CN117832462B - Preparation method of fluorine-doped carbon-loaded red phosphorus anode material, sodium battery and preparation method - Google Patents
Preparation method of fluorine-doped carbon-loaded red phosphorus anode material, sodium battery and preparation method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 115
- 239000010405 anode material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 20
- 239000011734 sodium Substances 0.000 title claims abstract description 20
- 239000002135 nanosheet Substances 0.000 claims abstract description 97
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 63
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 43
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- 239000004202 carbamide Substances 0.000 claims abstract description 17
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- DHZIIRMIXLYCRQ-UHFFFAOYSA-N benzene-1,4-dicarbonyl isocyanate Chemical compound O=C=NC(=O)C1=CC=C(C(=O)N=C=O)C=C1 DHZIIRMIXLYCRQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
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- 230000000149 penetrating effect Effects 0.000 claims abstract description 3
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 5
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The application relates to the technical field of sodium ion batteries, in particular to a preparation method and a material of a fluorine-doped carbon-loaded red phosphorus negative electrode material, a sodium battery and a preparation method, wherein the preparation method of the fluorine-doped carbon nano-sheet-loaded red phosphorus negative electrode material comprises the following steps: reacting urea and terephthalyl isocyanate in a solvent to obtain polymer molecules; carbonizing polymer molecules to obtain a carbon material with a nano-layer structure; mechanically grinding a carbon material and polytetrafluoroethylene to obtain a mixture, and sintering the mixture to obtain a carbon nano sheet doped with fluorine; and penetrating red phosphorus into the carbon nano-sheet in an evaporation-condensation mode to obtain the fluorine-doped carbon nano-sheet loaded red phosphorus anode material. According to the application, red phosphorus is nanocrystallized and embedded in the three-dimensional carbon matrix sheet layer, and chemical bonding is introduced, so that the sodium storage electrochemical performance of the red phosphorus anode can be effectively improved.
Description
Technical Field
The application relates to the technical field of sodium ion batteries, in particular to a preparation method of a fluorine-doped carbon nano-sheet-loaded red phosphorus anode material and a prepared material, a sodium ion battery containing the material and a preparation method.
Background
The rechargeable lithium ion battery is an important catalyst for starting the development of the fields of portable electronic products, electric automobiles, large-scale power grid energy storage and the like due to high energy density and long cycle life. However, the uneven distribution of lithium and limited resources have turned attention to other alternative rechargeable battery technologies. Sodium ion batteries are currently being developed as one of the potential alternatives to lithium ion batteries due to their high abundance and low cost of resources and similar electrochemical behavior. However, the large size of sodium ions results in a slow diffusion rate, a non-ideal long-current cycling stability, and significant volume changes during repeated charge and discharge.
Red phosphorus is considered to be an ideal negative electrode material because of its high specific capacity and low operating potential. However, the red phosphorus has large volume change and inherent poor conductivity in the sodium modification and sodium removal processes, so that the capacity of the red phosphorus is rapidly attenuated, the redox reaction kinetics is slow, and the practical application of the red phosphorus on the negative electrode material of the sodium ion battery is severely limited.
Therefore, a carbon matrix capable of effectively containing red phosphorus nano particles is developed, the electron conductivity of an electrode material is improved, and meanwhile, the volume effect is buffered, so that the method has great practical significance for obtaining the red phosphorus anode material with high specific capacity and high stability.
Disclosure of Invention
In order to obtain a red phosphorus anode material with high specific capacity and high stability, and solve the problems that the red phosphorus anode material has low electronic conductivity and large volume change in the cycling process of a sodium ion battery, the application provides a preparation method of a fluorine-doped carbon nano sheet-loaded red phosphorus anode material, the prepared material, a sodium ion battery containing the material and a preparation method.
