CN113410579A - Monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material and preparation method and application thereof - Google Patents
Monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material and preparation method and application thereof Download PDFInfo
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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Abstract
The invention relates to a monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material and a preparation method and application thereof. The material has multiple synergistic effects of physical adsorption, chemical adsorption, photo/electro-catalytic conversion and the like on polysulfide. The material is used for the coating of the lithium sulfur battery separator, so that shuttling of polysulfide can be effectively inhibited, and the conversion of polysulfide is accelerated, thereby improving the electrical performance of the lithium sulfur battery.
Description
Technical Field
The invention belongs to the field of energy storage of lithium-sulfur batteries, and particularly relates to a monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material, and a preparation method and application thereof, in particular to application in a membrane modified coating of a lithium-sulfur battery.
Background
The problems of environmental pollution, energy shortage and the like caused by fuel vehicles are faced. New energy vehicles are developed, wherein the improvement of the performance of the power battery is the key for solving the problem of low endurance mileage of the new energy vehicles. The lithium-sulfur battery is a power battery with great development prospect because of the advantages of high theoretical capacity, environment-friendly active sulfur, low cost and rich reserves.
However, the shuttle effect of polysulfide during the charging and discharging process of lithium sulfur batteries greatly limits the application of lithium sulfur batteries, and various materials are used for membrane modification to inhibit the shuttle effect through physical barrier, chemical adsorption and electric/photo-catalytic action in order to solve the problem. For example, carbon materials, polymer materials, metal compound materials, etc., but the single physical barrier effect of carbon materials or polymer materials is not enough to sufficiently inhibit the shuttle of polysulfide, and although metal compound materials can limit the shuttle of polysulfide to some extent by chemical adsorption and electro/photocatalysis, the low conductivity of metal compound materials is not favorable for large current charge and discharge, and the activity of the agglomerated metal compound is low, which is not favorable for fully exerting the photo/electrocatalytic effect.
The single-atom metal is concerned in the field of lithium-sulfur battery catalysis because the atom utilization rate of the single-atom metal is as high as one hundred percent, and the conductivity of a substrate is not influenced, but the metal atoms are easy to agglomerate at high temperature and difficult to uniformly disperse, and the conventional impregnation method is not easy to uniformly disperse the metal atoms, so that particles formed by metal agglomeration need subsequent acid treatment and other steps, the preparation steps are complex, and the metal waste is caused. The preparation of the supported monatomic catalyst by using metal-containing compounds such as MOF and the like as precursors is an effective method, but the content of metal monatomic and the product morphology are uncontrollable, so that the performance of the catalyst cannot be regulated. In summary, there is a need to develop a simple and controllable method for synthesizing a multifunctional monatomic metal electro/photocatalytic material as a lithium-sulfur battery separator coating, so as to further improve the electrical properties of the lithium-sulfur battery.
The single-atom metal/nitrogen co-doped hollow carbon sphere lithium-sulfur battery diaphragm coating material with physical adsorption, chemical adsorption and electro/photocatalysis functions is obtained by a simple polymer packaging method, and has important significance for improving the performance of the lithium-sulfur battery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a monatomic metal/nitrogen co-doped hollow carbon sphere photo-electro-catalytic material, a preparation method thereof and application thereof in a lithium-sulfur battery diaphragm modification coating. The material has multiple synergistic effects of physical adsorption, chemical adsorption, photo/electro-catalytic conversion and the like on polysulfide. The material is used for the coating of the lithium sulfur battery separator, so that shuttling of polysulfide can be effectively inhibited, and the conversion of polysulfide is accelerated, thereby improving the electrical performance of the lithium sulfur battery.
The invention adopts the following technical scheme that the monoatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material exists in an atomic form, the structure of the material is a hollow carbon sphere structure, and the metal is one or more of iron, cobalt, nickel, vanadium and zinc.
The invention also provides a preparation method of the monatomic metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material, which comprises the steps of adopting a polymer encapsulation method, realizing uniform dispersion of metal salt by utilizing the interaction of dopamine and the metal salt, and then carrying out pyrolysis, etching and drying.
