CN113206225B - Hollow carbon sphere anchored with metal sulfide, preparation method thereof and application of hollow carbon sphere in preparation of potassium ion battery cathode - Google Patents

Hollow carbon sphere anchored with metal sulfide, preparation method thereof and application of hollow carbon sphere in preparation of potassium ion battery cathode Download PDF

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CN113206225B
CN113206225B CN202110390151.2A CN202110390151A CN113206225B CN 113206225 B CN113206225 B CN 113206225B CN 202110390151 A CN202110390151 A CN 202110390151A CN 113206225 B CN113206225 B CN 113206225B
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hollow carbon
acetylacetonate
metal
anchored
ion battery
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CN113206225A (en
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吴松平
宋杨
琚家豪
付丽丽
孙浩
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Guangdong Dianchi Qianli New Energy Co.,Ltd.
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South China University of Technology SCUT
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a hollow carbon sphere anchored with metal sulfide, a preparation method thereof and application thereof in preparing a potassium ion battery cathode; the preparation method of the hollow carbon sphere comprises the following steps: (1) Dissolving metal salt of acetylacetone in organic solvent, stirring and heating to prepare metal oxide particles; (2) Preparing metal oxide particles coated by organic polymers by electrostatic spraying; (3) Coating dopamine hydrochloride solution to prepare an organic polymer ball; and (4) carbonizing and vulcanizing to prepare the hollow carbon spheres. The spherical particles are manufactured without a template, and the spherical high molecules are formed by completely utilizing the surface tension in water; saves raw materials and has environmental protection. The method is quite rare in the manufacturing of the electrode material, has great innovation, and has great hint on the design of the hollow structure of the electrode material. The hollow carbon spheres containing the metal sulfide have excellent electrical property as a negative electrode material of a potassium ion battery.

Description

Hollow carbon sphere anchored with metal sulfide, preparation method thereof and application of hollow carbon sphere in preparation of potassium ion battery cathode
Technical Field
The invention belongs to the technical field of potassium ion battery cathode materials, and particularly relates to a hollow carbon sphere anchored with metal sulfide, a preparation method of the hollow carbon sphere and application of the hollow carbon sphere in preparation of a potassium ion battery cathode.
Background
With the rapid development of the industrial society, lithium ion batteries have been widely used in various fields. But there are still serious concerns facing the high cost of lithium ion batteries and the limitation of lithium resources. Thus, a need has arisen to produce a new type of battery that replaces lithium ion batteries, primarily sodium ion batteries and potassium ion batteries. The potassium ion battery also has the obvious advantages that: 1. the potassium ion battery is stored in the earth crust quite abundantly, which means that the potassium ion battery is low in cost. 2. The volume expansion of the potassium ion battery is greatly reduced compared with that of the lithium ion battery, and the potassium ion battery has higher safety performance. 3. The energy density of potassium ion batteries is higher and close to that of lithium ion batteries. In conclusion, the potassium ion battery has excellent application prospect in the future. Therefore, it is of great significance to design a potassium ion battery with high energy density and long cycle life.
Metal sulfides have shown excellent performance in potassium ion batteries. However, the stability is still far from ideal due to its long cycle. In the current research, the combination of the metal sulfide and the carbon material is found to have better cycle stability. If the two advantages of the stability of the carbon material and the high capacity of the metal sulfide can be combined, the competitiveness of the carbon-containing metal sulfide potassium ion battery anode material is very outstanding.
There are methods for preparing the negative electrode material of the potassium ion battery by an electrostatic spinning method, such as: patent CN202010835167.5 proposes that antimony trichloride and carbon nanotubes are respectively dissolved in N, N-dimethylformamide solution with nickel acetate, stannous chloride and cobalt chloride in a certain proportion by ultrasonic stirring by an electrostatic spinning method, and after polymethyl methacrylate and polyacrylonitrile are added, electrostatic spinning is performed, and then the material is carbonized to obtain the final product. However, in the method, two types of organic polymers (polymethyl methacrylate and polyacrylonitrile) are added when the spinning solution precursor is prepared, and the structural structure is only a one-dimensional tubular structure. In contrast, this patent requires only one organic substance (polymethyl methacrylate) to configure the electrospray precursor, and finally constructs a three-dimensional spherical structure by decomposition of polymethyl methacrylate. The method adopted by the patent is simpler and more convenient, and the structure of the final product is a three-dimensional structure, so that the potassium storage capacity is better.