In a first aspect, the application provides a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which adopts the following technical scheme:
the preparation method of the fluorine-doped carbon nano sheet-loaded red phosphorus anode material comprises the following steps:
Reacting urea and terephthalyl isocyanate in a solvent to obtain polymer molecules;
Carbonizing the polymer molecules in an inert gas environment to obtain a carbon material with a nano-layer structure;
Mechanically grinding the carbon material and polytetrafluoroethylene to obtain a mixture, and sintering the mixture to obtain a carbon nano sheet doped with fluorine;
And penetrating red phosphorus into the carbon nano-sheet in an evaporation-condensation mode to obtain the fluorine-doped carbon nano-sheet loaded red phosphorus anode material.
By adopting the technical scheme, urea and terephthalyl isocyanate are used as raw materials, and the carbon nano-sheet is obtained through polymerization reaction; on the basis of the original carbon nano lamellar structure, polytetrafluoroethylene is used as a fluorine source, and fluorine atoms are introduced into the carbon matrix in a high-temperature heat treatment mode, so that a fluorine-rich doped three-dimensional carbon nano material is obtained; and then, the red phosphorus is infiltrated into the three-dimensional structure in an evaporation-condensation mode, so that the red phosphorus/carbon composite anode material applicable to the sodium ion battery is obtained.
According to the application, the three-dimensional carbon material can effectively buffer the volume change of red phosphorus in the sodium ion deintercalation process, and can improve the electron conductivity of the red phosphorus/carbon electrode. In addition, the introduced fluorine atoms can form C-F strong chemical bonds, which is beneficial to further strengthening the interaction between red phosphorus and the carbon material, so that the red phosphorus can be stably attached in the nano lamellar to prepare the carbon material with the nano lamellar structure. By the preparation method, the fluorine-doped carbon nano sheet loaded red phosphorus anode material with high capacity and high stability, which is effectively applied to sodium ion batteries, can be obtained.
In a specific embodiment, the mass ratio of urea to terephthal-isocyanate is 8-12:1.
By adopting the technical scheme, urea and terephthalyl isocyanate are used as monomers, and continuous stable nano-structure high polymer with urea as a repeating unit is formed by bonding and polymerizing the amino group of an isocyanic acid group in the terephthalyl isocyanate and the amino group of the urea; the mass ratio of urea to terephthalyl isocyanate is optimized, so that the yield of the synthesized polymer molecules is higher.
In a specific embodiment, the carbonization treatment is performed at a temperature of 400-500 ℃ for a time of 25-35min.
By adopting the technical scheme, the polyurea carbon material with excellent electrochemical performance can be obtained by reasonably controlling the high-temperature carbonization temperature and time under the protection of inert gas. The polyurea carbon material provided by the application has excellent electrochemical characteristics of the nano carbon material, and can realize molecular-level regulation of the nano carbon material, and has high thermal stability and good structural stability.
In a specific embodiment, the mass ratio of the carbon nanoplatelets to polytetrafluoroethylene is from 5 to 15:1.
By adopting the technical scheme, fluorine atoms are doped in the carbon nano material to form C-F strong chemical bonds, and the electronegativity of the F atoms is high, and the electron density is biased to one side of the F atoms, so that the C-F bonds have polarity, the surface energy of the carbon material is reduced, the mutual combination between red phosphorus and the carbon material is enhanced, and the red phosphorus can be stably attached in the nano sheet layer; when fluorine is doped, the content of fluorine atoms introduced into the carbon material is too high, the dispersion is uneven, the doping effect is difficult to be exerted, and the performance of a subsequent battery is reduced; when the content of fluorine atoms introduced into the carbon material is too low, the doped carbon material cannot exert the battery performance, the doping effect is not ideal, and the corresponding battery capacity is reduced; the application can further improve the dispersion uniformity of fluorine atoms in the carbon material by optimizing the mass ratio of the carbon nano-sheet to the polytetrafluoroethylene, thereby improving the subsequent battery performance.
In a specific embodiment, the mass ratio of the carbon nano-sheet to red phosphorus is 0.5-1.5:1.
By adopting the technical scheme, red phosphorus has proper oxidation-reduction point positions, dendrite formation in the charge-discharge process can be avoided, and the safety of the battery is good; by loading red phosphorus on the carbon nano-sheet matrix, the severe change of the volume of the red phosphorus particles in the charge and discharge process can be effectively buffered, and the cycle performance of the composite material is improved, so that the composite material has high specific capacity and excellent cycle performance, and is beneficial to the research and development and application of the high-performance sodium ion battery.
