CN114956063A - Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery - Google Patents

Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery Download PDF

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CN114956063A
CN114956063A CN202210193228.1A CN202210193228A CN114956063A CN 114956063 A CN114956063 A CN 114956063A CN 202210193228 A CN202210193228 A CN 202210193228A CN 114956063 A CN114956063 A CN 114956063A
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fluorinated modified
modified graphene
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潘俊安
谭鑫
潘勇
罗振亚
谢淑红
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Xiangtan University
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Abstract

The invention discloses a preparation method of a nitrogen-doped fluorinated modified graphene potassium electrical anode material, which is characterized by preparing an N-layer graphene oxide aqueous solution by using a Hummers method; carrying out hydrothermal reaction on a graphene oxide aqueous solution and a fluorine source, centrifuging deionized water, and drying to obtain fluorinated modified graphene; placing the fluorinated modified graphene and a nitrogen source in a reaction kettle with a polytetrafluoroethylene lining for reaction, dispersing the fluorinated modified graphene and the nitrogen source in ethanol after washing, and performing suction filtration, washing and drying to obtain a nitrogen-doped fluorinated modified graphene negative electrode material; the size of the N-layer graphene oxide is 1-50 mu m, wherein N is more than or equal to 3 and less than or equal to 10, and N is a positive integer; the mass ratio of the graphene oxide to the fluorine source is 1: 1-3; the mass ratio of the fluorinated modified graphene to the nitrogen source is 2-4: 1; the nitrogen-doped fluorinated modified graphene anode material has the advantages that the fluorine content is 3% -4%, the nitrogen content is 15% -22%, the method is simple in process, and the prepared nitrogen-doped fluorinated modified graphene anode material has excellent electrochemical performance.

Description

Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery
Technical Field
The invention relates to the field of preparation of potassium electric cathode materials, in particular to a preparation method of a nitrogen-doped graphene potassium electric cathode material.
Background
The potassium ion battery is expected to make up the defects of the lithium battery by virtue of abundant potassium resources, higher voltage and better ion transmission characteristics, becomes a new secondary battery, provides a direction for the important development of sustainable energy storage devices, and shows great development potential in the field of energy storage.
Carbon materials are considered to be extremely promising due to their high electrical conductivity, eco-friendliness and structural stability, among which graphene is one of SP 2 The novel material with a single-layer two-dimensional honeycomb lattice structure is formed by tightly stacking hybridized and connected carbon atoms, has excellent optical, electrical and mechanical properties, and the unique two-dimensional framework and the larger specific surface area of the graphene material can improve the storage of potassium ions.
Heteroatom doping, such as N, O, P, S and the like, is introduced, so that the conductivity and electrochemical performance of the carbon material can be remarkably improved, the diffusion coefficient of potassium ions can be effectively improved by the nitrogen-doped graphene, but the nitrogen-doped graphene reported at present has the problem of low nitrogen doping amount.
In the prior art, in Chinese patent CN109110751A, graphene is used as a carbon source, dicyandiamide is used as a fluorine source, and the prepared nitrogen-doped graphene material has the defect of low nitrogen content.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a nitrogen-doped fluorinated modified graphene potassium electrical anode material, which solves the problems of complex preparation process, high reaction temperature, complex experimental operation, high energy consumption, high reaction cost, low nitrogen content and the like in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the preparation method of the nitrogen-doped fluorinated modified graphene negative electrode material comprises the following steps:
firstly, preparing a graphene oxide aqueous solution by using a Hummers method, then carrying out hydrothermal reaction on the graphene oxide aqueous solution and a fluorine source to obtain fluorinated modified graphene, mixing the fluorinated modified graphene and the nitrogen source, carrying out ultrasonic treatment, placing the mixture in a reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, cooling the solution to room temperature, centrifuging, washing with water, carrying out ethanol suction filtration, and drying to obtain the nitrogen-doped fluorinated modified graphene negative electrode material.
