CN112980436B - Carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material and preparation method thereof - Google Patents
Carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 239000002135 nanosheet Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 40
- 239000010405 anode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004080 punching Methods 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000011056 performance test Methods 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910013872 LiPF Inorganic materials 0.000 claims description 6
- 101150058243 Lipf gene Proteins 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention discloses a carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material and a preparation method thereof. In the carbon quantum dot derived carbon nano sheet composite nano silicon dioxide anode material, the thickness of the carbon quantum dot derived carbon nano sheet is less than or equal to 2nm, the carbon quantum dot derived carbon nano sheet contains sulfur with the mass ratio of 0.8% -1.3%, the shape of silicon dioxide is spherical, the crystal structure is an amorphous structure, and the average particle size is about 150nm. Mixing carbon quantum dots and sulfur doping agents, preparing sulfur doped carbon quantum dot derivative carbon nano sheets by calcining and heating, ultrasonically dispersing the carbon quantum dot derivative carbon nano sheets in absolute ethyl alcohol, adding ammonia water, ethyl orthosilicate and deionized water, mixing, and preparing the sulfur doped carbon quantum dot derivative carbon nano sheet composite silicon dioxide anode material by a sol-gel method and freeze drying. The preparation process is simple and has low energy consumption; the carbon quantum dot derived carbon nano sheet is used as an inner core supporting framework, the material thickness is uniform, the structure is stable, and the electric conduction is enhanced, so that the circulation stability is enhanced.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) are of great interest due to high energy density and long cycle life. Commercial graphite with a theoretical capacity of 372mAh/g cannot meet the increasing power demand, so that a silicon-based anode material with a higher theoretical specific capacity (4200 mAh/g) is considered as the optimal anode material for next-generation lithium ion batteries, however, the great volume expansion (> 300%) during lithiation thereof causes the defects of structural fracture, phase change during electrochemical reaction and the like, which causes rapid capacity decay and significantly limits the commercial application thereof.
In recent years, amorphous silica with theoretical capacity as high as 1965mAh/g has attracted attention, and lithiation reaction thereof generates Li 2 O may act as a buffer component for the volume change. However, its application is limited due to low initial coulombic efficiency and low conductivity. In order to solve the problems of the pure silicon dioxide cathode material, the invention creatively uses carbon quantum dot derived carbon nano-sheet composite silicon dioxide to prepare the lithium battery cathode material, the first discharge specific capacity of the lithium battery cathode material can reach 1124.8mAh/g under the current density of 200mA/g, the first charge specific capacity can reach 725.7mAh/g, and the reversible specific capacity of 568.7mAh/g can be maintained after 60 cycles; at a current density of 4A/g, a reversible specific capacity of 568.7mAh/g can be maintained after 200 cycles.
Disclosure of Invention
The invention aims to provide a carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material and a preparation method thereof.
In the carbon quantum dot derived carbon nano sheet composite nano silicon dioxide anode material, the thickness of the carbon quantum dot derived carbon nano sheet is less than or equal to 2nm, the carbon quantum dot derived carbon nano sheet contains sulfur with the mass ratio of 0.8% -1.3%, the shape of silicon dioxide is spherical, the crystal structure is an amorphous structure, and the average grain diameter is about 150nm.
The preparation method of the carbon quantum dot derived carbon nano sheet composite nano silicon dioxide anode material comprises the following specific steps:
(1) And (3) putting 40mL of 40% concentration acetaldehyde solution into a 100mL beaker, slowly adding 8g of NaOH solid under intense magnetic stirring to react for 1 hour, standing for 72 hours at room temperature, taking out the black oily solid obtained by the reaction, putting the black oily solid into the beaker, adding 50mL of 1mol/L hydrochloric acid solution, stirring for 1 hour, repeatedly centrifuging with deionized water to wash to neutrality, and putting the solid powder into a baking oven to keep the temperature at 70 ℃ for 12 hours to obtain the carbon quantum dot.