In a specific embodiment, the sintering is specifically: and (3) placing the mixture in an inert gas environment, heating to 300-400 ℃ at 10 ℃/min, and sintering for 30min.
By adopting the technical scheme, the porosity, the density, the strength, the hardness and the like of the carbon nano-sheet can be influenced by the sintering temperature and the sintering time, so that the subsequent load rate of red phosphorus is influenced; the sintering temperature and the sintering time are too long, so that the performance of the carbon nano-sheet is reduced, and even the defect of overburning occurs; the sintering temperature is too low or the sintering time is too short, and the performance of the carbon nano-sheet is reduced due to undersintering.
In a specific embodiment, the evaporation-condensation mode is specifically: and packaging the carbon nano-sheets and red phosphorus in a vacuum quartz tube, heating to 800-900 ℃, preserving heat for 5-10h, then cooling to 250-300 ℃, preserving heat for 10-15h, and finally cooling to room temperature to obtain the fluorine-doped nano-sheet-loaded red phosphorus anode material.
By adopting the technical scheme, the operation steps are simple, and the high-capacity and high-stability anode material effectively applied to the sodium ion battery can be prepared by optimizing the process parameters during evaporation-condensation.
In a second aspect, the application provides a fluorine-doped carbon nano-sheet-loaded red phosphorus anode material, which adopts the following technical scheme:
the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material is prepared by adopting the preparation method of the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
By adopting the technical scheme, the preparation method is simple and has the capacity of large-scale industrialized production, red phosphorus is nanocrystallized and embedded in the three-dimensional carbon matrix sheet layer, and meanwhile, C-F chemical bonds are introduced, so that the sodium storage electrical property of the red phosphorus serving as a negative electrode can be effectively improved.
In a third aspect, the present application provides a sodium ion battery, which adopts the following technical scheme:
The sodium ion battery comprises the fluorine-doped carbon nano sheet-loaded red phosphorus anode material.
By adopting the technical scheme, the fluorine-doped nano-sheet-loaded red phosphorus anode material prepared by the application can be used as the anode material of a sodium ion battery, so that the problems of rapid capacity decay and slow redox reaction kinetics caused by large volume change and inherent poor conductivity of red phosphorus in the sodium treatment and sodium removal processes can be effectively avoided, and the electrochemical performance of the red phosphorus anode can be effectively improved.
In a fourth aspect, the present application provides a method for preparing a sodium ion battery, which adopts the following technical scheme:
The preparation method of the sodium ion battery comprises the following steps:
Uniformly mixing the fluorine-doped carbon nanomaterial with a conductive agent and a binder, adding the mixture into N-methylpyrrolidone, uniformly mixing the mixture to obtain slurry, and coating the slurry on an aluminum foil to obtain an electrode slice; the thickness of the electrode plate can be adjusted according to the viscosity degree of the slurry, and the range is 75-150 mu m; the battery takes glass fiber as a diaphragm, naPF 6 as sodium salt and EC/DEC (volume ratio is 1:1) solution as electrolyte;
And drying the electrode plate in a vacuum environment, cutting to obtain a wafer, and assembling the wafer and metal sodium to form the sodium ion battery.
By adopting the technical scheme, the fluorine-doped carbon nano sheet loaded red phosphorus anode material prepared by the application is applied to sodium ion batteries, and the sodium ion batteries with high capacity and ultra-long cycle performance can be obtained.
In summary, the present application includes at least one of the following beneficial technical effects:
1. According to the application, fluorine atoms are introduced into the carbon matrix through simple mechanical mixing heat treatment, so that uniform doping of the fluorine atoms can be realized rapidly and stably; meanwhile, red phosphorus is nanocrystallized and embedded in a three-dimensional carbon matrix sheet layer, so that the sodium storage electrochemical performance of the red phosphorus anode material can be effectively improved;
2. According to the application, the mass ratio of the carbon nano-sheet to the polytetrafluoroethylene is optimized, so that the dispersion uniformity of fluorine atoms in a carbon material can be further improved, and the subsequent battery performance is improved;
3. the preparation method of fluorine-doped carbon nano-sheet loaded red phosphorus sodium ions adopts a simple heat treatment synthesis technology, and has the advantage of large-scale industrial production.