The preparation method of the nitrogen-doped fluorinated modified graphene potassium electric anode material comprises the following specific steps:
1) preparing a graphene oxide aqueous solution by using a Hummers method, slowly adding 2-4 g of natural crystalline flake graphite and 2-4 g of sodium nitrate into 92-96 ml of concentrated sulfuric acid at 0 ℃, uniformly stirring and mixing, slowly adding 12g of potassium permanganate into the mixed solution, stirring and reacting for 90min under an ice bath condition, reacting the mixture for 90min under 0 ℃ stirring, slowly heating to 35 ℃, reacting for 2h, slowly dropwise adding 80ml of deionized water into the mixed solution, after dropwise adding, sequentially adding 200ml of deionized water and 10ml of hydrogen peroxide (30%), stirring for 20min, removing acid and water-soluble ions by washing to obtain a graphene oxide slurry, diluting and mixing the graphene oxide slurry and the deionized water according to a volume ratio of 1: 10, dispersing in water by ultrasound (80W, 10min), finally centrifuging the dispersion for the first step (3000r/min, 5min), repeatedly centrifuging until visible particles are completely removed, performing second-step centrifugation (8000r/min, 10min) for further removing water-soluble particles, dispersing the solid obtained by centrifugation in deionized water, and repeatedly centrifuging to remove soluble impurities to obtain a graphene oxide aqueous solution with high purity;
2) uniformly mixing the graphene oxide obtained in the step 1) with a fluorine source according to a mass ratio of 1: 1-3, placing the obtained mixed solution in a beaker, performing ultrasonic treatment for 30-60 min, then placing the obtained mixed solution in a reaction kettle with a tetrafluoroethylene lining, performing hydrothermal reaction at 160-180 ℃ for 18-24 h after sealing and vacuumizing, dispersing the solution in deionized water after cooling to room temperature, repeatedly centrifuging (the centrifugation rate is 7000-8000 r/min, and the centrifugation time is 30-40 min) until the pH value of the mixed solution reaches neutral, performing suction filtration on the deionized water, placing in a vacuum drying oven, and drying at 50-60 ℃ for 20-30 h to obtain fluorinated modified graphene;
3) uniformly mixing the fluorinated modified graphene obtained in the step 2) with a nitrogen source according to a mass ratio of 2-4: 1, placing the obtained mixed solution in a beaker, performing ultrasonic treatment for 30-60 min, then placing the obtained mixed solution in a reaction kettle with a tetrafluoroethylene lining, sealing and vacuumizing, performing hydrothermal reaction at 140-160 ℃ for 12-16 h, dispersing the solution in deionized water after cooling to room temperature, repeatedly centrifuging for several times (the centrifugation rate is 7000-8000 r/min, and the centrifugation time is 30-40 min) until the pH value of the mixed solution reaches neutral, then dispersing the solution in an ethanol solution for suction filtration, repeatedly performing suction filtration for three times, placing the obtained solid in a vacuum drying box, and drying at 50-60 ℃ for 20-30 h to obtain a nitrogen-doped fluorinated modified graphene material;
4) taking the nitrogen-doped fluorinated modified graphene prepared in the step 3) as an active material, mixing the active material with a conductive agent and a binding agent according to the mass ratio of 8: 1, performing processes of size mixing, coating, drying, cutting into pieces and the like to obtain an electrode slice, and taking metal potassium as a counter electrode to assemble the potassium/nitrogen-doped fluorinated modified graphene battery.
In the step 1), the thickness of the graphene oxide is 0.6-1.2 nm, the number of layers is 3-10, the size of a lamella is 1-50 mu m, and the specific surface area is 65-85 m 2 /g。
In the step 1), the concentration of the graphene oxide aqueous solution is 4-5 mg/ml.
Wherein, in the step 2), the fluorine source is at least one of hydrofluoric acid, ammonium fluoride, potassium fluoride and sodium fluoride.
In the step 3), the nitrogen source is at least one of triethylamine, melamine, urea, cyanamide, dicyandiamide and polyaniline.