Disclosure of Invention
An object of the present invention is to provide a method for preparing hollow carbon spheres anchored with metal sulfides, so as to solve the problems mentioned in the background art.
It is another object of the present invention to provide a hollow carbon sphere anchored with metal sulfide to solve the above problems in the background art.
The present invention also aims to provide an application of hollow carbon spheres anchored with metal sulfides in a potassium ion battery, so as to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a hollow carbon sphere anchored with metal sulfide comprises the following steps:
(1) Dissolving acetylacetone metal salt in organic solvent, stirring and heating, keeping the temperature at 240-280 ℃ for 1-4h to obtain metal oxide particles uniformly dispersed in the organic solvent, centrifuging and washing the obtained metal oxide particles;
(2) Dispersing the metal oxide particles obtained in the step (1) and organic polymers in a solvent to obtain precursor slurry, and then performing electrostatic spraying on the obtained precursor slurry by using an electrostatic sprayer to obtain metal oxide particles coated by the organic polymers; the voltage of the electrostatic spraying is 5-50KV, and the feeding rate of the electrostatic spraying is 0.01-0.06ml/min;
the needle head can generate discharge phenomenon when the voltage is too high, and the spray can not be formed; the feeding speed is 0.01-0.06mL/min, and the slow feeding can cause the spraying to be discontinuous; too fast the spray forms non-uniform particles.
(3) Coating the metal oxide particles coated by the organic polymer obtained in the step (2) with a dopamine hydrochloride solution, and then centrifuging and drying the obtained product to obtain dopamine hydrochloride-coated organic polymer spheres containing metal oxides;
specifically, metal oxide particles coated with organic polymers are uniformly dispersed in deionized water, and then dopamine hydrochloride is added for coating, and the mixture is stirred for a period of time. And centrifuging and vacuum drying the obtained product to finally obtain the dopamine hydrochloride-coated polymethyl methacrylate spheres containing metal oxide particles.
(4) And (4) carbonizing and vulcanizing the organic polymer spheres obtained in the step (3) to obtain hollow carbon spheres anchored with metal sulfides.
Further, the metal salt of acetylacetone in step (1) is at least one of copper acetylacetonate, iron acetylacetonate, manganese acetylacetonate, cobalt acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate, chromium acetylacetonate, vanadium acetylacetonate, and zinc acetylacetonate.
Further, the organic solvent in the step (1) is any one of oleylamine, oleic acid and diphenyl ether.
Further, the solvent in the step (2) is any one of ethanol, N-dimethylformamide, N-dimethylacetamide, acetone and chloroform.
Further, the organic polymer in the step (2) is any one of polymethyl methacrylate and polyacrylonitrile.
Further, the concentration of the dopamine hydrochloride solution in the step (3) is 0.5-1g/L; when the concentration of dopamine hydrochloride is too low, the coating is not uniform; too high a concentration of dopamine hydrochloride can result in deposition of dopamine hydrochloride particles.
Further, the pH value of the dopamine hydrochloride solution in the step (3) is 8.4-8.5; too low or too high pH value can result in poor effect of coating spherical particles.
Further, the coating time in the step (3) is 2-12h. If the wrapping time is too short, the carbon shell is too thin; too long a wrapping time can result in an excessively thick carbon shell.
Further, the temperature rise rate of carbonization in the step (4) is 1-10 ℃/min, and the temperature range of carbonization is 300-500 ℃; too low a carbonization temperature can cause dopamine hydrochloride not to form a carbon shell; the carbonization temperature is too high, which can cause the metal oxide in the polymethyl methacrylate spheres to be reduced;
further, the temperature rise rate of the vulcanization in the step (4) is 1-10 ℃/min, and the temperature range of the vulcanization is 400-600 ℃. Too low a sulfidation temperature can result in the metal oxide not reaching the sulfidation temperature; if the sulfidation temperature is too high, the sulfide formed will be reduced by C.
The hollow carbon sphere anchored with the metal sulfide is prepared by the preparation method.