(2) Weighing 1g of the carbon quantum dots obtained in the step (1) and 6g of sulfur doping agent, placing the carbon quantum dots and 6g of sulfur doping agent into a mortar, placing the mortar into a 5mL aluminum oxide crucible, placing the mortar into a tube furnace, heating to 800 ℃ at 3 ℃/min under nitrogen atmosphere, preserving heat for 1 hour, cooling to room temperature, washing and filtering the mortar with deionized water for 3-5 times, placing the mortar into an oven, heating to 70 ℃, and preserving heat for 12 hours to obtain the carbon quantum dot derivative carbon nano-sheet.
(3) Dispersing 50-200 mg of the carbon quantum dot derivative carbon nano-sheets obtained in the step (2) in 8mL of analytically pure absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, adding ammonia water with the mass percent concentration of 28% to enable the pH value of a system to be 8-10, adding 0.5mL of analytically pure ethyl silicate, standing for 12 hours, adding 1mL of deionized water to form gel, and putting into a freeze dryer for freeze drying to obtain the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material.
(4) Mixing 0.1g of carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material obtained in the step (3), ketjen black and polyvinylidene fluoride according to the mass ratio of 5:3:2, adding 1-1.5 mL of analytically pure N-methyl-2-pyrrolidone solvent, grinding into slurry, coating on a copper foil current collector, coating with the thickness of 10 mu m, placing into a vacuum drying oven, heating to 110 ℃, preserving heat for 10 hours, cooling to room temperature, and punching into a round pole piece with the diameter of 16mm by using a sheet punching machine.
(5) The lithium metal sheet is used as a counter electrode, the diaphragm is made of polypropylene with a microporous structure, and the electrolyte is dissolved with LiPF with the concentration of 1mol/L 6 The EC+DMC+DEC solution, the volume ratio of EC, DMC and DEC is 1:1:1, the CR2025 type battery is assembled in a glove box protected by argon, after sealing, the battery is stood for 12 hours, the electrochemical performance test is carried out, the test voltage is 3-0.01V, and the current density is 200 mA/g-4A/g.
The sulfur doping agent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sulfur.
The invention has the following advantages:
(1) In the prepared carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material, the carbon quantum dot derived carbon nano sheet is used as a core supporting framework, so that the structure is stable, the electric conduction is enhanced, and the circulation stability is enhanced.
(2) On the cost advantage of preparation, the technology realizes the preparation of the quantum dot derived carbon nano sheet composite silicon dioxide anode material by a simple sol-gel method and freeze drying treatment, has the characteristics of less operation steps and low energy consumption, and fully reflects the cost advantage.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the carbon quantum dot-derived carbon nanoplatelets prepared in example 1 of the present invention.
Fig. 2 is an X-ray diffraction (XRD) pattern of the carbon quantum dot-derived carbon nanoplatelets prepared in example 1 of the present invention.
Fig. 3 is a charge-discharge graph of the first two times of the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material prepared in example 1 of the present invention.
Fig. 4 is a cycle performance chart of the carbon quantum dot derived carbon nano-sheet composite silicon dioxide anode material prepared in example 1 of the present invention.
Fig. 5 is a charge-discharge graph of the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material prepared in example 2 of the present invention.
Fig. 6 is a cycle performance chart of the carbon quantum dot derived carbon nano-sheet composite silicon dioxide anode material prepared in example 2 of the present invention.
FIG. 7 is a charge/discharge curve of a carbon quantum dot-derived carbon nano-sheet composite silicon dioxide negative electrode material prepared in example 3 of the present invention,
Fig. 8 is a cycle performance chart of the carbon quantum dot derived carbon nano-sheet composite silicon dioxide anode material prepared in example 3 of the present invention.
Fig. 9 is a Scanning Electron Microscope (SEM) image of the carbon quantum dot-derived carbon nano-sheet composite silicon dioxide anode material prepared in example 4 of the present invention.
FIG. 10 is a charge/discharge curve of a carbon quantum dot-derived carbon nano-sheet composite silica anode material according to example 4 of the present invention
Fig. 11 is a cycle performance chart of the carbon quantum dot derived carbon nano-sheet composite silicon dioxide anode material prepared in example 4 of the present invention.
FIG. 12 shows that the carbon quantum dot-derived carbon nano-sheet composite silicon dioxide anode material prepared in example 4 of the present invention has a current density of 2A g -1 The following cycle performance graph.