In the step 4), the conductive agent is at least one of ketjen black, acetylene black, carbon nanotubes and carbon fibers.
Wherein, in the step 4), the binder is polytetrafluoroethylene or polyvinylidene fluoride.
In the step 4), N-Methyl pyrrolidone (NMP) is used as a solvent, the nitrogen-doped fluorinated modified graphene, the conductive agent and the binder are prepared into slurry, the slurry is coated on a carbon-coated aluminum foil, and the electrode sheet is prepared by cutting pieces after drying.
The invention has the advantages that:
1) the scale graphite material provided by the invention has the advantages of rich raw materials, simple preparation process by a hydrothermal method, convenience in operation, high feasibility and low cost, and can realize large-scale production;
2) the nitrogen-doped fluorinated modified graphene material provided by the invention has excellent structural performance, not only can the stability of the material be ensured when potassium ions are embedded and removed, but also the transmission efficiency of the material can be enhanced as a conductive network;
3) the nitrogen doping provided by the invention can increase the interlayer spacing of graphene, effectively reduce the diffusion barrier of potassium ions between large layers, and more importantly, the existence of a large amount of fluorine atoms effectively modifies the surface property of graphene, and simultaneously assists in increasing the doping content of nitrogen atoms, so that the potassium ion battery has more excellent electrochemical performance, thereby having good application prospect.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) of the nitrogen-doped fluorinated modified graphene potassium anode material prepared by the present invention.
Fig. 2 is a material X-ray photoelectron spectrum (XPS) of the nitrogen-doped fluorinated modified graphene potassium electro-negative electrode material prepared by the present invention.
FIG. 3 is a performance diagram of the nitrogen-doped fluorinated modified graphene potassium electrical anode material prepared by the invention after circulating for 150 circles at a current density of 40 mA/g.
Fig. 4 is a flowchart of a nitrogen-doped fluorinated modified graphene material prepared according to the present invention.
Detailed Description
The invention is further explained in detail below with reference to the drawings and examples:
in the aspect of changing the microstructure of the graphene, due to the introduction of fluorine atoms, a large number of defects and reaction sites are generated on the surface of the graphene, so that the doping content of the nitrogen atoms can be improved, the graphene shows a large number of folds and curled structures, the interlayer spacing of graphene stacking is increased, and the insertion and extraction of potassium ions are facilitated, and the preparation method is implemented according to the following steps:
1) preparing graphene oxide by using a Hummers method (the Hummers method is a conventional published method and is not described in detail);
2) carrying out hydrothermal reaction on the graphene oxide obtained in the step 1) and a fluorine source to prepare fluorinated modified graphene;
3) carrying out hydrothermal reaction on the fluorinated modified graphene obtained in the step 2) and a nitrogen source to prepare nitrogen-doped fluorinated modified graphene;
4) taking the nitrogen-doped fluorinated modified graphene prepared in the step 3) as an active material, mixing the active material with Ketjen black and polyvinylidene fluoride according to a ratio of 8: 1, taking N-Methyl pyrrolidone (NMP) as a solvent, performing processes of size mixing, coating, drying, cutting and the like to obtain an electrode plate, and taking metal potassium as a counter electrode to assemble the potassium/nitrogen-doped fluorinated modified graphene battery.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example one
In the preparation of the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material in the embodiment, the fluorine content is 4% and the nitrogen content is 22%, and the influence of the preparation method provided in the embodiment on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material is verified through specific tests, specifically as follows:
1) preparing graphene oxide by using an improved Hummers method (the Hummers method is a conventional published method and is not described in detail);
2) weighing 200mg of the graphene oxide obtained in the step 1), dissolving in 40ml of distilled water, preparing a 5mg/ml solution in a ratio, ultrasonically forming a uniform dispersion liquid, weighing 600mg of potassium fluoride, placing in 20ml of distilled water until the potassium fluoride is completely dissolved, slowly dripping the potassium fluoride solution into the graphene oxide dispersion liquid, transferring into a reaction kettle with a 100ml polytetrafluoroethylene lining, sealing and vacuumizing, carrying out hydrothermal reaction at 180 ℃ for 20 hours, cooling the solution to room temperature, dispersing in deionized water, wherein the centrifugation rate is 7000r/min, the centrifugation time is 30min, repeatedly centrifuging for several times until the pH value of the mixed solution is neutral, carrying out suction filtration on the deionized water, placing in a vacuum drying oven, and drying at 60 ℃ for 24 hours to obtain fluorinated modified graphene;