The application of the hollow carbon sphere anchored with the metal sulfide in the preparation of the potassium ion battery comprises the following steps:
adding the hollow carbon spheres, a conductive agent Super P and a binder polyvinylidene fluoride into an N-methyl pyrrolidone solution, and stirring to form homogeneous slurry; then uniformly coating the homogeneous slurry on a current collector; and drying the current collector after slurry coating, pressing and vacuum drying to obtain the potassium ion battery cathode.
Further, the mass ratio of the hollow carbon spheres, the conductive agent Super P and the binder polyvinylidene fluoride is 6-8;
further, the diameter of the current collector is 14-16mm, and the current collector is a copper foil current collector;
further, the drying temperature is 80 +/-30 ℃;
further, the pressure of the compression is 16-18Mpa, and the compression is performed by using a powder tablet press;
further, the temperature of the vacuum drying is 60-100 ℃, and the time of the vacuum drying is 4-8h;
further, the vacuum-dried current collector is placed in inert gas for standing for 10-12h.
The inventor synthesizes the sulfur and nitrogen double-doped hollow carbon sphere containing sulfide on the wall by combining an electrostatic spraying method and a dopamine hydrochloride coating method through simple and effective scientific design. The method has the remarkable innovation that the surface tension of a high polymer in water is utilized to ensure the high molecular weight of electrostatic sprayingThe small droplets form uniform spheres in water. The method for manufacturing the spherical particles by utilizing the surface tension of the macromolecules without a template is quite rare in the field of potassium ion battery cathodes. In the tube furnace, the polymer inside was melted to form a cavity, and the dopamine hydrochloride outside was carbonized. A unique hollow structure is formed. On the aspect of performance, cobalt sulfide in the hollow carbon spheres provides capacity, and on the one hand, the transmission distance is reduced, thereby being beneficial to rapid diffusion and extraction of potassium ions on the carbon shell. On the other hand, the breakage of the sulfide in the hollow carbon shell due to volume expansion is well suppressed by the carbon shell, the stability of the electrode material is improved, and the reversible capacity of the material is increased. This idea innovatively inlays the active substance on the carbon shell, not just inside the carbon shell. The material with the hollow structure has higher reversible capacity which is 0.1A g -1 At the current density, the alloy still has 322mAh g after 100 circles -1 The reversible specific capacity of (a); even at 1A g -1 Under the current density, after 1000 circles, the alloy still has 207mAh g -1 The reversible specific capacity of the composite material is high, and the composite material has excellent rate performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) The spherical particles are manufactured without a template, and the spherical high molecules are formed by completely utilizing the surface tension in water; saves raw materials and has environmental protection. The method is quite rare to manufacture in electrode materials and has great innovation. And has a great hint on the design of the hollow structure of the electrode material in the future.
(2) The hollow carbon ball containing the metal sulfide has a larger cavity, and is very beneficial to the de-intercalation and de-extraction of potassium ions. And the active substance is inlaid on the carbon wall instead of the inside of the carbon shell, so that the transmission distance of electrons is shortened, and the electrical property is improved.
(3) The hollow carbon sphere containing the metal sulfide synthesized by the invention is used as a negative electrode material of a potassium ion battery, and has excellent electrochemical performance. At 100mA g -1 At a current density of (2), cycle 10Still has 332mAh g after 0 turn -1 1A g -1 At a current density of 207mAh g after 1000 cycles -1 The reversible specific capacity of (a).
It can be seen that the hollow carbon spheres containing the metal sulfide synthesized by the invention have very excellent cycle performance when being used as a negative electrode material of a potassium ion battery, even if the hollow carbon spheres are 1A g -1 Under the condition of large current, the electrochemical material still has higher reversible specific capacity, very stable electrochemical performance, great popularization and application value and market competitiveness.
Drawings
FIG. 1 is an SEM image of the PMMA-coated metal oxide obtained in example 5 of the present invention after electrostatic spraying.
FIG. 2 is a TEM image of metal-containing sulfide obtained by coating dopamine hydrochloride and then performing carbonization and vulcanization in example 5 of the invention.
Fig. 3 is an electrical property diagram of a potassium ion battery cathode made of the hollow carbon sphere anchored with metal sulfide obtained in example 5 of the present invention.
