CN112002893A - Research of taking antimony-based composite metal sulfide as potassium ion battery negative electrode material - Google Patents
Research of taking antimony-based composite metal sulfide as potassium ion battery negative electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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Abstract
The carbon-coated antimony-based composite metal sulfide used as the cathode material of the potassium ion battery and the preparation method thereof, wherein the chemical general formula of the metal sulfide is Sb1‑xMxSy@ C, where M is one of light metals Mg and Al, 0<x<Y is more than or equal to 0.5 and less than or equal to 1.5 and less than or equal to 2. The invention also discloses a preparation method of the carbon-coated antimony-based composite metal sulfide of the potassium ion battery negative electrode material. The metal oxide is used as a precursor, and the carbon-coated antimony-based composite metal sulfide negative electrode material is prepared by a similar vapor deposition method. The invention has simple process and easy repetition, and is beneficial to realizing the large-range application of the materials.
Description
Technical Field
The invention belongs to the field of potassium ion battery cathode materials, and particularly relates to a carbon-coated antimony-based composite metal sulfide and a preparation method thereof.
Background
In recent years, potassium ion batteries have abundant reserves, wide distribution and low price, and the physicochemical property of K is similar to that of Li,a new type of ion battery having an energy density comparable to that of a lithium ion battery has attracted attention. Meanwhile, carbon materials represented by graphite are found to provide 279 mA h g when used as negative electrode materials of potassium ion batteries-1But the energy density and cycle life of the carbon materials reported at present are not ideal.
Compared with a graphite cathode, the antimony-based cathode material has higher theoretical specific capacity and a safer potassium-embedded platform. However, antimony-based materials have severe volume expansion (> 150%) during constant charging and discharging, which easily causes the collapse of the material structure, thereby causing the battery capacity to decay too fast. Therefore, the research subject is to optimize the antimony-based material mainly from two aspects of alloying so as to improve the electrochemical performance of the antimony-based material. The sulfide of antimony synthesized by methods such as freeze drying, high-temperature calcination and the like has higher specific capacity than the simple substance antimony; on the other hand, an intermediate product, namely potassium sulfide, generated in the process of charging and discharging of the material can be used as an internal support of the material, so that the material has higher stability. However, antimony-based materials undergo severe volume expansion during the circulation process, which easily causes pulverization of the materials to cause structural collapse of electrode materials, thereby causing rapid attenuation of battery capacity and poor circulation performance. The current modification method comprises the steps of constructing a microstructure, compounding with a carbon material, introducing inert substances (Ti, V, Co, Zn, Ni and the like), introducing light metals (Mg, Al and the like) as structural supports and the like, relieving mechanical stress in the volume expansion process, and thus effectively improving the potassium storage performance of the material. The sulfide is directly compounded with the carbon material (see patent "antimony sulfide-based cathode material with high reversible capacity and preparation and application thereof", China patent application publication No. CN 107331842A), the carbon composite material is synthesized by the regulation and control method by adopting a mechanical ball milling method, the uniform distribution of particles is difficult to realize, and the performance is difficult to stabilize. Therefore, compared with direct compounding of carbon materials, the carbon-coated antimony-based composite light metal sulfide material has the advantages of high reaction activity, high volume specific capacity, safety, reliability, wide resources, low raw material price and the like, so that the carbon-coated antimony-based composite light metal sulfide material has great development potential as a new generation of power battery cathode material, and arouses attention of people.
In conclusion, the invention takes the metal oxide as the precursor and prepares the carbon-coated antimony-based composite metal sulfide with good conductivity and cycle performance by a simple vapor deposition-like method.
Disclosure of Invention
The technical problem to be solved by the invention is to prepare the carbon-coated antimony-based composite metal sulfide with good conductivity and cycle performance by using a simple similar vapor deposition method.
The technical scheme adopted by the invention for solving the technical problems is as follows: carbon-coated antimony-based composite metal sulfide, Sb, as cathode material of potassium ion battery1-xMxSyWherein M is one of light metals Mg and Al, 0<x<0.5,1.25≤y≤2。
The preparation method of the metal sulfide of the potassium ion battery negative electrode material comprises the following steps:
(1) dissolving a certain amount of antimony metal salt and a certain amount of light metal salt in a certain volume of solvent A to obtain a solution B1 with a certain concentration, dispersing/dissolving a certain amount of carbon source and nitrogen source in a solution B1 to obtain a solution B2, carrying out hydrothermal reaction for a certain time at a certain temperature, and carrying out centrifugation, washing and freeze drying to obtain a carbon-coated metal oxide precursor;
(2) putting a certain amount of sublimed sulfur powder in a magnetic boat and placing the magnetic boat at the position of a deflection air inlet end of the tube furnace, placing the metal oxide obtained in the step (1) close to the sublimed sulfur powder magnetic boat at the position of the deflection air outlet end, and carrying out heat treatment at a certain temperature for a certain time under an inert atmosphere to obtain a metal sulfide final product.