3) weighing 200mg of the fluorinated modified graphene obtained in the step 2), uniformly ultrasonically dispersing in 40ml of distilled water, weighing 100mg of melamine, placing in 20ml of distilled water, stirring at 60 ℃ until the melamine is completely dissolved, slowly dripping the melamine solution into the fluorinated modified graphene dispersion solution, transferring into a reaction kettle with a 100ml of tetrafluoroethylene lining, sealing, vacuumizing, carrying out hydrothermal reaction at 160 ℃ for 16h, cooling the solution to room temperature, dispersing in deionized water, centrifuging at the centrifugal rate of 7000r/min for 30min, repeatedly centrifuging until the pH value of the mixed solution reaches neutral, dispersing the solution in an ethanol solution, carrying out suction filtration, repeatedly carrying out suction filtration for 3 times, placing the obtained solid in a vacuum drying oven, and drying at 60 ℃ for 24h to obtain a nitrogen-doped fluorinated modified graphene material;
4) taking the nitrogen-doped fluorinated modified graphene prepared in the step 3) as an active material, mixing with a conductive agent, a binder and the like, coating, drying, cutting into pieces and the like to obtain an electrode slice, and assembling the potassium/nitrogen-doped fluorinated modified graphene battery by taking metal potassium as a counter electrode.
The method for preparing the potassium ion button cell by using the nitrogen-doped fluorinated modified graphene prepared by the embodiment as an active substance comprises the following steps:respectively weighing nitrogen-doped fluorinated modified graphene, Keqin black and polyvinylidene fluoride according to the ratio of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 DEC (1: 1); the 2032 button cell is adopted for assembly, the whole process is carried out in a glove box, the assembly sequence is negative electrode shell-potassium sheet-electrolyte-diaphragm-electrolyte-electrode sheet-gasket-spring sheet-positive electrode shell, the packaging treatment is carried out after the assembly is finished, and finally the performance is tested.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Example two
In this embodiment, for example, when the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared, the fluorine content is 3.7% and the nitrogen content is 20%, specific tests prove that the preparation method provided in this embodiment has a specific influence on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material, and specifically the following steps are performed:
in this embodiment, compared with the first embodiment, the mass of the potassium fluoride weighed in the step 2) is adjusted from 600mg to 400mg, and other experimental conditions are the same as those in the first embodiment, so that the fluorine content in the prepared nitrogen-doped fluorinated modified graphene material is 3.7%, and the nitrogen content is 20%;
then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding appropriate amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, and coating the slurry on carbon-coated aluminum foil with a thickness of 200 μmVacuum drying for 24h to obtain an electrode plate; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
EXAMPLE III
In this embodiment, for example, when the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared, the fluorine content is 3% and the nitrogen content is 15%, the influence of the preparation method provided in this embodiment on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material is verified through a specific test, and the specific test is as follows:
in this embodiment, compared with the first embodiment, the mass of the potassium fluoride weighed in the step 2) is adjusted from 600mg to 200mg, and other experimental conditions are the same as those in the first embodiment, so that the fluorine content in the prepared nitrogen-doped fluorinated modified graphene material is 3%, and the nitrogen content is 15%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 DEC (1: 1), assembling into a nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Example four
In this embodiment, for example, when the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared, the fluorine content is 3.3% and the nitrogen content is 17%, a specific test is performed to verify the influence of the preparation method provided in this embodiment on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material, specifically as follows:
in this embodiment, compared with the first embodiment, 200mg of the fluorinated modified graphene weighed in the step 3) is adjusted to 300mg, and other experimental conditions are the same as those in the first embodiment, so that the fluorine content in the prepared nitrogen-doped fluorinated modified graphene material is 3.3%, and the nitrogen content is 17%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