Detailed Description
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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
5g of nickel acetylacetonate was charged into a three-necked flask containing 50mL of oleylamine, stirred well, and Ar was continuously introduced. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain nickel oxide particles uniformly dispersed in oleylamine, and centrifuging to obtain the nickel oxide particles. The resulting particles were washed, and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV and the feeding speed of 0.04mL/min, carrying out electrostatic spraying by using an electrostatic sprayer to obtain uniform nickel oxide particles coated by polymethyl methacrylate balls. Subjecting the product toAdding into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.5g L -1 . After stirring well for 12h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
Taking 0.2g of one-dimensional porous carbon fiber containing sulfide nanoparticles prepared in the embodiment, 0.025g of polyvinylidene fluoride (PVDF) and 0.025 Super P as conductive agents, mixing and grinding the mixture, transferring the mixture into a small glass bottle, adding 2.5ml of NMP, magnetically stirring the mixture for 2 hours to form homogeneous slurry, then uniformly coating the homogeneous slurry on a copper foil current collector cut into a size of 14mm, then placing an electrode plate coated with the slurry on a heater, drying the electrode plate at the temperature of 80 +/-30 ℃, then pressing the dried electrode plate by using a powder tablet press, wherein the pressing pressure is 18MPa, drying the electrode plate at the temperature of 80 ℃ in a vacuum drying box for 6 hours after pressing, finally placing the dried electrode plate in a special glove box in an argon atmosphere for 10 hours, and taking out the electrode plate to obtain the potassium ion battery cathode. And metal potassium is used as a counter electrode to be assembled into a CR2032 type button cell in a glove box, and electrochemical performance test is carried out.
Example 2
5g of zinc acetylacetonate was charged into a three-necked flask containing 50mL of oleylamine, stirred well, and Ar was continuously introduced. Raising the temperature to 250 ℃, preserving the heat for 1 hour to obtain zinc oxide particles which are uniformly dispersed in oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV, the feeding speed is 0.04mL/min, and the zinc oxide particles coated by the polymethyl methacrylate spheres are obtained by electrostatic spraying with an electrostatic sprayer. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.6g L -1 . After stirring well for 4h, the resulting product was collected by centrifugation. After vacuum dryingKeeping the temperature at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 3
5g of copper acetylacetonate, 50mL of oleylamine were placed in a three-necked flask, stirred well, and Ar passed continuously. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain copper oxide particles uniformly dispersed in oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed and mixed with polymethyl methacrylate and 10mL of N, N-dimethylformamide. Under the condition of 15kV and the feeding speed of 0.04mL/min, carrying out electrostatic spraying by using an electrostatic spraying machine to obtain uniform copper oxide particles wrapped by polymethyl methacrylate balls. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.7g L -1 . After stirring well for 2h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. And mixing the obtained product with sulfur powder, mixing the obtained material with the sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 4
Manganese acetylacetonate (5 g) was charged into a three-necked flask containing 50mL of oleylamine, sufficiently stirred, and Ar was continuously introduced. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain manganese oxide particles uniformly dispersed in the oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed, and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV, the feeding speed is 0.04mL/min, and uniform manganese oxide particles coated by polymethyl methacrylate balls are obtained by electrostatic spraying with an electrostatic sprayer. The product was added to 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, followed by additionAdding dopamine hydrochloride, and controlling the concentration of the dopamine hydrochloride to be 0.5g L -1 . After stirring well for 14h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 5
5g of cobalt acetylacetonate was added to a solution containing 50mL of oleylamine in a three-necked flask, sufficiently stirred, and Ar was continuously introduced. Heating to 250 ℃, preserving heat for 1h to obtain cobalt oxide particles uniformly dispersed in oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV, the feeding speed is 0.04mL/min, and uniform copper oxide particles coated by polymethyl methacrylate balls are obtained by electrostatic spraying with an electrostatic sprayer. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.5g L -1 . After stirring well for 12h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 6