Further, the preparation method comprises the following steps:
step (1): polymerizing dopamine containing metal salt on the surface of silicon dioxide, and performing high-temperature pyrolysis carbonization to obtain a monatomic metal/nitrogen-doped carbon and silicon dioxide core-shell structure material;
step (2): etching the monatomic metal/nitrogen-doped carbon and silicon dioxide core-shell structure material obtained in the step (1) in a sodium hydroxide solution, and removing the hard template;
and (3): and (3) washing the reaction product obtained in the step (2) with water and ethanol for several times respectively, and drying to obtain the monoatomic metal/nitrogen co-doped hollow carbon sphere material.
In a preferred embodiment of the present invention, in the step (1), the metal salt is one or more of a metal iron salt, a metal cobalt salt, a metal nickel salt, a metal vanadium salt and a metal zinc salt; the ferric salt is one or more of ferric nitrate, ferric chloride, ferric acetylacetonate and iron porphyrin; the cobalt salt is one or more of cobalt nitrate, cobalt chloride, cobalt acetylacetonate and cobalt porphyrin; the nickel salt is one or more of nickel nitrate, nickel chloride and nickel acetylacetonate, and the metal vanadium salt is one or more of vanadium trichloride, vanadium sulfate and vanadyl acetylacetonate; the zinc salt is one or more of zinc nitrate, zinc chloride, zinc acetate and zinc acetylacetonate.
In a preferred embodiment of the invention, in the step (1), the high-temperature pyrolysis carbonization is performed at 750-900 ℃ in an argon protective atmosphere; the high-temperature pyrolysis carbonization treatment is preferably carried out at 900 ℃.
In a preferred embodiment of the invention, in the step (2), the concentration of the sodium hydroxide is 2-8 mol/L, preferably 4 mol/L; the etching temperature is 40-90 ℃, and preferably 45 ℃; the etching time is 24-36 h, preferably 36 h.
In a preferred embodiment of the present invention, in step (3), the drying environment is a vacuum environment, and the temperature is between 30 ℃ and 60 ℃, preferably the drying temperature is 60 ℃.
The invention also protects the application of the monatomic metal/nitrogen co-doped hollow carbon sphere material in a lithium-sulfur battery diaphragm coating, and the monatomic metal/nitrogen co-doped hollow carbon sphere material is coated on the surface of the diaphragm for modification.
In a preferred embodiment of the invention, the monatomic metal/nitrogen co-doped hollow carbon sphere material and the binder are uniformly ground to obtain a mixed slurry, the mixed slurry is coated on the surface of the diaphragm and dried for standby application, and the thickness of the coating is controlled to be 20-50 μm, preferably 25 μm.
In a preferred embodiment of the invention, the total mass of the monatomic metal/nitrogen-doped hollow carbon sphere material and the binder is taken as a reference, wherein the monatomic metal/nitrogen element co-doped hollow carbon sphere material accounts for 80-90%, preferably 90%, of the mass fraction; the mass fraction of the binder is 10-20%, preferably 10%.
In a preferred embodiment of the present invention, the mass ratio is 9:1 and grinding to obtain uniform slurry, coating the slurry on a diaphragm, wherein the thickness of the coating is about 25 mu m, and drying the modified diaphragm in vacuum for later use.
The invention also discloses a lithium-sulfur battery with the modified diaphragm, which is prepared by the method.
Compared with the prior art, the metal monoatomic layer is uniformly dispersed by adopting a polymer encapsulation method, and the substrate is designed into a hollow structure, so that the metal monoatomic/nitrogen co-doped hollow carbon sphere material is obtained. According to the prepared material, the hollow carbon ball substrate has high conductivity and a porous structure, can accelerate electron transmission, adsorbs polysulfide through physical adsorption, and is beneficial to fully exposing metal catalytic sites on the surface to better play a catalytic role; the metal sites have the dual functions of chemical adsorption and photo/electro catalysis, so that polysulfides can be rapidly captured and the conversion of the polysulfides can be accelerated. Therefore, the monatomic metal/nitrogen co-doped hollow carbon sphere material can realize multiple effects of physical adsorption, chemical adsorption, photo/electro-catalysis and the like on polysulfide. The invention has the following beneficial effects:
(1) the polymer encapsulation method adopted by the invention can more easily prevent the agglomeration of metal atoms, realize the dispersion of the metal atoms in one step and effectively regulate the content of metal single atoms and the morphology of the catalyst.