EXAMPLE five
In this embodiment, for example, when the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared, the fluorine content is 3.1% and the nitrogen content is 15.5%, the influence of the preparation method provided in this embodiment on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material is verified through a specific test, and the specific test is as follows:
in this embodiment, compared with the first embodiment, 600mg of potassium fluoride weighed in the step 2) is adjusted to 200mg, the hydrothermal temperature is adjusted from 180 ℃ to 160 ℃, 200mg of fluorinated modified graphene weighed in the step 3) is adjusted to 400mg, other experimental conditions are the same as those in the first embodiment, and the fluorine content and the nitrogen content in the prepared nitrogen-doped fluorinated modified graphene material are 3.1% and 15.5%, respectively.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride into a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
EXAMPLE six
In this embodiment, for example, when the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared, the fluorine content is 3.5% and the nitrogen content is 19%, specific tests prove that the preparation method provided in this embodiment has a specific influence on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material, and specifically the following steps are performed:
in this embodiment, compared with the first embodiment, 600mg of potassium fluoride weighed in the step 2) is adjusted to 400mg, the hydrothermal temperature is adjusted from 180 ℃ to 170 ℃, the hydrothermal time is adjusted from 20h to 18h, the hydrothermal temperature in the step 3) is adjusted from 160h to 150h, the hydrothermal time is adjusted from 16h to 12h, and other experimental conditions are the same as those in the first embodiment, so that the fluorine content and the nitrogen content in the prepared nitrogen-doped fluorinated modified graphene material are 3.5% and 19%, respectively.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrroleThe step of preparing the electrode plate comprises the steps of (1) preparing alkyl ketone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24 hours to obtain the electrode plate; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test result of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment is shown in table 2.
EXAMPLE seven
In this embodiment, for example, when the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared, the fluorine content is 3.8% and the nitrogen content is 21%, specific tests prove that the preparation method provided in this embodiment has a specific influence on the fluorine-nitrogen ratio in the nitrogen-doped fluorinated modified graphene material, and the specific influence is as follows:
in this embodiment, compared with the first embodiment, the hydrothermal time in the step 2) is adjusted from 20h to 24h, the hydrothermal temperature in the step 3) is adjusted from 200mg to 300mg, the hydrothermal temperature is adjusted from 160h to 150h, the hydrothermal time is adjusted from 16h to 12h, and other experimental conditions are the same as those in the first embodiment, so that the fluorine content and the nitrogen content in the nitrogen-doped fluorinated modified graphene material are 3.8% and 21%, respectively.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methylpyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying the coated aluminum foil in vacuum for 24 hours to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Comparative example 1
Compared with the first embodiment, in the comparative example, potassium fluoride and melamine are not added, and the fluorine content and the nitrogen content in the prepared nitrogen-doped graphene material are respectively 0% and 0%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped graphene, the ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methylpyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying the coated aluminum foil in vacuum for 24 hours to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 DEC (1: 1) to assemble the nitrogen-doped graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped graphene material prepared in this embodiment are shown in table 2.
Comparative example No. two
Compared with the first embodiment, in the comparative example, potassium fluoride is not added, other experimental conditions are the same as those in the first embodiment, and the fluorine content and the nitrogen content in the prepared nitrogen-doped graphene material are respectively 0% and 3.4%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 DEC (1: 1), assembling into a nitrogen-doped graphene potassium ion button cell, and testingThe cycle performance thereof.
The electrochemical performance test results of the nitrogen-doped graphene material prepared in this embodiment are shown in table 2.