FIG. 13 shows that the carbon quantum dot-derived carbon nano-sheet composite silicon dioxide anode material prepared in example 4 of the present invention has a current density of 4A g -1 The following cycle performance graph.
Detailed Description
Example 1:
(1) And (3) putting 40mL of 40% concentration acetaldehyde solution into a 100mL beaker, slowly adding 8g of NaOH solid under intense magnetic stirring to react for 1 hour, standing for 72 hours at room temperature, taking out the black oily solid obtained by the reaction, putting the black oily solid into the beaker, adding 50mL of 1mol/L hydrochloric acid solution, stirring for 1 hour, repeatedly centrifuging with deionized water to wash to neutrality, and putting the solid powder into a baking oven to keep the temperature at 70 ℃ for 12 hours to obtain the carbon quantum dot.
(2) Weighing 1g of the carbon quantum dots obtained in the step (1) and 6g of sodium dodecyl sulfate, placing the carbon quantum dots and 6g of sodium dodecyl sulfate in a mortar, placing the mortar in a 5mL aluminum oxide crucible, placing the mortar in a tube furnace, heating to 800 ℃ at 3 ℃/min under nitrogen atmosphere, preserving heat for 1 hour, cooling to room temperature, washing and filtering the mortar with deionized water for 3 times, and placing the mortar in an oven to heat to 70 ℃ and preserving heat for 12 hours to obtain the carbon quantum dot derivative carbon nano-sheets. And (3) carrying out Scanning Electron Microscope (SEM) test analysis on the carbon quantum dot derived carbon nano-sheet, wherein the microscopic morphology of the carbon quantum dot derived carbon nano-sheet is a sheet structure with the thickness less than or equal to 2nm as shown in figure 1. X-ray diffraction (XRD) analysis (fig. 2) was performed on the carbon quantum dot-derived carbon nanoplatelets, indicating that the material is amorphous carbon.
(3) Dispersing 50mg of the carbon quantum dot derivative carbon nano-sheets obtained in the step (2) in 8mL of analytically pure absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, adding ammonia water with the mass percent concentration of 28% to enable the pH value of a system to be 8, adding 0.5mL of analytically pure ethyl silicate, standing for 12 hours, adding 1mL of deionized water to form gel, and putting into a freeze dryer for freeze drying to obtain the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material.
(4) Mixing 0.1g of the carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material obtained in the step (3), ketjen black and polyvinylidene fluoride according to the mass ratio of 5:3:2, adding 1mL of analytically pure N-methyl-2-pyrrolidone, grinding into slurry, coating on a copper foil current collector, coating with the thickness of 10 mu m, placing into a vacuum drying oven, heating to 110 ℃, preserving heat for 10 hours, cooling to room temperature, and punching into a round pole piece with the diameter of 16mm by using a sheet punching machine.
(5) The metal lithium sheet is used as a counter electrode, the diaphragm is made of polypropylene with a microporous structure, and the electrolyte is LiPF dissolved with the concentration of 1mol/L 6 The EC+DMC+DEC solution, the volume ratio of EC, DMC and DEC is 1:1:1, the CR2025 type battery is assembled in a glove box protected by argon, after sealing, the battery is stood for 12 hours, the electrochemical performance test is carried out, the test voltage is 3-0.01V, and the current density is 200mA/g. The electrochemical performance test shows that the first charge-discharge specific capacities of the composite material are 408.7 and 1467mAh/g (figure 3), the reversible capacity still remained after 100 cycles is 379.8mAh/g, and the coulomb efficiency is maintained above 90% (figure 4), thus the composite material has better electrochemical performance.
Example 2:
(1) And (3) putting 40mL of 40% concentration acetaldehyde solution into a 100mL beaker, slowly adding 8g of NaOH solid under intense magnetic stirring to react for 1 hour, standing for 72 hours at room temperature, taking out the black oily solid obtained by the reaction, putting the black oily solid into the beaker, adding 50mL of 1mol/L hydrochloric acid solution, stirring for 1 hour, repeatedly centrifuging with deionized water to wash to neutrality, and putting the solid powder into a baking oven to keep the temperature at 70 ℃ for 12 hours to obtain the carbon quantum dot.