(2) The monoatomic metal/nitrogen co-doped hollow carbon sphere material modified diaphragm disclosed by the invention has multiple effects of physical adsorption, chemical adsorption and photo/electro-catalysis on polysulfide, and can effectively improve the electrical performance of a lithium-sulfur battery.
(3) The modified diaphragm prepared by the invention effectively improves the performance of the lithium-sulfur battery, and can be popularized and used for other battery systems; the electrical property of the lithium-sulfur battery with the modified diaphragm prepared by the invention is obviously improved.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is a HAADF-STEM diagram of a monoatomic iron/nitrogen-co-doped hollow carbon sphere (A Fe-NHC) provided in example 1;
FIG. 2 is a cross-sectional view of a monoatomic iron/nitrogen co-doped hollow carbon sphere (A Fe-NHC) modified membrane provided in example 1;
FIG. 3 is a graph of cycle performance of a lithium-sulfur battery based on a monoatomic iron/nitrogen co-doped hollow carbon sphere modified membrane (A Fe-NHC/PP) provided in example 1;
fig. 4 shows a preparation process of the lithium-sulfur battery based on the monoatomic iron/nitrogen co-doped hollow carbon sphere modified separator (afe-NHC/PP) provided in example 1.
Detailed Description
The process of the present invention is illustrated below by means of specific examples, without limiting the scope of the invention as claimed.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1: preparation of monoatomic iron/nitrogen co-doped hollow carbon sphere material
Weighing 1 g of silicon dioxide hard template, and performing ultrasonic treatment for 30 min to fully and uniformly disperse the silicon dioxide hard template in 150ml of water to obtain a solution a; weighing 750 mg of dopamine hydrochloride and 50mg of iron porphyrin, adding the dopamine hydrochloride and the iron porphyrin into 30 ml of water, and uniformly stirring to obtain a solution b; weighing 500 mg of tris (hydroxymethyl) aminomethane, adding the tris (hydroxymethyl) aminomethane into 20 ml of deionized water, and uniformly mixing to obtain a solution c; and (3) sequentially dropwise adding the solution b and the solution c into the solution a, mechanically stirring for 6h at room temperature of 800 r, sequentially washing the product with water and ethanol for three times respectively, centrifugally collecting, and drying the centrifugally collected product in an oven at 60 ℃ for 12 h to obtain brown powder. Then drying the powder in N2Carrying out heat treatment in the atmosphere, heating to 900 ℃, carbonizing and pyrolyzing for 2 hours at 900 ℃ to obtain an intermediate product, carrying out silicon dioxide template etching on the intermediate product in a 4M sodium hydroxide solution at the etching temperature of 45 ℃, the etching time of 36 hours and the stirring rate of 800 r, washing the intermediate product with water for three times after etching is finished, washing with ethanol for three times, centrifuging and collecting to obtain a final product. The light dots circled in red as shown in FIG. 1 represent metallic iron atoms, indicating the successful synthesis of a monatomic iron catalyst.
Example 2: preparation of monoatomic cobalt/nitrogen co-doped hollow carbon sphere material
Weighing 1 g of silicon dioxide hard template, ultrasonically dispersing in 150ml of deionized water, and uniformly stirring to obtain a solution a; weighing 750 mg of dopamine hydrochloride and 20 mg of cobalt acetylacetonate, adding the dopamine hydrochloride and the 20 mg of cobalt acetylacetonate into 30 ml of water, and uniformly stirring to obtain a solution b; weighing 500 mg of tris (hydroxymethyl) aminomethane, adding the tris (hydroxymethyl) aminomethane into 20 ml of deionized water, and uniformly mixing to obtain a solution c; and (3) sequentially dropwise adding the solution b and the solution c into the solution a, mechanically stirring for 1 h at room temperature of 800 r, sequentially washing the product with water and ethanol for three times respectively, centrifugally collecting, and drying the centrifugally collected product in an oven at 60 ℃ for 12 h to obtain brown powder. The dried powder is then placed in a tube furnace, N2Carrying out heat treatment in the atmosphere, heating to 900 ℃, carbonizing and pyrolyzing for 2 h at 900 ℃ to obtain Co-NC @ SiO2And (2) etching the silicon dioxide template in 4M sodium hydroxide solution at the etching temperature of 45 ℃ for 36h at the stirring speed of 800 r, washing the silicon dioxide template by water for three times after etching is finished, washing by ethanol for three times, centrifuging and collecting to obtain the final product A Co-NHC black powder.