Further, in the step (1), the antimony salt is one or a mixture of antimony chloride, antimony fluoride and antimony acetate;
further, in the step (1), the light metal salt is one or a mixture of several of nitrate, acetate and chloride;
further, in the step (1), the molar ratio W of the light metal salt to the antimony salt in the two metal salts is equal to 0.1-1;
further, in the step (1), the solvent A is one or a mixture of more of ethylene glycol, NMP (N-methylpyrrolidone) and N, N-dimethylformamide;
further, in the step (1), the concentration of the solution B1 is 0.005-2 mol/L;
further, in the step (1), the carbon source is one or a mixture of several of graphene, carbon nanotubes and graphite;
further, in the step (1), the mass of the carbon source is 5-20% of the mass of a theoretical product;
further, in the step (1), the nitrogen source is one or a mixture of urea and ammonia water;
further, in the step (1), the molar ratio of the nitrogen source to the metal salt is 2-10;
further, in the step (1), the hydrothermal reaction time is 5-20 h;
further, in the step (1), the hydrothermal reaction temperature is 160-220 ℃;
further, in the step (2), the mass ratio of the sublimed sulfur powder to the metal oxide is 5-50;
further, in the step (2), the heat treatment temperature is 400-1000 ℃;
further, in the step (2), the heat treatment time is 30min-10 h.
Further, in the step (2), the inert atmosphere is one or a mixture of more of high-purity nitrogen, high-purity argon, a mixed gas of hydrogen and nitrogen containing 1% -10% of hydrogen, and a mixed gas of hydrogen and argon containing 1% -10% of hydrogen;
the invention has the beneficial effects that: the carbon-coated antimony-based composite metal sulfide is prepared by a hydrothermal-pyrolysis method, and the scheme is simple and convenient to operate, easy to repeat and beneficial to large-scale popularization and application.
Drawings
FIG. 1 is an XRD pattern of the product prepared in example 2 of the present invention;
FIG. 2 is a graph of the cycle performance of the product prepared in example 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Weighing 3.8 mmol of antimony chloride and 0.2 mmol of aluminum chloride, dissolving in 100 mL of ethylene glycol, weighing 5 mg of graphene, dispersing in the ethylene glycol, adding 20 mmol of ammonia water after full dispersion, mixing fully, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24h, centrifuging, washing, and freeze-drying to obtain a metal oxide precursor;
(2) putting 1g of sublimed sulfur in a magnetic boat at the position of a deflection air inlet end of a tube furnace, weighing 2 mmol of the oxide precursor obtained in the step (1), and putting the oxide precursor in the magnetic boat; placing the sublimed sulfur magnetic boat close to the air outlet end, and reacting for 4 hours at 300 ℃ in an inert atmosphere to obtain antimony aluminum sulfide final product Sb0.95Al0.05S1.5。
Weighing 0.07g of prepared antimony aluminum sulfide, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV 900, binder), fully grinding, adding 0.4 mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (potassium hydrogen fluoride) as a KPF (positive pressure drop)6The solution (solvent EC: DEC volume ratio of 1: 1) was used as an electrolyte, and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power of 0.1C, the first discharge specific capacity of the antimony sulfide aluminum material is 908.1 mA h g-1The first charge capacity is 777.3 mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 0.5C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 341.3 mA hr g-1。
Example 2
(1) Weighing 3.6 mmol of antimony chloride and 0.4 mmol of magnesium chloride, dissolving in 100 mL of ethylene glycol, weighing 10 mg of graphene, dispersing in the ethylene glycol, adding 20 mmol of ammonia water after full dispersion, mixing fully, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24h, centrifuging, washing, and freeze-drying to obtain a metal oxide precursor;
(2) putting 1g of sublimed sulfur in a magnetic boat at the position of a deflection air inlet end of a tube furnace, weighing 2 mmol of the oxide precursor obtained in the step (1), and putting the oxide precursor in the magnetic boat; placing the sublimed sulfur magnetic boat close to the air outlet end, and reacting for 4h at 400 ℃ in an inert atmosphere to obtain a final antimony magnesium sulfide product Sb0.9Mg0.1S1.45。
Weighing 0.07g of prepared antimony magnesium sulfide, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV 900, binder), fully grinding, adding 0.4 mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (potassium hydrogen fluoride) as a KPF (potassium hydrogen fluoride) for 1 mm6The solution (solvent EC: DEC volume ratio of 1: 1) was used as an electrolyte, and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. Analysis by scanning electron microscopy revealed (figure 1) that the carbon-coated antimony magnesium sulfide material was a nanoparticle attached to graphene. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power, the first discharge specific capacity of the antimony sulfide magnesium material is 859.5 mA h g-1The first charge capacity is 498.0 mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 0.3C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 179.8 mA hr g-1。
