon limited-domain tin oxide-based negative electrode material is characterized by comprising double-layer carbon and tin oxide-based materials, wherein the tin oxide-based materials are coated on the surface of inner-layer carbon, and the outer-layer carbon is coated on the surface of the tin oxide-based materials and mutually bridged to form a three-dimensional network structure;
the tin oxide-based material is a tin oxide material or a tin oxide/tin sulfide material.
2. The three-dimensional bridged double-carbon-limited tin oxide-based negative electrode material as claimed in claim 1, wherein the mass fraction of tin oxide groups in the double-carbon-limited tin oxide-based negative electrode material is 60-90%, and the mass fraction of double carbon is 10-40%.
3. The method for preparing a three-dimensional bridged dual-carbon-restricted-domain tin oxide-based negative electrode material of claim 1, wherein when the tin oxide-based material is a tin oxide material, the preparation method is as follows:
s1, dissolving glucose in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A to obtain carbon spheres;
s3, dissolving the carbon spheres and the tin chloride in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, carrying out hydrothermal reaction on the precursor solution B to obtain tin oxide coated carbon spheres;
s5, dissolving the tin oxide coated carbon spheres and the carbon source in deionized water, and uniformly stirring to obtain a precursor solution C;
s6, carrying out hydrothermal reaction on the precursor solution C to obtain the target product three-dimensional bridged double-carbon-confinement tin oxide cathode material.
4. The method for preparing the three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material as claimed in claim 3, wherein in the step S1, the dosage ratio of glucose to deionized water is 3g:30ml;
in the step S3, the dosage ratio of the carbon spheres, the stannic chloride and the deionized water is 0.12g: (0.26-0.78) g:30ml;
in step S5, the carbon source is glucose, dopamine hydrochloride or starch.
5. The preparation method of the three-dimensional bridged two-carbon limited-area tin oxide-based negative electrode material according to claim 3, wherein in the step S2, the hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 8h;
in the steps S4 and S6, the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 12h.
6. The method of preparing the three-dimensional bridged dual-carbon-restricted-domain tin oxide-based negative electrode material of claim 1, wherein when the tin oxide-based material is a tin oxide/tin sulfide material, the method is as follows:
s1, dissolving glucose in deionized water, and uniformly stirring to obtain a precursor solution A;
s2, carrying out hydrothermal reaction on the precursor solution A to obtain carbon spheres;
s3, dissolving the carbon spheres and the tin chloride in deionized water, and uniformly stirring to obtain a precursor solution B;
s4, carrying out hydrothermal reaction on the precursor solution B to obtain tin oxide coated carbon spheres;
s5, dissolving the tin oxide coated carbon spheres and the sulfur source in deionized water, and uniformly stirring to obtain a precursor solution D; carrying out hydrothermal reaction on the precursor solution D to obtain tin oxide/tin sulfide coated carbon spheres;
s6, dissolving the tin oxide/tin sulfide coated carbon spheres and a carbon source in deionized water, and uniformly stirring to obtain a precursor solution E;
s7, carrying out hydrothermal reaction on the precursor solution E to obtain a target product three-dimensionally bridged double-carbon limited-range tin oxide/tin sulfide negative electrode material.
7. The method for preparing the three-dimensional bridged dual-carbon-restricted tin oxide-based negative electrode material according to claim 6, wherein in step S5, the sulfur source is thiourea or thioacetamide; the mass ratio of the tin oxide coated carbon spheres to the sulfur source is 1:1 to 10:1;
in the step S6, the usage ratio of the tin oxide/tin sulfide coated carbon spheres, the carbon source and the deionized water is 0.5g:0.12g:30ml.
8. The preparation method of the three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material as claimed in claim 6, wherein in the step S5, the temperature of the precursor solution D for hydrothermal reaction is 180-200 ℃ and the time is 6-12 h.
9. Use of the three-dimensional bridged dual-carbon-restricted tin oxide-based negative electrode material of claim 1 or 2 for the preparation of a potassium-ion battery.
10. Use according to claim 9, characterized in that the tin oxide-based negative electrode material, PVDF and acetylene black are mixed in a ratio of 7:2:1 into slurry, uniformly coating the slurry on a copper foil, drying to obtain a working electrode, and matching the working electrode with a counter electrode metal sodium to assemble a battery.
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