Example 3: preparation of monoatomic nickel/nitrogen co-doped hollow carbon material
Weighing 1 g of silicon dioxide hard template, ultrasonically dispersing in 150ml of deionized water, and uniformly stirring to obtain a solution a; weighing 750 mg of dopamine hydrochloride and 30 mg of nickel acetylacetonate, adding into 30 ml of water, and uniformly stirring to obtain a solution b; weighing 500 mg of tris (hydroxymethyl) aminomethane, adding the tris (hydroxymethyl) aminomethane into 20 ml of deionized water, and uniformly mixing to obtain a solution c; and (3) sequentially dropwise adding the solution b and the solution c into the solution a, mechanically stirring for 1 h at room temperature of 800 r, sequentially washing the product with water and ethanol for three times respectively, centrifugally collecting, and drying the centrifugally collected product in an oven at 60 ℃ for 12 h to obtain brown powder. The dried powder is then placed in a tube furnace, N2Carrying out heat treatment in the atmosphere, heating to 900 ℃, carbonizing and pyrolyzing for 2 h at 900 ℃ to obtain A Ni-NC @ SiO2And (2) carrying out silicon dioxide template etching on the silicon dioxide template in 4M sodium hydroxide solution, wherein the etching temperature is 45 ℃, the etching time is 36h, the stirring speed is 800 r, and the final product A Ni-NHC black powder is obtained by carrying out three times of water washing and three times of ethanol washing and centrifugation after the etching is finished.
Example 4: preparation of modified diaphragm made of monoatomic iron/nitrogen co-doped hollow carbon sphere material
Weighing the catalyst and the PVDF binder according to a mass ratio of 9:1, adding the catalyst and the PVDF binder into a mortar, adding a proper amount of diluent NMP, grinding for 40 min to obtain uniform slurry, coating the uniform slurry on one side of a 2400 PP commercial diaphragm with the surface loading of about 1 mg/cm2And drying the modified diaphragm in a vacuum oven at 60 ℃ for 12 h, and cutting the modified diaphragm into a circular sheet with the diameter of 16 mm by using a cutting machine to serve as the diaphragm of the lithium-sulfur battery. As shown in fig. 2, the coating thickness was about 25 μm. Fig. 4 shows a preparation process of a lithium-sulfur battery based on a monoatomic iron/nitrogen co-doped hollow carbon sphere modified separator.
The cycling performance of the assembled button cell is tested in a blue test system, as shown in fig. 3, the initial discharge capacity of the lithium-sulfur cell based on the monoatomic iron/nitrogen co-doped hollow carbon sphere modified diaphragm is 1150.6mA h/g under the current density of 1C, and after the cell is cycled for 120 times, the specific capacity of 945.4 mA h/g is reserved in the cell. The electrical performance of the lithium-sulfur battery is obviously improved. Meanwhile, if the electrochemical performance test is carried out under the simulated solar illumination, the polysulfide conversion is accelerated based on the monatomic metal photocatalysis, and the electrochemical performance of the lithium-sulfur battery is further improved.
Example 5: preparation of modified diaphragm made of monoatomic cobalt/nitrogen co-doped hollow carbon sphere material
Weighing A Co-NHC and PVDF binder according to the mass ratio of 9:1, adding into a mortar, adding a proper amount of diluent NMP, grinding for 40 min to obtain uniform slurry, coating on one side of 2400 PP commercial diaphragm with the surface loading of about 1 mg/cm2And drying the modified diaphragm in a vacuum oven at 60 ℃ for 12 h, and cutting the modified diaphragm into a circular sheet with the diameter of 16 mm by using a cutting machine to serve as the diaphragm of the lithium-sulfur battery.
The assembled button cell is tested for the cycle performance in a blue test system, and the initial capacity of the cell adopting the A Co-NHC/PP membrane is 1084.9 mA h/g. After 100 times of charging and discharging, 837.7mA h/g specific capacity is still kept. The cycle performance of the lithium-sulfur battery is obviously improved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. 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.