5g of chromium acetylacetonate was added to a solution containing 50mL of oleylamine in a three-necked flask, stirred well, and Ar was continuously introduced. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain copper oxide particles uniformly dispersed in oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed, and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV, the feeding speed is 0.04mL/min, and the uniform polymethyl methacrylate is obtained by electrostatic spraying with an electrostatic sprayerCopper oxide particles coated with methyl enoate spheres. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.8g L -1 . After stirring well for 14h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon spheres containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 7
5g of molybdenum acetylacetonate was added to a solution containing 50mL of oleylamine in a three-necked flask, stirred well, and Ar was continuously introduced. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain copper oxide particles uniformly dispersed in oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV and the feeding speed of 0.04mL/min, carrying out electrostatic spraying by using an electrostatic spraying machine to obtain uniform copper oxide particles wrapped by polymethyl methacrylate balls. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.9g L -1 . After stirring well for 18h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 8
5g of vanadium acetylacetonate was added to a solution containing 50mL of oleylamine in a three-necked flask, stirred well, and Ar was continuously introduced. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain copper oxide particles uniformly dispersed in oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed and mixed with polymethyl methacrylate by adding 10mL of N, N-dimethylformamide. Under the condition of 15kV and the feeding speed of 0.04mL/min, carrying out electrostatic spraying by using an electrostatic spraying machine to obtain uniform copper oxide particles wrapped by polymethyl methacrylate balls. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 0.7g L -1 . After stirring well for 10h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon sphere containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
Example 9
5g of iron acetylacetonate was added to a solution containing 50mL of oleylamine in a three-necked flask, stirred well, and Ar was continuously introduced. And raising the temperature to 250 ℃, preserving the heat for 1h to obtain copper oxide particles uniformly dispersed in the oleylamine, and centrifuging to obtain nickel oxide particles. The resulting particles were washed. And mixed with polymethyl methacrylate in 10mL of N, N-dimethylformamide. Under the condition of 15kV and the feeding speed of 0.04mL/min, carrying out electrostatic spraying by using an electrostatic spraying machine to obtain uniform copper oxide particles wrapped by polymethyl methacrylate balls. Adding the product into 300mL of water containing 0.2g of tris (hydroxymethyl) aminomethane, adding dopamine hydrochloride, and controlling the concentration of dopamine hydrochloride to be 1g L -1 . After stirring well for 8h, the resulting product was collected by centrifugation. After vacuum drying, the temperature is kept at 450 ℃ for 2h at the heating rate of 5 ℃/min. Mixing the obtained product with sulfur powder, and keeping the temperature at 600 ℃ for 2h at the heating rate of 5 ℃/min. And cooling to obtain the hollow carbon spheres containing the metal sulfide which can be used for the cathode of the potassium ion battery.
The button cell manufacturing process was the same as example 1.
And (3) performance testing: the materials prepared in the above examples were characterized by X-ray diffraction (XRD), raman spectroscopy (Raman spectroscopy), fourier transform infrared spectroscopy (FT-IR), scanning Electron Microscope (SEM), transmission Electron Microscope (TEM), and thermogravimetric analysis (TGA), and their particle sizes, morphologies, and pores were fully analyzed.
FIG. 1 is an SEM image of the PMMA-coated metal oxide obtained in example 5 of the present invention after electrostatic spraying. The obtained particles were found to be spherical and to have good dispersibility. And the surface of the ball has fine pores, which are caused by volatilization of N, N-dimethylformamide in electrostatic spraying.
FIG. 2 is a TEM image of metal-containing sulfide obtained by coating dopamine hydrochloride and then performing carbonization and vulcanization in example 5 of the present invention. It can be seen that the final product does contain a hollow spherical structure and the internal cavity is large, which is very advantageous for the storage of potassium ions.
Fig. 3 is an electrical property diagram of a potassium ion battery cathode made of the hollow carbon sphere anchored with metal sulfide obtained in example 5 of the present invention. At 100mA g -1 At a current density of 332mAh g after 100 cycles -1 Specific discharge capacity of (2). The material has excellent potassium storage capacity.
After the battery prepared in the embodiment is placed for 24 hours, a battery tester (Shenzhen Xinwei) and BTS7.5.6 software are adopted, the testing temperature is 25 ℃, and the current density is 100mA g -1 ～2000mA g -1 In the case, the battery was subjected to constant current charge and discharge (discharge cutoff voltage of 0.01V, charge voltage of 3V), and the cycle performance and rate performance of the battery were tested. The electrochemical properties of the samples are detailed in table 1 below. It was subjected to Cyclic Voltammetry (CV) and alternating current impedance testing using an electrochemical workstation (CHI 600E, shanghai chenhua).