Example 3
(1) Weighing 3.6 mmol of antimony fluoride and 0.4 mmol of aluminum chloride, dissolving in 100 mL of NMP solution, weighing 5 mg of graphene, dispersing in the NMP solution, adding 15 mmol of urea after full dispersion, transferring into a hydrothermal kettle after full mixing, carrying out hydrothermal reaction at 180 ℃ for 24h, centrifuging, washing, and freeze-drying to obtain a metal oxide precursor;
(2) 1g of sublimed sulfur is placed in a magnetic boat and is arranged at the position of a deflection air inlet end of a tube furnace,weighing 2 mmol of the oxide precursor obtained in the step (1) and placing the oxide precursor in a magnetic boat; placing the sublimed sulfur magnetic boat close to the air outlet end, and reacting for 4 hours at 300 ℃ in an inert atmosphere to obtain antimony aluminum sulfide final product Sb0.9Al0.1S1.5。
Weighing 0.07g of prepared antimony aluminum sulfide, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV 900, binder), fully grinding, adding 0.4 mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (potassium hydrogen fluoride) as a KPF (positive pressure drop)6The solution (solvent EC: DEC volume ratio of 1: 1) was used as an electrolyte, and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V under the multiplying power of 0.1C, the first discharge specific capacity of the antimony sulfide aluminum material is 783.9 mA h g-1The first charge capacity is 522.6 mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 0.5C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 164.3 mA hr g-1。
Example 4
(1) Weighing 3 mmol of antimony chloride and 1 mmol of magnesium chloride, dissolving the antimony chloride and the magnesium chloride in 100 mL of ethylene glycol, weighing 10 mg of graphene, dispersing the graphene in the ethylene glycol, adding 20 mmol of ammonia water after full dispersion, mixing the mixture fully, transferring the mixture into a hydrothermal kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, and obtaining a metal oxide precursor after centrifugation, washing and freeze drying;
(2) putting 0.5g of sublimed sulfur in a magnetic boat at the position of a deflection air inlet end of a tube furnace, weighing 2 mmol of the oxide precursor obtained in the step (1) and putting the oxide precursor in the magnetic boat; placing the sublimed sulfur magnetic boat close to the air outlet end, and reacting for 4 hours at 300 ℃ in an inert atmosphere to obtain a final product Sb of the magnesium antimony sulfide0.75Mg0.25S1.375。
0.07g of antimony magnesium sulfide, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV 900, binder) prepared in the above are weighedFully grinding, adding 0.4 mL of NMP, dispersing and mixing, uniformly mixing, drawing slurry on a copper foil to prepare a sheet, blowing air to dry at 80 ℃, cutting into a wafer with the diameter of 12mm, assembling in a glove box under argon atmosphere, taking a metal potassium sheet as a counter electrode, and carrying out 1M KPF6The solution (solvent EC: DEC volume ratio of 1: 1) was used as an electrolyte, and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. According to the cyclic performance test (figure 2), when the constant-current charge and discharge test is carried out at 25 ℃ and 0.1C multiplying power between 0.1 and 3.0V, the first discharge specific capacity of the antimony-magnesium sulfide material is 859.5 mA h g-1The first charge capacity is 498.0 mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 0.3C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 179.8 mA hr g-1。
Example 5
(1) Weighing 2.4 mmol of antimony acetate and 1.6 mmol of aluminum acetate, dissolving in 100 mL of ethylene glycol solution, weighing 10 mg of graphene, dispersing in the ethylene glycol, adding 30 mmol of urea after full dispersion, mixing fully, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, centrifuging, washing, and freeze-drying to obtain a metal oxide precursor;
(2) putting 1g of sublimed sulfur in a magnetic boat at the position of a deflection air inlet end of a tube furnace, weighing 2 mmol of the oxide precursor obtained in the step (1), and putting the oxide precursor in the magnetic boat; placing the sublimed sulfur magnetic boat close to the air outlet end, and reacting for 4 hours at 300 ℃ in an inert atmosphere to obtain antimony aluminum sulfide final product Sb0.6Al0.4S1.5。
Weighing 0.07g of prepared antimony aluminum sulfide, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV 900, binder), fully grinding, adding 0.4 mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (potassium hydrogen fluoride) as a KPF (positive pressure drop)6The solution (EC: DEC 1:1 by volume) as electrolyte, glass fiber membrane (GF/D, Whatman)Used as a diaphragm and assembled into a CR2032 button cell. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power, the first discharge specific capacity of the antimony sulfide aluminum material is 678.3 mA h g-1The first charge capacity is 515.0 mA hr g-1. Performing constant current charge and discharge test at 25 deg.C and 0.5C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 204.1 mA hr g-1。