Drawings
FIG. 1 is an SEM image of polyurea from example 1;
FIG. 2 is an SEM image of the carbon material of example 1;
FIG. 3 is an SEM image of carbon nanoplatelets of example 1;
FIG. 4 is a TEM image of the carbon nanoplatelets of example 1;
FIG. 5 is a charge-discharge graph of the sodium ion battery of example 1;
Fig. 6 is a graph of charge-discharge cycle performance of the sodium ion battery of example 1.
Detailed Description
The application is further illustrated by the following examples and figures 1-6.
Example 1
The embodiment discloses a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 10g of urea and 1g of terephthalyl diisocyanate into tetrahydrofuran solvent, and stirring at 15 ℃ to uniformly react for 1.5h to obtain suspension; centrifuging the suspension at a rotating speed of 3500r/min, then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 45 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 500 ℃ at 10 ℃/min under an argon environment, carbonizing for 30min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(3) Mechanically grinding and mixing 10g of carbon material and 1g of polytetrafluoroethylene for 3.5 hours, transferring the mixture into an argon atmosphere tube furnace after the mixing is finished, heating to 350 ℃ at 10 ℃/min under an argon environment, and sintering for 30min to obtain carbon nano-sheets doped with fluorine;
(4) Packaging the 5g carbon nano-sheets and 5g red phosphorus together in a vacuum quartz tube, heating to 900 ℃ at 8 ℃/min, preserving heat 480 min, then cooling to 260 ℃ at 1 ℃/min, preserving heat 1440: 1440 min, and then naturally cooling to obtain the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The obtained fluorine-doped carbon nano-sheet loaded red phosphorus anode material is tested and analyzed, as shown in fig. 1, which is a polyurea SEM image obtained after polymerization, fig. 2, which is a SEM image of the carbon material, fig. 3, which is a SEM image of the carbon nano-sheet, and fig. 4, which is a TEM image of the carbon nano-sheet, and it can be seen that the whole structure of the material remains intact after doping fluorine atoms.
The embodiment also discloses a fluorine-doped carbon nano-sheet loaded red phosphorus anode material prepared by adopting the preparation method.
The embodiment also discloses a sodium ion battery which comprises the fluorine-doped carbon nano sheet-loaded red phosphorus anode material.
The embodiment also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained fluorine-doped carbon nano sheet-loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil through a knife coating method to obtain an electrode sheet with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 12 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with an electrolyte of 1mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Example 2
The embodiment discloses a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 10g of urea and 1g of terephthalyl diisocyanate into tetrahydrofuran solvent, and stirring at 15 ℃ to uniformly react for 1.5h to obtain suspension; centrifuging the suspension at a rotating speed of 3500r/min, then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 45 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 500 ℃ at 10 ℃/min under an argon environment, carbonizing for 30min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(3) Mechanically grinding and mixing 10g of carbon material and 2g of polytetrafluoroethylene for 3.5 hours, transferring the mixture into an argon atmosphere tube furnace after the mixing is finished, heating to 350 ℃ at 10 ℃/min under an argon environment, and sintering for 30min to obtain carbon nano-sheets doped with fluorine;
(4) Packaging the 5g carbon nano-sheets and 5g red phosphorus together in a vacuum quartz tube, heating to 900 ℃ at 8 ℃/min, preserving heat 480 min, then cooling to 260 ℃ at 1 ℃/min, preserving heat 1440: 1440 min, and then naturally cooling to obtain the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The embodiment also discloses a fluorine-doped carbon nano-sheet loaded red phosphorus anode material prepared by adopting the preparation method.
The embodiment also discloses a sodium ion battery which comprises the fluorine-doped carbon nano sheet-loaded red phosphorus anode material.