TABLE 1
Figure BDA0003016449320000111
Figure BDA0003016449320000121
The invention provides a metal sulfide-containing organic solvent used in a negative electrode material of a potassium ion battery, which is prepared by changing the type and organic solvent of acetylacetone saltThe preparation is organic polymer, dopamine hydrochloride coating speed and coating time, and electrostatic spray voltage and feeding speed which are adaptive to the dopamine hydrochloride coating speed are used for searching materials with optimal performance, and the electrochemical performance of corresponding materials is also researched. By comparing 9 examples, the concentration of dopamine hydrochloride is 0.5g L when the coating time is 2-18h -1 -1g L -1 The prepared hollow carbon spheres containing the metal sulfide have good electrochemical performance when being used as a negative electrode of the potassium ion battery, and can reach the current density of 200-1000mA g -1 After the circulation is performed for 100-1000 circles, 207-396mAh g is kept -1 The reversible capacity of (a).
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 (9)

1. A preparation method of a hollow carbon sphere anchored with metal sulfide is characterized by comprising the following steps:
(1) Dissolving acetylacetone metal salt in organic solvent, stirring and heating, and keeping the temperature at 240-280 ℃ for 1-4h to obtain metal oxide particles; the metal salt of acetylacetone is at least one of copper acetylacetonate, iron acetylacetonate, manganese acetylacetonate, cobalt acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate, chromium acetylacetonate, vanadium acetylacetonate and zinc acetylacetonate;
(2) Dispersing the metal oxide particles obtained in the step (1) and organic polymers in a solvent to obtain precursor slurry, and then performing electrostatic spraying on the obtained precursor slurry by using an electrostatic spraying machine to obtain metal oxide particles coated by the organic polymers; the voltage of the electrostatic spraying is 5-50KV, and the feeding rate of the electrostatic spraying is 0.01-0.06ml/min;
(3) Coating the metal oxide particles coated by the organic polymer obtained in the step (2) with a dopamine hydrochloride solution, and then centrifuging and drying the obtained product to obtain dopamine hydrochloride-coated organic polymer spheres containing metal oxides; the concentration of the dopamine hydrochloride solution is 0.5-1g/L; the coating time is 2-12h;
(4) Carbonizing and vulcanizing the organic polymer spheres obtained in the step (3) to obtain hollow carbon spheres anchored with metal sulfides; the temperature range of carbonization is 300-500 ℃, and the temperature range of vulcanization is 400-600 ℃.
2. The method of claim 1, wherein the organic solvent used in the step (1) is any one of oleylamine, oleic acid, and diphenyl ether.
3. The method of claim 1, wherein the solvent used in the step (2) is any one of ethanol, N-dimethylformamide, N-dimethylacetamide, acetone, and chloroform.
4. The method for preparing hollow carbon spheres anchored with metal sulfides according to claim 1, wherein the organic polymer in step (2) is any one of polymethyl methacrylate and polyacrylonitrile.
5. The method for preparing hollow carbon spheres anchored with metal sulfides according to claim 1, wherein the pH value of the dopamine hydrochloride solution in the step (3) is 8.4-8.5.
6. The method for preparing hollow carbon spheres anchored with metal sulfides according to claim 1, wherein the temperature rise rate of the carbonization in the step (4) is 1-10 ℃/min; the temperature rise rate of the vulcanization is 1-10 ℃/min.
7. A hollow carbon sphere anchored with a metal sulfide, characterized by being produced by the production method according to any one of claims 1 to 6.
8. The use of a hollow carbon sphere anchored with a metal sulfide as claimed in claim 7 for the preparation of a potassium ion battery negative electrode, comprising the steps of:
adding the hollow carbon spheres, a conductive agent Super P and a binder polyvinylidene fluoride into an N-methyl pyrrolidone solution, and stirring to form homogeneous slurry; then uniformly coating the homogeneous slurry on a current collector; and then drying the current collector after slurry coating, pressing and vacuum drying to obtain the potassium ion battery cathode.
9. The application of the carbon ball material as claimed in claim 8, wherein the mass ratio of the hollow carbon ball, the conductive agent Super P and the binder polyvinylidene fluoride is 6-8:1:1; the diameter of the current collector is 14-16mm, and the current collector is a copper foil current collector; the drying temperature is 80 +/-30 ℃; the pressure of the pressing is 16-18Mpa, and a powder tablet press is used for the pressing; the temperature of the vacuum drying is 60-100 ℃, and the time of the vacuum drying is 4-8h; and placing the vacuum-dried current collector in inert gas for standing for 10-12h.
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