(2) Weighing 1g of the carbon quantum dots obtained in the step (1) and 6g of sodium dodecyl sulfate, placing the carbon quantum dots and 6g of sodium dodecyl sulfate in a mortar, placing the mortar in a 5mL aluminum oxide crucible, placing the mortar in a tube furnace, heating to 800 ℃ at 3 ℃/min under nitrogen atmosphere, preserving heat for 1 hour, cooling to room temperature, washing and filtering the mortar with deionized water for 4 times, and placing the mortar in an oven to heat to 70 ℃ and preserving heat for 12 hours to obtain the carbon quantum dot derivative carbon nano-sheets.
(3) Dispersing 100mg of the carbon quantum dot derivative carbon nano-sheets obtained in the step (2) in 8mL of analytically pure absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, adding ammonia water with the mass percent concentration of 28% to enable the pH value of a system to be 9, adding 0.5mL of analytically pure ethyl silicate, standing for 12 hours, adding 1mL of deionized water to form gel, and putting into a freeze dryer for freeze drying to obtain the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material.
(4) Mixing 0.1g of the carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material obtained in the step (3), ketjen black and polyvinylidene fluoride according to the mass ratio of 5:3:2, adding 1mL of analytically pure N-methyl-2-pyrrolidone, grinding into slurry, coating on a copper foil current collector, coating with the thickness of 10 mu m, placing into a vacuum drying oven, heating to 110 ℃, preserving heat for 10 hours, cooling to room temperature, and punching into a round pole piece with the diameter of 16mm by using a sheet punching machine.
(5) The metal lithium sheet is used as a counter electrode, the diaphragm is made of polypropylene with a microporous structure, and the electrolyte is LiPF dissolved with the concentration of 1mol/L 6 The EC+DMC+DEC solution, the volume ratio of EC, DMC and DEC is 1:1:1, the CR2025 type battery is assembled in a glove box protected by argon, after sealing, the battery is stood for 12 hours, the electrochemical performance test is carried out, the test voltage is 3-0.01V, and the current density is 200mA/g. The electrochemical performance test shows that the first charge-discharge specific capacities of the composite material are 673.4 and 1990.7mAh/g respectively (figure 5), the reversible capacity which is still reserved after 100 cycles is 510.2mAh/g, and the coulomb efficiency is maintained above 90 percent (figure 6), so that the composite material has better electrochemical performance.
Example 3:
(1) And (3) putting 40mL of 40% concentration acetaldehyde solution into a 100mL beaker, slowly adding 8g of NaOH solid under intense magnetic stirring to react for 1 hour, standing for 72 hours at room temperature, taking out the black oily solid obtained by the reaction, putting the black oily solid into the beaker, adding 50mL of 1mol/L hydrochloric acid solution, stirring for 1 hour, repeatedly centrifuging with deionized water to wash to neutrality, and putting the solid powder into a baking oven to keep the temperature at 70 ℃ for 12 hours to obtain the carbon quantum dot.
(2) Weighing 1g of the carbon quantum dots obtained in the step (1) and 6g of sodium dodecyl sulfate, placing the carbon quantum dots and 6g of sodium dodecyl sulfate in a mortar, placing the mortar in a 5mL aluminum oxide crucible, placing the mortar in a tube furnace, heating to 800 ℃ at 3 ℃/min under nitrogen atmosphere, preserving heat for 1 hour, cooling to room temperature, washing and filtering the mortar with deionized water for 5 times, and placing the mortar in an oven to heat to 70 ℃ and preserving heat for 12 hours to obtain the carbon quantum dot derivative carbon nano-sheets.
(3) Dispersing 150mg of the carbon quantum dot derivative carbon nano-sheets obtained in the step (2) in 8mL of analytically pure absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, adding ammonia water with the mass percent concentration of 28% to enable the pH value of a system to be 10, adding 0.5mL of analytically pure ethyl silicate, standing for 12 hours, adding 1mL of deionized water to form gel, and putting into a freeze dryer for freeze drying to obtain the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material.
