CN112174127A - Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application - Google Patents
Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application Download PDFInfo
- Publication number
- CN112174127A CN112174127A CN202011049838.1A CN202011049838A CN112174127A CN 112174127 A CN112174127 A CN 112174127A CN 202011049838 A CN202011049838 A CN 202011049838A CN 112174127 A CN112174127 A CN 112174127A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- composite material
- graphite composite
- preparation
- doped graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 42
- 239000010439 graphite Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 44
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 22
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 22
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000001338 self-assembly Methods 0.000 claims abstract description 14
- 239000004964 aerogel Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000000017 hydrogel Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000007710 freezing Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a nitrogen-sulfur double-doped graphene/graphite composite material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) ultrasonically dispersing graphene oxide and thiourea in deionized water; (2) adding ascorbic acid into the solution until the ascorbic acid is completely dissolved; (3) heating the solution in water bath until the solution is viscous; (4) adding natural graphite into the viscous solution until the natural graphite is uniformly dispersed in the solution; (5) transferring the uniform viscous solution into a water bath kettle, and heating for self-assembly; (6) after the self-assembly reaction is finished, cooling to obtain black columnar hydrogel; (7) and (3) freezing and drying to obtain black columnar aerogel, and calcining to obtain the nitrogen-sulfur double-doped graphene/graphite composite material. According to the invention, the graphene/graphite composite material is subjected to doping modification, so that respective advantages of graphene and graphite can be brought into play together, the electrochemical performance of the lithium ion battery cathode material is improved, the operation process is simplified, and the method is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a nitrogen-sulfur double-doped graphene/graphite composite material, a preparation method and application, and belongs to the field of lithium ion batteries.
Background
Compared with the common battery, the lithium ion battery has the advantages of high energy density, rapid charge and discharge efficiency, long cycle life, better high and low temperature performance, environmental protection and the like, is widely applied and popularized in daily life and industry, and is in a vigorous development period. At present, new energy automobiles are vigorously developed in China, lithium ion batteries are used as main sources for providing power for the new energy automobiles, so that the energy density and the rate capability of the lithium ion batteries are very necessary to be improved, an important method for improving the energy density of the lithium ions is to improve the capacity of an electrode material, and because the specific capacity of a negative electrode is much higher than that of a positive electrode, the improvement of the capacity of the batteries mainly depends on the improvement of the composition of the negative electrode material.
The current commercialized negative electrode material is mainly graphite, which is used as the negative electrode of the power battery and mainly has the following problems: (1) the theoretical capacity of the graphite cathode is lower and is only 372mAh/g, and the current excellent commercial graphite cathode can reach more than 360mAh/g and is closer to the theoretical value. (2) The multiplying power performance is poor, and the battery is not suitable for large-current charging and discharging. (3) In an electrolyte containing an organic solvent, graphite undergoes a solvent co-intercalation phenomenon, and the graphitized layer structure is gradually exfoliated. Therefore, the modification treatment is carried out on the graphite, and the high-performance composite electrode material is developed, so that the method has important scientific significance and industrial value.
Graphene has been widely studied in lithium ion batteries because of its high thermal conductivity (5300W/mK), high electron mobility (1.5 × 104cm2/Vs), high mechanical strength, and the like. The graphene is used as a negative electrode material, has higher theoretical specific capacity, and has reversible capacity of about 744 mA.h/g, which is twice of that of the graphite negative electrode material. In addition, the graphene has high stability due to high heat conductivity, and lithium ions can be rapidly inserted and removed in the charging and discharging process due to large interlayer spacing of the graphene, so that the rate capability can be improved. However, due to the huge specific surface area, the graphene is low in coulombic efficiency for the first time, is not suitable for being used as an electrode independently, and can play a role in complementing advantages after being compounded with graphite, so that the graphene composite modified graphite cathode has positive significance.
Since the discovery of graphene, researchers have conducted a great deal of research on its modified preparation. Modification of hetero-atom doping is one of the important research directions. Through hetero-atom doping, on one hand, the conductivity of the graphene can be increased, and meanwhile, a defect structure caused by doping provides more lithium storage sites, so that the graphene has better electrochemical performance compared with the graphene.