The embodiment also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained fluorine-doped carbon nano sheet-loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil through a knife coating method to obtain an electrode sheet with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 12 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with an electrolyte of 1mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Example 3
The embodiment discloses a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 10g of urea and 1g of terephthalyl diisocyanate into tetrahydrofuran solvent, and stirring at 15 ℃ to uniformly react for 1.5h to obtain suspension; centrifuging the suspension at a rotating speed of 3500r/min, then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 45 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 500 ℃ at 10 ℃/min under an argon environment, carbonizing for 30min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(3) Mechanically grinding and mixing 15g of carbon material and 1g of polytetrafluoroethylene for 3.5 hours, transferring the mixture into an argon atmosphere tube furnace after the mixing is finished, heating to 350 ℃ at 10 ℃/min under an argon environment, and sintering for 30min to obtain carbon nano-sheets doped with fluorine;
(4) Packaging the 5g carbon nano-sheets and 5g red phosphorus together in a vacuum quartz tube, heating to 900 ℃ at 8 ℃/min, preserving heat 480 min, then cooling to 260 ℃ at 1 ℃/min, preserving heat 1440: 1440 min, and then naturally cooling to obtain the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The embodiment also discloses a fluorine-doped carbon nano-sheet loaded red phosphorus anode material prepared by adopting the preparation method.
The embodiment also discloses a sodium ion battery which comprises the fluorine-doped carbon nano sheet-loaded red phosphorus anode material.
The embodiment also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained fluorine-doped carbon nano sheet-loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil through a knife coating method to obtain an electrode sheet with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 12 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with an electrolyte of 1mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Example 4
The embodiment discloses a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 8g of urea and 1g of terephthalyl isocyanate into tetrahydrofuran solvent, stirring at 10 ℃ to uniformly react for 2 hours to obtain suspension; centrifuging the suspension at a rotating speed of 3000r/min, and then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 40 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 400 ℃ at 10 ℃/min under an argon environment, carbonizing for 35min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(3) Mechanically grinding and mixing 10g of carbon material and 1g of polytetrafluoroethylene for 2 hours, transferring the mixture into an argon atmosphere tube furnace after the mixing is finished, heating to 300 ℃ at 10 ℃/min under an argon environment, and sintering for 30min to obtain carbon nano-sheets doped with fluorine;
(4) Packaging the 2.5g carbon nano-sheets and 5g red phosphorus together in a vacuum quartz tube, heating to 800 ℃ at 8 ℃/min, preserving heat 600 min, then cooling to 300 ℃ at 1 ℃/min, preserving heat 600 min, and then naturally cooling to obtain the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The embodiment also discloses a fluorine-doped carbon nano-sheet loaded red phosphorus anode material prepared by adopting the preparation method.
The embodiment also discloses a sodium ion battery which comprises the fluorine-doped carbon nano sheet-loaded red phosphorus anode material.
The embodiment also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained fluorine-doped carbon nano sheet-loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil through a knife coating method to obtain an electrode sheet with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 10 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with an electrolyte of 1mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Example 5
The embodiment discloses a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 12g of urea and 1g of terephthalyl isocyanate into tetrahydrofuran solvent, stirring at 20 ℃ to uniformly react for 1h to obtain suspension; centrifuging the suspension at a rotating speed of 4000r/min, and then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 50 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 450 ℃ at 10 ℃/min under an argon environment, carbonizing for 25min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(3) Mechanically grinding and mixing 10g of carbon material and 1g of polytetrafluoroethylene for 5 hours, transferring the mixture into an argon atmosphere tube furnace after the mixing is finished, heating to 400 ℃ at 10 ℃/min under an argon environment, and sintering for 30min to obtain carbon nano-sheets doped with fluorine;
(4) And packaging the 7.5g carbon nano-sheets and 5g red phosphorus in a vacuum quartz tube, heating to 900 ℃ at 8 ℃/min, preserving heat 300 min, cooling to 250 ℃ at 1 ℃/min, preserving heat 900: 900 min, and naturally cooling to obtain the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The embodiment also discloses a fluorine-doped carbon nano-sheet loaded red phosphorus anode material prepared by adopting the preparation method.