Claims (10)
1. A single-atom metal/nitrogen co-doped hollow carbon sphere photo/electro-catalytic material is characterized in that metal exists in an atom form, the structure of the material is a hollow carbon sphere structure, and the metal is one or more of iron, cobalt, nickel, vanadium and zinc.
2. The preparation method of the monatomic metal/nitrogen-codoped hollow carbon sphere photo/electrocatalytic material as claimed in claim 1, characterized in that a polymer encapsulation method is adopted, the metal salt is uniformly dispersed by utilizing the interaction of dopamine and the metal salt, and then the monatomic metal/nitrogen-codoped hollow carbon sphere photo/electrocatalytic material is obtained by pyrolysis, etching and drying.
3. The method of claim 2, comprising the steps of:
step (1): polymerizing dopamine containing metal salt on the surface of silicon dioxide, and performing high-temperature pyrolysis carbonization to obtain a monatomic metal/nitrogen-doped carbon and silicon dioxide core-shell structure material;
step (2): etching the monatomic metal/nitrogen-doped carbon and silicon dioxide core-shell structure material obtained in the step (1) in a sodium hydroxide solution, and removing the hard template;
and (3): and (3) washing the reaction product obtained in the step (2) with water and ethanol for several times respectively, and drying to obtain the monoatomic metal/nitrogen co-doped hollow carbon sphere material.
4. The preparation method of claim 3, wherein in the step (1), the metal salt is one or more of a metal iron salt, a metal cobalt salt, a metal nickel salt, a metal vanadium salt and a metal zinc salt; the ferric salt is one or more of ferric nitrate, ferric chloride, ferric acetylacetonate and iron porphyrin; the cobalt salt is one or more of cobalt nitrate, cobalt chloride, cobalt acetylacetonate and cobalt porphyrin; the nickel salt is one or more of nickel nitrate, nickel chloride and nickel acetylacetonate, and the metal vanadium salt is one or more of vanadium trichloride, vanadium sulfate and vanadyl acetylacetonate; the zinc salt is one or more of zinc nitrate, zinc chloride, zinc acetate and zinc acetylacetonate; in the step (1), the high-temperature pyrolysis carbonization is carried out at 750-900 ℃ under the protection atmosphere of argon; the high-temperature pyrolysis carbonization treatment is preferably carried out at 900 ℃.
5. The preparation method according to claim 3, wherein in the step (2), the concentration of the sodium hydroxide is 2-8 mol/L, preferably 4 mol/L; the etching temperature is 40-90 ℃, and preferably 45 ℃; the etching time is 24-36 h, preferably 36 h; in step (3), the drying environment is a vacuum environment, and the temperature is between 30 ℃ and 60 ℃, and the preferred drying temperature is 60 ℃.
6. The use of the monatomic metal/nitrogen-co-doped hollow carbon sphere photo/electro-catalytic material of claim 1 or the monatomic metal/nitrogen-co-doped hollow carbon sphere photo/electro-catalytic material prepared by the preparation method of any one of claims 2 to 5 in a coating of a lithium-sulfur battery separator, wherein the monatomic metal/nitrogen-co-doped hollow carbon sphere material is coated on the surface of the separator for modification.
7. The application of claim 6, wherein the monoatomic metal/nitrogen-codoped hollow carbon sphere material and the binder are uniformly ground to obtain a mixed slurry, the mixed slurry is coated on the surface of the diaphragm and dried for standby, and the thickness of the coating is controlled to be 20-50 μm, preferably 25 μm.
8. The application of claim 7, wherein the total mass of the monatomic metal/nitrogen-doped hollow carbon sphere material and the binder is taken as a reference, wherein the monatomic metal/nitrogen-doped hollow carbon sphere material accounts for 80-90%, preferably 90%, of the mass fraction; the mass fraction of the binder is 10-20%, preferably 10%.
9. Use according to claim 7, characterized in that the mass ratio is 9:1 and grinding to obtain uniform slurry, coating the slurry on a diaphragm, wherein the thickness of the coating is about 25 mu m, and drying the modified diaphragm in vacuum for later use.
10. A lithium-sulfur battery having the modified separator, wherein the modified separator is prepared by the method of any one of claims 6 to 9.
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Application publication date: 20210917 |