Regarding a patent (publication number: CN104882608A) of Shanghai silicate research institute, Guo, et al, regarding nitrogen and sulfur co-doped graphene, thiourea, a formaldehyde solution and graphene oxide are mixed, and then are self-assembled at 60-100 ℃ for 6-24 hours, and then are subjected to heat treatment at 600-1000 ℃ for 1-6 hours to obtain the nitrogen and sulfur co-doped graphene.
The patent (publication number: CN108745402A) of Wang Fang of Bin State academy of academic is that urea and sodium thiosulfate are used as a nitrogen source and a sulfur source respectively, and a hydrothermal and subsequent high-temperature drying (150 ℃ -200 ℃) method is adopted to prepare the nitrogen-sulfur co-doped graphene.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nitrogen-sulfur double-doped graphene/graphite composite material, a preparation method and application thereof.
In order to achieve the purpose, the preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material comprises the following steps:
(1) ultrasonically dispersing graphene oxide and thiourea in deionized water until the thiourea is completely dispersed in the aqueous solution;
(2) weighing ascorbic acid, adding the ascorbic acid into the solution obtained in the step (1), and carrying out ultrasonic treatment until the ascorbic acid is completely dissolved;
(3) heating the solution obtained in the step (2) under the condition of water bath until the solution is in a viscous state;
(4) weighing a certain amount of natural graphite, adding the natural graphite into the viscous solution obtained in the step (3), and stirring the natural graphite by strong magnetic force until the natural graphite is uniformly dispersed in the solution;
(5) transferring the uniform viscous solution obtained in the step (4) into a water bath kettle, and heating for self-assembly;
(6) after the self-assembly reaction is finished, cooling to room temperature to obtain black columnar hydrogel, soaking the black columnar hydrogel in a mixed solution of deionized water and ethanol, and then freeze-drying the black columnar hydrogel for 36-48 h;
(7) and (3) after freeze drying, obtaining black columnar aerogel, putting the black columnar aerogel into a quartz boat, and calcining for 3-5h in a tube furnace to finally obtain the nitrogen-sulfur double-doped graphene/graphite composite material.
Further, the mass ratio of the graphene oxide to the thiourea in the step (1) is 1 (1-3).
Further, the mass ratio of the ascorbic acid added in the step (2) to the graphene oxide in the step (1) is 2: 1.
Further, the temperature of water bath heating in the step (3) is 40-60 ℃, and the time is 1-2 hours.
Further, the mass ratio of the addition amount of the natural graphite in the step (4) to the graphene oxide in the step (1) is 7: 1; and (4) stirring for 1-2 hours at the rotating speed of 400-500 rpm for strong magnetic stirring in the step (4).
Further, the temperature of water bath heating in the step (5) is 80-90 ℃, and the heating time is 2-3 hours.
Further, the volume ratio of the deionized water to the alcohol in the step (6) is 5:1, and the freeze drying condition is-58 ℃ and the vacuum degree is less than or equal to 10 pa.
Further, the calcining in the step (7) is carried out under the protection of argon, the heating rate is 5 ℃/min, and the temperature is increased to 600-800 ℃.
In addition, the invention also provides a nitrogen-sulfur double-doped graphene/graphite composite material prepared by the preparation method.
Finally, the invention also provides application of the nitrogen-sulfur double-doped graphene/graphite composite material in a lithium ion battery cathode material.
Compared with the prior art, the graphene/graphite composite material is doped with the nitrogen and sulfur elements, the conductivity of the graphene is improved by doping the nitrogen elements, more active sites are added to the graphene by doping the sulfur elements, the graphene is in a fold shape, the structure is favorable for wetting the electrolyte, a channel is provided for lithium ion transmission, the rate capability of a graphite cathode is improved, and the graphene/graphite composite material is suitable for large-current charge and discharge.
Drawings
FIG. 1 is a scanning electron microscope image of the nitrogen-sulfur doped graphene/graphite composite material, wherein the ratio of rGO to thiourea is 1: 2;
fig. 2 and 3 are EDS diagrams of the nitrogen-sulfur doped graphene/graphite composite material of the present invention, and the ratio of rGO to thiourea is 1: 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention.