The embodiment also discloses a sodium ion battery which comprises the fluorine-doped carbon nano sheet-loaded red phosphorus anode material.
The embodiment also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained fluorine-doped carbon nano sheet-loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil through a knife coating method to obtain an electrode sheet with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 15 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with an electrolyte of 1mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Comparative example 1
The comparative example discloses a method for preparing a sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil by a knife coating method to obtain an electrode slice with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 12 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with the electrolyte of 0.5mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with the volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Comparative example 2
The comparative example discloses a preparation method of a carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 10g of urea and 1g of terephthalyl diisocyanate into tetrahydrofuran solvent, and stirring at 15 ℃ to uniformly react for 1.5h to obtain suspension; centrifuging the suspension at a rotating speed of 3500r/min, then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 45 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 500 ℃ at 10 ℃/min under an argon environment, carbonizing for 30min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(4) Packaging the 5g carbon material and 5g red phosphorus in a vacuum quartz tube, heating to 900 ℃ at 8 ℃/min, preserving heat 480 and min, then cooling to 260 ℃ at 1 ℃/min, preserving heat 1440 and min, and then naturally cooling to obtain the carbon nano-sheet loaded red phosphorus anode material.
The comparative example also discloses a carbon nano-sheet loaded red phosphorus anode material prepared by the preparation method.
The comparative example also discloses a sodium ion battery comprising the carbon nano-sheet-supported red phosphorus anode material.
The comparative example also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained carbon nano sheet loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil to obtain an electrode sheet with the thickness of 100 mu m by a knife coating method;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 12 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with an electrolyte of 1mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Comparative example 3
The comparative example discloses a preparation method of a fluorine-doped carbon nano-sheet loaded red phosphorus anode material, which comprises the following steps:
(1) Adding 10g of urea and 1g of terephthalyl diisocyanate into tetrahydrofuran solvent, and stirring at 15 ℃ to uniformly react for 1.5h to obtain suspension; centrifuging the suspension at a rotating speed of 3500r/min, then placing the centrifuged suspension in a vacuum oven, and vacuum drying at 45 ℃ for 3 hours to obtain micron-sized polyurea molecules;
(2) Placing the micron-sized polyurea molecules into a tube furnace, heating to 500 ℃ at 10 ℃/min under an argon environment, carbonizing for 30min, and naturally cooling to obtain a lamellar carbon material with a nano structure;
(3) Mechanically grinding and mixing 10g of carbon material and 1g of polytetrafluoroethylene for 3.5 hours, transferring the mixture into an argon atmosphere tube furnace after the mixing is finished, heating to 350 ℃ at 10 ℃/min under an argon environment, and sintering for 30min to obtain carbon nano-sheets doped with fluorine;
(4) Packaging the 5g carbon nano-sheets and 5g red phosphorus together in a vacuum quartz tube, heating to 900 ℃ at 8 ℃/min, preserving heat 480 min, then cooling to 260 ℃ at 1 ℃/min, preserving heat 1440: 1440 min, and then naturally cooling to obtain the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The comparative example also discloses a fluorine-doped carbon nano-sheet loaded red phosphorus anode material prepared by the preparation method.
The comparative example also discloses a sodium ion battery comprising the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material.
The comparative example also discloses a preparation method of the sodium ion battery, which comprises the following steps:
(1) Uniformly grinding 8g of the obtained fluorine-doped carbon nano sheet-loaded red phosphorus anode material, 1g of acetylene black (conductive agent) and 1g of polyvinylidene fluoride (binder), adding N-methyl pyrrolidone, mixing and grinding to obtain uniform slurry, and preparing the slurry on an aluminum foil through a knife coating method to obtain an electrode sheet with the thickness of 100 mu m;
(2) Drying the electrode slice in a vacuum environment at 60 ℃ for 12 hours, and cutting the electrode slice into a wafer with the diameter of 10 mm; sodium sheets are used as a negative electrode, naPF 6 with the electrolyte of 0.5mol/ml is dissolved in a mixed solution formed by ethylene carbonate and diethyl carbonate with the volume ratio of 1:1, and glass fibers are used as a diaphragm to assemble the sodium ion battery.