Comparative example No. three
Compared with the first embodiment, the method has the advantages that melamine is not added, other experimental conditions are the same as those of the first embodiment, and the fluorine content and the nitrogen content of the prepared nitrogen-doped fluorinated modified graphene material are respectively 3.9% and 0%;
then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Comparative example No. four
In this comparative example, compared with the first example, the potassium fluoride weighed in the step 2) is adjusted from 600mg to 60mg, and other experimental conditions are the same as those in the first example, so that the fluorine content in the prepared nitrogen-doped fluorinated modified graphene material is 0.6%, and the nitrogen content is 4.2%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding N-methyl pyrrolidone until a uniform slurry is obtained, and adding 2% of N-methyl pyrrolidoneCoating the aluminum foil with the thickness of 00 mu m on the carbon-coated aluminum foil, and drying the aluminum foil in vacuum for 24 hours to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Comparative example five
In the comparative example, compared with the first example, 100mg of melamine weighed in the step 3) is adjusted to 20mg, and other experimental conditions are the same as those in the first example, so that the fluorine content of the prepared nitrogen-doped fluorinated modified graphene material is 3.8%, and the nitrogen content is 9%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride into a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Comparative example six
In the comparative example, compared with the example one, the hydrothermal temperature in the step 2) is adjusted from 180 ℃ to 200 ℃, the hydrothermal time is adjusted from 20h to 30h, the hydrothermal temperature in the step 3) is adjusted from 160h to 200h, the hydrothermal time is adjusted from 16h to 24h, and other experimental conditions are the same as those in the example one, so that the prepared nitrogen-doped fluorinated modified graphene material has the fluorine content of 2% and the nitrogen content of 7.5%.
Then, according to the battery assembling method of the embodiment I, the nitrogen-doped fluorinated modified graphene, the Ketjen black and the polyvinylidene fluoride are weighed according to the proportion of 8: 1; placing polyvinylidene fluoride in a small beaker, adding a certain amount of N-methyl pyrrolidone, and stirring to form a gel; uniformly mixing nitrogen-doped fluorinated modified graphene and conductive ketjen black, and slowly adding the mixture into a beaker; adding a proper amount of N-methyl pyrrolidone until uniformly dispersed slurry is obtained, then coating the slurry on a carbon-coated aluminum foil in a thickness of 200 mu m, and drying in vacuum for 24h to obtain an electrode slice; the metal potassium is used as a counter electrode, the diaphragm is a Celgard-2500 series glass fiber diaphragm, and the electrolyte is 0.8M KPF 6 And (2) DEC (1: 1) to assemble the nitrogen-doped fluorinated modified graphene potassium ion button cell, and testing the cycle performance of the button cell.
The electrochemical performance test results of the nitrogen-doped fluorinated modified graphene material prepared in this embodiment are shown in table 2.
Referring to table 1, a comparative summary is made of the nitrogen-doped fluorinated modified graphene prepared in the examples and the comparative examples of the present invention, and it can be seen that:
1) in the first embodiment, when the mass ratio of the fluorinated modified graphene to the melamine is 2: 1, the hydrothermal reaction temperature of the fluorinated modified graphene and the melamine is 160 ℃, and the hydrothermal reaction time is 16 hours, the nitrogen-doped fluorinated modified graphene material with the highest nitrogen content can be obtained;
2) it is known from the comparative examples that as the fluorine content increases, the nitrogen content also increases, and the existence of a large number of fluorine atoms effectively modifies the surface properties of graphene and assists in increasing the doping content of nitrogen atoms.
Figure BDA0003525733170000171
Figure BDA0003525733170000181
TABLE 1
Referring to table 2, for comparison of electrochemical performance of the potassium ion button cells in examples and comparative examples, the current density was 40mA/g, from which it can be seen that:
1) in the first embodiment, when the nitrogen-doped fluorinated modified graphene prepared by the method is used as a negative electrode active material, wherein the nitrogen content is 22%, the potassium ion battery is prepared, and the battery still has a discharge specific capacity of 302mAh/g after 100 cycles under the current density of 40mA/g, so that the battery has excellent cycle performance;
2) the embodiment and the comparative example show that the cycle performance and the corresponding specific discharge capacity of the nitrogen-doped fluorinated modified graphene are obviously improved compared with the common nitrogen-doped graphene material serving as the negative active material, the specific discharge capacity of the nitrogen-doped fluorinated modified graphene prepared by the invention serving as the negative active material is 272-302 mAh/g, and the specific discharge capacity of the common nitrogen-doped graphene oxide serving as the negative active material is only 202 mAh/g;
3) in an embodiment, the nitrogen-doped fluorinated modified graphene material is used as a negative active material, and the prepared potassium ion battery has the advantages of higher nitrogen content, better cycle performance and higher specific discharge capacity.