Example 6
(1) Weighing 3.2 mmol of antimony chloride and 1.8 mmol of magnesium chloride, dissolving the antimony chloride and the magnesium chloride in 100 mL of N, N-dimethylformamide solution, weighing 5 mg of graphene, dispersing the graphene in the N, N-dimethylformamide solution, adding 20 mmol of ammonia water after full dispersion, fully mixing, transferring the mixture into a hydrothermal kettle, carrying out hydrothermal reaction at 220 ℃ for 12 hours, and obtaining a metal oxide precursor after centrifugation, washing and freeze drying;
(2) putting 0.5g of sublimed sulfur in a magnetic boat at the position of a deflection air inlet end of a tube furnace, weighing 2 mmol of the oxide precursor obtained in the step (1) and putting the oxide precursor in the magnetic boat; placing the sublimed sulfur magnetic boat close to the air outlet end, and reacting for 4 hours at 300 ℃ in an inert atmosphere to obtain a final product Sb of the magnesium antimony sulfide0.8Mg0.2S1.4。
Weighing 0.07g of prepared antimony magnesium sulfide, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV 900, binder), fully grinding, adding 0.4 mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (potassium hydrogen fluoride) as a KPF (potassium hydrogen fluoride) for 1 mm6The solution (solvent EC: DEC volume ratio of 1: 1) was used as an electrolyte, and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power, the first discharge specific capacity of the antimony sulfide magnesium material is 790.2 mA h g-1The first charge capacity is 536.4 mA hr g-1. Performing constant current charge and discharge test at 25 deg.C and 0.5C rate in 0.1-3.0V interval, and circulating for 50 weeksThe specific discharge capacity is 154.8 mA h g-1。
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (10)
1. The carbon-coated antimony-based composite metal sulfide of the cathode material of the potassium ion battery is characterized in that: sb1-xMxSyWherein M is one of light metals Mg and Al, 0<x<0.5,1.25≤y≤2。
2. The method for preparing the metal sulfide of the negative electrode material of the potassium ion battery according to claim 1, characterized by comprising the steps of:
(1) dissolving a certain amount of antimony metal salt and a certain amount of light metal salt in a certain volume of solvent A to obtain a solution B1 with a certain concentration, dispersing/dissolving a certain amount of carbon source and nitrogen source in a solution B1 to obtain a solution B2, carrying out hydrothermal reaction for a certain time at a certain temperature, and carrying out centrifugation, washing and freeze drying to obtain a carbon-coated metal oxide precursor;
(2) putting a certain amount of sublimed sulfur powder in a magnetic boat and placing the magnetic boat at the position of a deflection air inlet end of the tube furnace, placing the metal oxide obtained in the step (1) close to the sublimed sulfur powder magnetic boat at the position of the deflection air outlet end, and carrying out heat treatment at a certain temperature for a certain time under an inert atmosphere to obtain a metal sulfide final product.
3. The method for preparing the metal sulfide of the anode material of the potassium ion battery according to claim 2, wherein in the step (1), the concentration of the solution B1 is 0.005-2 mol/L.
4. The method for preparing metal sulfide of the anode material of the potassium ion battery according to claim 2, wherein in the step (1), the molar ratio W of the light metal salt to the antimony salt is equal to 0.1-1.
5. The method for preparing the metal sulfide of the negative electrode material of the potassium-ion battery according to claim 2, wherein in the step (1), the solvent A is one of ethylene glycol, NMP (N-methylpyrrolidone) and N, N-dimethylformamide.
6. The method for preparing the metal sulfide of the potassium ion battery negative electrode material according to claim 2, wherein in the step (1), the hydrothermal reaction temperature is 160 ℃ to 220 ℃.
7. The preparation method of the metal sulfide as the negative electrode material of the potassium ion battery as claimed in claim 2, wherein the hydrothermal reaction time in the step (1) is 5-20 h.
8. The method for preparing the metal sulfide of the lithium ion battery negative electrode material according to claim 3, wherein in the step (3), the mass ratio of the sublimed sulfur powder to the metal alloy is 5-50.
9. The method for preparing the metal sulfide of the anode material of the potassium ion battery according to claim 2, wherein the heat treatment temperature in the step (3) is 400 ℃ to 1000 ℃.
10. The method for preparing the metal sulfide of the anode material of the potassium ion battery according to claim 2, wherein in the step (3), the heat treatment time is 30min to 10 h.
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