Electrochemical performance test: the sodium ion batteries formed in examples 1 to 5 and comparative examples 1 to 3 were tested for initial specific capacity at a current density of 500mA/g and for battery capacity after 80 cycles, and the results are shown in table 1 and fig. 5.
TABLE 1 Performance test data sheets for examples 1-5 and comparative examples 1-3
Referring to Table 1, FIGS. 5 and 6, in combination with examples 1-5 and comparative examples 1-2, it can be seen that the sodium ion battery of example 1 has an initial specific capacity of 980mAh/g at a current density of 500mA/g, the capacity remaining at 900 mAh/g after 80 cycles; comparative example 1 sodium ion battery at a current density of 500mA/g, the battery had an initial specific capacity of 110mAh/g, and the capacity was maintained at 35mAh/g after 80 cycles; comparative example 2 sodium ion battery at a current density of 500mA/g, the battery had an initial specific capacity of 305mAh/g, and the capacity was maintained at 150 mAh/g after 80 cycles; the electrochemical performances of the sodium ion batteries prepared in the embodiment of the application are excellent in those of the sodium ion batteries prepared in the comparative example 1 and the comparative example 2. The three-dimensional carbon material can effectively buffer the volume change of the red phosphorus in the sodium ion deintercalation process, and can improve the electron conductivity of the red phosphorus/carbon electrode. In addition, the introduced fluorine atoms can form C-F strong chemical bonds, which is beneficial to further strengthening the interaction between red phosphorus and the carbon material, so that the red phosphorus can be stably attached in the nano lamellar to prepare the carbon material with the nano lamellar structure. By the preparation method, the fluorine-doped carbon nano sheet loaded red phosphorus anode material with high capacity and high stability, which is effectively applied to sodium ion batteries, can be obtained.
Referring to Table 1, in combination with examples 1-3, it can be seen that the sodium ion battery of example 2 has an initial specific capacity of 900 mAh/g at a current density of 500mA/g, with the capacity maintained at 500mAh/g after 80 cycles. After doping fluorine elements, the carbon material has too high content of introduced fluorine atoms and uneven dispersion, which affect the performance of subsequent batteries, and the doping effect is difficult to be exerted, and the corresponding battery capacity is lower than that of the embodiment 1; example 3 sodium ion battery at a current density of 500mA/g, the battery had an initial specific capacity of 800 mAh/g, and the capacity was maintained at 500mAh/g after 80 cycles. After the material prepared by the embodiment is doped with fluorine, the content of fluorine atoms introduced into the carbon material is too low, so that the doped carbon material cannot exert the battery performance, the doping effect is not ideal, and the corresponding battery capacity is lower than that of embodiment 1. From the above, it can be seen that the electrochemical performance of the obtained sodium ion battery is optimal when the mass ratio of the carbon material to polytetrafluoroethylene is 10:1.
Referring to Table 1, in combination with example 1 and comparative example 3, it can be seen that the sodium ion battery prepared in comparative example 3 has an initial specific capacity of 500 mAh/g at a current density of 500mA/g, and the capacity is maintained at 300mAh/g after 80 cycles. With 0.5mol/ml of NaPF 6 electrolyte, it is difficult to form a strong and stable SEI layer during battery cycling due to the electrolyte contrast of 1mol/mlNaPF 6 , resulting in significant capacity fade of the battery during cycling. The corresponding battery capacity was lower than in example 1.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. The preparation method of the fluorine-doped carbon nano sheet-loaded red phosphorus anode material comprises the following steps:
Reacting urea and terephthalyl isocyanate in a solvent to obtain polymer molecules;
Carbonizing the polymer molecules in an inert gas environment to obtain a carbon material with a nano-layer structure;
Mechanically grinding the carbon material and polytetrafluoroethylene to obtain a mixture, heating the mixture to 300-400 ℃ at 10 ℃/min in an inert gas environment, and sintering for 30min to obtain a carbon nano sheet doped with fluorine;
penetrating red phosphorus into the carbon nano-sheet in an evaporation-condensation mode to obtain a fluorine-doped carbon nano-sheet-loaded red phosphorus anode material;
the mass ratio of the carbon nano-sheet to the polytetrafluoroethylene is 5-15:1;
The fluorine-doped carbon nano sheet loaded red phosphorus anode material is applied to sodium ion batteries.