Figure BDA0003525733170000182
Figure BDA0003525733170000191
TABLE 2
In summary, compared with the nitrogen-doped graphene in the prior art, the excellent cycle stability of the nitrogen-doped fluorinated modified graphene potassium electrical anode material provided by the embodiment of the invention is mainly attributed to the existence of graphene nitrogen and a semi-ionic C-F bond, so that the charge transfer internal resistance of the electrode material is further reduced, meanwhile, the diffusion barrier of potassium ions is effectively reduced between large layers, more importantly, the existence of a large amount of fluorine atoms effectively modifies the surface property of graphene, simultaneously assists in increasing the doping content of nitrogen atoms, further increases the diffusion coefficient of potassium ions, and the combined action of the several aspects greatly improves the cycle stability of the battery.
In addition, the nitrogen-doped fluorinated modified graphene is applied to a potassium electric anode material, so that a high-specific-capacity potassium ion battery with 302mAh/g after 100 cycles under 40mA/g current density is obtained.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modification, equivalent replacement, or improvement made within the spirit and scope of the present invention should be included in the present invention.

Claims (10)

1. A preparation method of a nitrogen-doped fluorinated modified graphene potassium electrical anode material is characterized by comprising the following steps:
preparing an N-layer graphene oxide aqueous solution by using a Hummers method;
carrying out hydrothermal reaction on the graphene oxide aqueous solution and a fluorine source, and centrifuging and drying to obtain fluorinated modified graphene;
placing the fluorinated modified graphene and a nitrogen source in a reaction kettle with a polytetrafluoroethylene lining, dispersing the fluorinated modified graphene and the nitrogen source in ethanol after hydrothermal reaction, and then obtaining a nitrogen-doped fluorinated modified graphene negative electrode material after suction filtration, washing and drying; the size of the N-layer graphene oxide is 1-50 mu m, wherein N is more than or equal to 3 and less than or equal to 10, and N is a positive integer; the mass ratio of the graphene oxide to the fluorine source is 1: 1-3; the mass ratio of the fluorinated modified graphene to the nitrogen source is 2-4: 1; in the nitrogen-doped fluorinated modified graphene negative electrode material, the fluorine content is 3% -4%, and the nitrogen content is 15% -22%.
2. The preparation method of the nitrogen-doped fluorinated modified potassium graphene anode material according to claim 1, wherein the method further comprises the following specific steps:
1) preparing a graphene oxide aqueous solution by using a Hummers method, slowly adding 2-4 g of natural crystalline flake graphite and 2-4 g of sodium nitrate into 92-96 ml of concentrated sulfuric acid at 0 ℃, uniformly stirring and mixing, slowly adding 12g of potassium permanganate into the mixed solution, stirring and reacting for 90min under an ice bath condition, slowly heating the mixture to 35 ℃ after the mixture reacts for 90min under stirring at 0 ℃, reacting for 2h, slowly dropwise adding 80ml of deionized water into the mixed solution, after dropwise adding, sequentially adding 200ml of deionized water and 10ml of hydrogen peroxide (30%), stirring for 20min, reacting to obtain a graphene oxide slurry, and washing with water to be neutral to obtain the graphene oxide aqueous solution;
2) uniformly mixing the graphene oxide aqueous solution obtained in the step 1) with a fluorine source according to a mass ratio of 1: 1-3, placing the obtained mixed solution in a beaker, performing ultrasonic treatment for 30-60 min, then placing the obtained mixed solution in a reaction kettle with a tetrafluoroethylene lining, sealing and vacuumizing, performing hydrothermal reaction at 160-180 ℃ for 18-24 h, cooling the solution to room temperature, dispersing the solution in deionized water, repeatedly centrifuging for several times until the pH value of the mixed solution reaches neutrality, performing suction filtration on the mixed solution by using the deionized water, placing the mixed solution in a vacuum drying box, and drying the mixed solution at 50-60 ℃ for 20-30 h to obtain fluorinated modified graphene;