A preparation method of a nitrogen-sulfur double-doped graphene/graphite composite material comprises the following steps:
(1) ultrasonically dispersing graphene oxide and thiourea prepared by a modified Hummers method in deionized water according to a mass ratio of 1 (1-3) until the thiourea is completely dispersed in the water solution;
(2) weighing ascorbic acid with the mass 2 times that of the graphene oxide, adding the ascorbic acid into the solution obtained in the step (1), and performing ultrasonic treatment until the ascorbic acid is completely dissolved;
(3) heating the solution obtained in the step (2) in a water bath at 40-60 ℃ for 1-2 h until the solution is viscous;
(4) weighing natural graphite with the mass 7 times that of the graphene oxide, adding the natural graphite into the viscous solution obtained in the step (3), and stirring the natural graphite with strong magnetic force for 1-2 hours at 400-500 rpm until the natural graphite is uniformly dispersed in the solution;
(5) transferring the uniform viscous solution obtained in the step (4) into a water bath kettle, heating at 80-90 ℃ for 2-3 h, and carrying out self-assembly reaction;
(6) after the self-assembly reaction is finished, cooling to room temperature to obtain black columnar hydrogel, soaking in a mixed solution of deionized water and ethanol according to a volume ratio of 5:1, and freeze-drying at-58 ℃ under a vacuum degree of less than or equal to 10pa for 36-48 h;
(7) and (3) after freeze drying, obtaining black columnar aerogel, putting the black columnar aerogel into a quartz boat, heating the quartz boat to 600-800 ℃ in a tube furnace at a heating rate of 5 ℃/min, and calcining for 3-5h to finally obtain the nitrogen-sulfur double-doped graphene/graphite composite material.
Example 1
A preparation method of a nitrogen-sulfur double-doped graphene/graphite composite material comprises the following steps:
(1) ultrasonically dispersing 0.1g of graphene oxide prepared by adopting a modified Hummers method and 0.1g of thiourea in 20ml of deionized water until the thiourea is completely dispersed in the aqueous solution;
(2) weighing 0.2g of ascorbic acid, adding the ascorbic acid into the solution obtained in the step (1), and carrying out ultrasonic treatment for 1h until the ascorbic acid is completely dissolved;
(3) heating the solution obtained in the step (2) in a water bath at 50 ℃ for 1h until the solution is in a viscous state;
(4) weighing 0.7g of natural graphite, adding the natural graphite into the viscous solution obtained in the step (3), and magnetically stirring the solution at the rotating speed of 500rpm for 1 hour until the natural graphite is uniformly dispersed in the solution;
(5) transferring the uniform viscous solution obtained in the step (4) into a water bath kettle, and heating at 90 ℃ for self-assembly for 2 hours;
(6) after the self-assembly reaction is finished, cooling to room temperature to obtain black columnar hydrogel, soaking in a solution of deionized water and ethanol (V% ═ 5:1) for 12 hours, and then freeze-drying for 36 hours;
(7) and (3) after freeze drying, obtaining black columnar aerogel, putting the black columnar aerogel into a quartz boat, and calcining for 3 hours in an argon-filled tube furnace at the temperature rising rate of 5 ℃/min to 800 ℃ to finally obtain the nitrogen-sulfur double-doped graphene/graphite composite material.
Example 2
A preparation method of a nitrogen-sulfur double-doped graphene/natural graphite composite material comprises the following steps:
(1) ultrasonically dispersing 0.1g of graphene oxide prepared by a modified Hummers method and 0.2g of thiourea in 20ml of deionized water until the thiourea is completely dispersed in the aqueous solution;
(2) weighing 0.2g of ascorbic acid, adding the ascorbic acid into the solution obtained in the step (1), and carrying out ultrasonic treatment for 1h until the ascorbic acid is completely dissolved;
(3) heating the solution obtained in the step (2) in a water bath at 50 ℃ for 1h until the solution is in a viscous state;
(4) weighing 0.7g of natural graphite, adding the natural graphite into the viscous solution obtained in the step (3), and magnetically stirring for 2 hours at the rotating speed of 400rpm until the natural graphite is uniformly dispersed in the solution;
(5) transferring the uniform viscous solution obtained in the step (4) into a water bath kettle, and heating at 85 ℃ for self-assembly for 2.5 hours;
(6) after the self-assembly reaction is finished, cooling to room temperature to obtain black columnar hydrogel, soaking in a solution of deionized water and ethanol (V% ═ 5:1) for 12 hours, and then freeze-drying at-58 ℃ and under the vacuum degree of less than or equal to 10pa for 48 hours;
(7) and (3) after freeze drying, obtaining black columnar aerogel, putting the black columnar aerogel into a quartz boat, and calcining for 4 hours in an argon-filled tube furnace at the temperature rising rate of 5 ℃/min to 700 ℃ to finally obtain the nitrogen-sulfur double-doped graphene/graphite composite material.