(4) Mixing 0.1g of the carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material obtained in the step (3), ketjen black and polyvinylidene fluoride according to the mass ratio of 5:3:2, adding 1.2mL of analytically pure N-methyl-2-pyrrolidone, grinding into slurry, coating on a copper foil current collector, coating with the thickness of 10 mu m, placing into a vacuum drying oven, heating to 110 ℃, preserving heat for 10 hours, cooling to room temperature, and punching into a round pole piece with the diameter of 16mm by using a sheet punching machine.
(5) The metal lithium sheet is used as a counter electrode, the diaphragm is made of polypropylene with a microporous structure, and the electrolyte is LiPF dissolved with the concentration of 1mol/L 6 The EC+DMC+DEC solution, the volume ratio of EC, DMC and DEC is 1:1:1, the CR2025 type battery is assembled in a glove box protected by argon, after sealing, the battery is stood for 12 hours, the electrochemical performance test is carried out, the test voltage is 3-0.01V, and the current density is 200mA/g. The electrochemical performance test shows that the first charge-discharge specific capacities of the composite material are 725.7 and 1914.8mAh/g respectively (figure 7), the reversible capacity still remained after 80 cycles is 638.2mAh/g, and the coulomb efficiency is maintained above 90% (figure 8), thus the composite material has better electrochemical performance.
Example 4:
(1) And (3) putting 40mL of 40% concentration acetaldehyde solution into a 100mL beaker, slowly adding 8g of NaOH solid under intense magnetic stirring to react for 1 hour, standing for 72 hours at room temperature, taking out the black oily solid obtained by the reaction, putting the black oily solid into the beaker, adding 50mL of 1mol/L hydrochloric acid solution, stirring for 1 hour, repeatedly centrifuging with deionized water to wash to neutrality, and putting the solid powder into a baking oven to keep the temperature at 70 ℃ for 12 hours to obtain the carbon quantum dot.
(2) Weighing 1g of the carbon quantum dots obtained in the step (1) and 6g of sodium dodecyl sulfate, placing the carbon quantum dots and 6g of sodium dodecyl sulfate in a mortar, placing the mortar in a 5mL aluminum oxide crucible, placing the mortar in a tube furnace, heating to 800 ℃ at 3 ℃/min under nitrogen atmosphere, preserving heat for 1 hour, cooling to room temperature, washing and filtering the mortar with deionized water for 5 times, and placing the mortar in an oven to heat to 70 ℃ and preserving heat for 12 hours to obtain the carbon quantum dot derivative carbon nano-sheets.
(3) Dispersing 200mg of the carbon quantum dot derivative carbon nano-sheets obtained in the step (2) in 8mL of analytically pure absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, adding ammonia water with the mass percent concentration of 28% to enable the pH value of a system to be 10, adding 0.5mL of analytically pure ethyl silicate, standing for 12 hours, adding 1mL of deionized water to form gel, and putting into a freeze dryer for freeze drying to obtain the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material. The carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material is subjected to Scanning Electron Microscope (SEM) test analysis, and as shown in figure 9, the microstructure of the composite material is a sheet-shaped structure with uniform thickness.
(4) Mixing 0.1g of the carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material obtained in the step (3), ketjen black and polyvinylidene fluoride according to the mass ratio of 5:3:2, adding 1.5mL of analytically pure N-methyl-2-pyrrolidone, grinding into slurry, coating on a copper foil current collector, coating with the thickness of 10 mu m, placing into a vacuum drying oven, heating to 110 ℃, preserving heat for 10 hours, cooling to room temperature, and punching into a round pole piece with the diameter of 16mm by using a sheet punching machine.
(5) The metal lithium sheet is used as a counter electrode, the diaphragm is made of polypropylene with a microporous structure, and the electrolyte is LiPF dissolved with the concentration of 1mol/L 6 The EC+DMC+DEC solution, the volume ratio of EC, DMC and DEC is 1:1:1, the CR2025 type battery is assembled in a glove box protected by argon, after sealing, the battery is stood for 12 hours, the electrochemical performance test is carried out, the test voltage is 3-0.01V, and the current density is 200mA/g. The electrochemical performance test shows that the first charge-discharge specific capacities of the composite material are 1124.8 and 2812.9mAh/g respectively (figure 10), the reversible capacity still remained after 80 cycles is 775.9mAh/g (figure 11), and the effect is shownShowing better electrochemical performance. The cycle performance of the composite material under the conditions of high current density of 2A/g and 4A/g is shown in figures 12 and 13, wherein the reversible specific capacity of 501.9mAh/g is reserved after 120 cycles (figure 12), and the reversible specific capacity of 426.4mAh/g is reserved after 200 cycles (figure 13), and the coulomb efficiency is maintained to be more than 90%.