3) uniformly mixing the fluorinated modified graphene obtained in the step 2) with a nitrogen source according to a mass ratio of 2-4: 1, placing the obtained mixed solution in a beaker, performing ultrasonic treatment for 30-60 min, then placing the obtained mixed solution in a reaction kettle with a tetrafluoroethylene lining, sealing and vacuumizing, performing hydrothermal reaction at 140-160 ℃ for 12-16 h, cooling the solution to room temperature, dispersing the solution in deionized water, repeatedly centrifuging for several times until the pH value of the mixed solution is neutral, then dispersing the solution in an ethanol solution for suction filtration, repeating the suction filtration for three times, placing the obtained solid in a vacuum drying oven, and drying for 20-30 h at 50-60 ℃ to obtain a nitrogen-doped fluorinated modified graphene material;
4) taking the nitrogen-doped fluorinated modified graphene prepared in the step 3) as an active material, mixing the active material with a conductive agent and a binder according to the mass ratio of 8: 1, performing processes of size mixing, coating, drying, cutting and the like to obtain an electrode slice, and assembling the potassium/nitrogen-doped fluorinated modified graphene battery by taking metal potassium as a counter electrode.
3. The hydrothermal method for preparing the nitrogen-doped fluorinated modified graphene potassium cathode material according to claim 1, wherein the graphene oxide has a thickness of 0.6-1.2 nm, a number of layers of 3-10, a sheet size of 1-50 μm, and a specific surface area of 65-85 m 2 /g。
4. The method for preparing the nitrogen-doped fluorinated modified graphene potassium electrical anode material according to claim 1, wherein the fluorine source is one or more fluorine-containing compounds selected from hydrofluoric acid, ammonium fluoride, potassium fluoride and sodium fluoride.
5. The method for preparing the nitrogen-doped fluorinated modified potassium graphene anode material according to claim 1, wherein the nitrogen source is one or more nitrogen-containing compounds selected from triethylamine, melamine, urea, cyanamide, dicyandiamide and polyaniline.
6. The preparation method of the nitrogen-doped fluorinated modified graphene potassium electrical anode material according to claim 2, wherein in the step 1), the concentration of the graphene oxide aqueous solution is 4-5 mg/ml.
7. The method for preparing the nitrogen-doped fluorinated modified potassium graphene anode material according to claim 2, wherein in the step 4), the conductive agent is at least one of ketjen black, acetylene black, carbon nanotubes and carbon fibers.
8. The method for preparing the nitrogen-doped fluorinated modified graphene potassium cathode material according to claim 2, wherein in the step 4), the binder is polytetrafluoroethylene or polyvinylidene fluoride.
9. The method for preparing the nitrogen-doped fluorinated modified graphene potassium electrical anode material according to claim 2, wherein in the step 4), N-Methyl pyrrolidone (NMP) is used as a solvent, the nitrogen-doped fluorinated modified graphene, the conductive agent and the binder are prepared into slurry, the slurry is coated on a carbon-coated aluminum foil, and the electrode sheet is prepared by cutting pieces after drying.
10. The potassium/nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material is prepared by the preparation method of the nitrogen-doped fluorinated modified graphene potassium electrical negative electrode material according to claims 1 to 9, the nitrogen-doped fluorinated modified graphene negative electrode material, a conductive agent and a binder are subjected to size mixing, coating, drying and cutting to obtain an electrode plate, and potassium metal is used as a counter electrode to assemble the potassium/nitrogen-doped fluorinated modified graphene battery.
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