2. The method for preparing the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material according to claim 1, which is characterized in that: the mass ratio of the urea to the terephthalyl isocyanate is 8-12:1.
3. The method for preparing the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material according to claim 1, which is characterized in that: the carbonization treatment is carried out at 400-500 ℃ for 25-35min.
4. The method for preparing the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material according to claim 1, which is characterized in that: the mass ratio of the carbon nano-sheet to the red phosphorus is 0.5-1.5:1.
5. The method for preparing the fluorine-doped carbon nano-sheet-loaded red phosphorus anode material according to claim 1, which is characterized in that: the evaporation-condensation mode is specifically as follows: and packaging the carbon nano-sheets and red phosphorus in a vacuum quartz tube, heating to 800-900 ℃, preserving heat for 5-10h, then cooling to 250-300 ℃, preserving heat for 10-15h, and finally cooling to room temperature to obtain the fluorine-doped nano-sheet-loaded red phosphorus anode material.
6. A fluorine-doped carbon nano-sheet loaded red phosphorus anode material is characterized in that: the fluorine-doped carbon nano-sheet supported red phosphorus anode material is prepared by a preparation method of the fluorine-doped carbon nano-sheet supported red phosphorus anode material according to any one of claims 1-5.
7. Sodium ion battery, its characterized in that: a fluorine-doped carbon nanoplatelet-loaded red phosphorus anode material comprising the fluorine-doped carbon nanoplatelet of claim 6.
8. The method for preparing the sodium ion battery as claimed in claim 7, wherein: the method comprises the following steps:
Uniformly mixing the fluorine-doped carbon nano sheet-loaded red phosphorus anode material with a conductive agent and a binder, adding the mixture into N-methyl pyrrolidone, uniformly mixing the mixture to obtain slurry, and coating the slurry on an aluminum foil to obtain an electrode sheet;
And drying the electrode plate in a vacuum environment, cutting to obtain a wafer, and assembling the wafer and metal sodium to form the sodium ion battery.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634210A (en) * | 2017-09-22 | 2018-01-26 | 常州大学 | A kind of high performance lithium/sode cell negative material and preparation method thereof |
| CN111082028A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | High-capacity negative electrode material, preparation method and lithium ion battery |
| CN115621445A (en) * | 2022-10-25 | 2023-01-17 | 湖北三峡实验室 | Novel phosphorus-carbon anode material based on red phosphorus and preparation method |
| CN116759582A (en) * | 2023-08-22 | 2023-09-15 | 大秦数字能源技术股份有限公司 | Self-supporting cotton biomass carbon-loaded red phosphorus sodium ion battery anode material and preparation method thereof |
| CN117133908A (en) * | 2023-10-26 | 2023-11-28 | 大秦数字能源技术股份有限公司 | Red phosphorus carbon battery anode material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634210A (en) * | 2017-09-22 | 2018-01-26 | 常州大学 | A kind of high performance lithium/sode cell negative material and preparation method thereof |
| CN111082028A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | High-capacity negative electrode material, preparation method and lithium ion battery |
| CN115621445A (en) * | 2022-10-25 | 2023-01-17 | 湖北三峡实验室 | Novel phosphorus-carbon anode material based on red phosphorus and preparation method |
| CN116759582A (en) * | 2023-08-22 | 2023-09-15 | 大秦数字能源技术股份有限公司 | Self-supporting cotton biomass carbon-loaded red phosphorus sodium ion battery anode material and preparation method thereof |
| CN117133908A (en) * | 2023-10-26 | 2023-11-28 | 大秦数字能源技术股份有限公司 | Red phosphorus carbon battery anode material and preparation method and application thereof |
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