Claims (1)
1. A preparation method of a carbon quantum dot derived carbon nano sheet composite silicon dioxide negative electrode material is characterized in that in the carbon quantum dot derived carbon nano sheet composite silicon dioxide negative electrode material, the thickness of a carbon quantum dot derived carbon nano sheet is less than or equal to 2nm, sulfur with the mass ratio of 0.8% -1.3% is contained, the shape of silicon dioxide is spherical, the crystal structure is an amorphous structure, and the average particle size is 150 nm;
the preparation method of the carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material comprises the following specific steps:
(1) Putting 40mL volume percent of 40% acetaldehyde solution into a 100mL beaker, slowly adding 8g of NaOH solid to react for 1 hour under intense magnetic stirring, standing for 72 hours in a room temperature environment, taking out black oily solid obtained by the reaction, putting the black oily solid into a beaker, adding 50mL concentration of 1mol/L hydrochloric acid solution to stir for 1 hour, repeatedly centrifuging with deionized water to wash to neutrality, and putting solid powder into a baking oven to keep the temperature at 70 ℃ for 12 hours to obtain carbon quantum dots;
(2) Weighing the carbon quantum dots obtained in the step (1) of 1g and a 6g sulfur dopant, putting the carbon quantum dots and the 6g sulfur dopant into a mortar, putting the mortar into a 5mL aluminum oxide crucible, putting the crucible into a tube furnace, heating to 800 ℃ at 3 ℃/min under nitrogen atmosphere, preserving heat for 1 hour, cooling to room temperature, washing and filtering the crucible with deionized water for 3-5 times, putting the crucible into an oven, heating to 70 ℃ and preserving heat for 12 hours to obtain carbon quantum dot derivative carbon nano-sheets;
(3) Dispersing 50-200 mg of the carbon quantum dot derivative carbon nano-sheets obtained in the step (2) in 8mL analytically pure absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, adding 28 mass percent of ammonia water to enable the pH value of a system to be 8-10, adding 0.5mL analytically pure ethyl silicate, standing for 12 hours, adding 1mL deionized water to form gel, and putting into a freeze dryer for freeze drying to obtain the carbon quantum dot derivative carbon nano-sheet composite silicon dioxide anode material;
(4) Mixing 0.1g of carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material obtained in the step (3), ketjen black and polyvinylidene fluoride according to the mass ratio of 5:3:2, adding 1-1.5 mL of analytically pure N-methyl-2-pyrrolidone, grinding into slurry, coating on a copper foil current collector, coating with the thickness of 10 mm, placing into a vacuum drying oven, heating to 110 ℃, preserving heat for 10 hours, cooling to room temperature, and punching into a round pole piece with the diameter of 16mm by a sheet punching machine;
(5) The lithium metal sheet is used as a counter electrode, the diaphragm is made of polypropylene with a microporous structure, and the electrolyte is dissolved with LiPF with the concentration of 1mol/L 6 The EC+DMC+DEC solution, the volume ratio of EC, DMC and DEC is 1:1:1, a CR2025 type battery is assembled in a glove box protected by argon, after sealing, the battery is stood for 12 hours, an electrochemical performance test is carried out, the test voltage is 3-0.01V, and the current density is 200 mA/g-4A/g;
the sulfur doping agent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sulfur.
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| Improving the hydrophilic and antifouling properties of polyvinylidene fluoride membrane by incorporation of novel nanohybrid GO@SiO2 particles;Zhenya Zhu et al.;《Chemical Engineering Journal》;20161210;第314卷;第266-276页 * |
| Synthesis of uniform silica nanospheres wrapped in nitrogen-doped carbon nanosheets with stable lithium-ion storage properties;Jinxiang Mao et al.;《J Mater Sci.》;20190625;第54卷;第12767-12781页 * |
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