Example 3
A preparation method of a nitrogen-sulfur double-doped graphene/natural graphite composite material comprises the following steps:
(1) ultrasonically dispersing 0.1g of graphene oxide prepared by a modified Hummers method and 0.3g of thiourea in 20ml of deionized water until the thiourea is completely dispersed in the aqueous solution;
(2) weighing 0.2g of ascorbic acid, adding the ascorbic acid into the solution obtained in the step (1), and carrying out ultrasonic treatment for 1h until the ascorbic acid is completely dissolved;
(3) heating the solution obtained in the step (2) in a water bath at 40 ℃ for 2h until the solution is in a viscous state;
(4) weighing 0.7g of natural graphite, adding the natural graphite into the viscous solution obtained in the step (3), and magnetically stirring the solution at the rotating speed of 450rpm for 1.5 hours until the natural graphite is uniformly dispersed in the solution;
(5) transferring the uniform viscous solution obtained in the step (4) into a water bath kettle, and heating at 80 ℃ for self-assembly for 3 hours;
(6) after the self-assembly reaction is finished, cooling to room temperature to obtain black columnar hydrogel, soaking in a solution of deionized water and ethanol (V% ═ 5:1) for 12 hours, and then freeze-drying for 40 hours;
(7) and (3) after freeze drying, obtaining black columnar aerogel, putting the black columnar aerogel into a quartz boat, and calcining for 5 hours in an argon-filled tube furnace at the temperature rise rate of 5 ℃/min to 600 ℃ to finally obtain the nitrogen-sulfur double-doped graphene/graphite composite material.
The performance analysis of the nitrogen-sulfur double-doped graphene/natural graphite composite material prepared in the above examples 1 to 3 was performed: as can be seen from the scanning electron microscope in fig. 1, the active material is composed of graphene and graphite, and the graphene is distributed in a corrugated shape, which is beneficial to the hydrophilicity of the electrolyte and the transmission of lithium ions; it can be seen from the EDS spectra of fig. 2 and 3 that the material is composed of C, O, N, S four elements, illustrating that N, S two elements are effectively introduced by incorporating thiourea in the synthesis.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material is characterized by comprising the following steps of:
(1) ultrasonically dispersing graphene oxide and thiourea in deionized water until the thiourea is completely dispersed in the aqueous solution;
(2) weighing ascorbic acid, adding the ascorbic acid into the solution obtained in the step (1), and carrying out ultrasonic treatment until the ascorbic acid is completely dissolved;
(3) heating the solution obtained in the step (2) under the condition of water bath until the solution is in a viscous state;
(4) weighing a certain amount of natural graphite, adding the natural graphite into the viscous solution obtained in the step (3), and stirring the natural graphite by strong magnetic force until the natural graphite is uniformly dispersed in the solution;
(5) transferring the uniform viscous solution obtained in the step (4) into a water bath kettle, and heating for self-assembly;
(6) after the self-assembly reaction is finished, cooling to room temperature to obtain black columnar hydrogel, soaking the black columnar hydrogel in a mixed solution of deionized water and ethanol, and then freeze-drying the black columnar hydrogel for 36-48 h;
(7) and (3) after freeze drying, obtaining black columnar aerogel, putting the black columnar aerogel into a quartz boat, and calcining for 3-5h in a tube furnace to finally obtain the nitrogen-sulfur double-doped graphene/graphite composite material.
2. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the mass ratio of the graphene oxide to the thiourea in the step (1) is 1 (1-3).
3. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the mass ratio of the ascorbic acid added in the step (2) to the graphene oxide in the step (1) is 2: 1.
4. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the water bath heating in the step (3) is performed at a temperature of 40-60 ℃ for 1-2 hours.
5. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the mass ratio of the addition amount of the natural graphite in the step (4) to the graphene oxide in the step (1) is 7: 1; and (4) stirring for 1-2 hours at the rotating speed of 400-500 rpm for strong magnetic stirring in the step (4).
6. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the water bath heating temperature in the step (5) is 80-90 ℃, and the heating time is 2-3 h.
7. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the volume ratio of the deionized water to the alcohol in the step (6) is 5:1, and the freeze drying conditions are-58 ℃ and the vacuum degree is less than or equal to 10 pa.
8. The preparation method of the nitrogen-sulfur double-doped graphene/graphite composite material according to claim 1, wherein the calcination in the step (7) is performed under the protection of argon gas, the temperature rise rate is 5 ℃/min, and the temperature rises to 600-800 ℃.
9. A nitrogen-sulfur double-doped graphene/graphite composite material, which is prepared by the preparation method of any one of claims 1 to 8.
10. The use of the nitrogen-sulfur double-doped graphene/graphite composite material according to any one of claims 1 to 9 in a negative electrode material of a lithium ion battery.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011049838.1A CN112174127A (en) | 2020-09-29 | 2020-09-29 | Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011049838.1A CN112174127A (en) | 2020-09-29 | 2020-09-29 | Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112174127A true CN112174127A (en) | 2021-01-05 |
Family
ID=73945759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011049838.1A Pending CN112174127A (en) | 2020-09-29 | 2020-09-29 | Nitrogen-sulfur double-doped graphene/graphite composite material, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112174127A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115025754A (en) * | 2021-12-28 | 2022-09-09 | 淮阴师范学院 | Preparation method of patterned nitrogen and sulfur co-doped graphene aerogel |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104882608A (en) * | 2015-05-06 | 2015-09-02 | 江南大学 | Preparation method of N-doped 3D graphene/graphite lithium ion battery negative material |
US20170125800A1 (en) * | 2014-06-11 | 2017-05-04 | Suzhou Institute Of Nano-Tech And Nano-Bionics, Chinese Academy Of Science | Nitrogen-doped graphene coated nano sulfur positive electrode composite material, preparation method, and application thereof |
CN109778225A (en) * | 2019-01-31 | 2019-05-21 | 上海应用技术大学 | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation |
CN110790262A (en) * | 2019-10-31 | 2020-02-14 | 西北工业大学 | Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method |
CN111509235A (en) * | 2020-04-29 | 2020-08-07 | 沈阳建筑大学 | Sulfur-nitrogen co-doped graphene modified graphite felt composite electrode and preparation method thereof |
-
2020
- 2020-09-29 CN CN202011049838.1A patent/CN112174127A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170125800A1 (en) * | 2014-06-11 | 2017-05-04 | Suzhou Institute Of Nano-Tech And Nano-Bionics, Chinese Academy Of Science | Nitrogen-doped graphene coated nano sulfur positive electrode composite material, preparation method, and application thereof |
CN104882608A (en) * | 2015-05-06 | 2015-09-02 | 江南大学 | Preparation method of N-doped 3D graphene/graphite lithium ion battery negative material |
CN109778225A (en) * | 2019-01-31 | 2019-05-21 | 上海应用技术大学 | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation |
CN110790262A (en) * | 2019-10-31 | 2020-02-14 | 西北工业大学 | Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method |
CN111509235A (en) * | 2020-04-29 | 2020-08-07 | 沈阳建筑大学 | Sulfur-nitrogen co-doped graphene modified graphite felt composite electrode and preparation method thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115025754A (en) * | 2021-12-28 | 2022-09-09 | 淮阴师范学院 | Preparation method of patterned nitrogen and sulfur co-doped graphene aerogel |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104617281B (en) | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material | |
CN107342411B (en) | Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material | |
CN103441247B (en) | A kind of high performance silicon/graphene oxide negative material constructed based on chemical bond and preparation method thereof | |
CN110416507B (en) | In-situ self-assembly three-dimensional flower-like cobalt disulfide/MXene composite material and preparation method and application thereof | |
CN109560278B (en) | Preparation method of lithium ion battery negative electrode material silicon oxide-carbon-graphite | |
CN104681798A (en) | Method for preparing silicon-based composite anode material of lithium ion battery | |
CN108281634A (en) | A kind of method and its application of graphene coated graphite negative material of lithium ion battery | |
CN104638240A (en) | Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method | |
CN104409702A (en) | Preparation method of N-doped coated graphene micron silicon composite material | |
CN112186182B (en) | One-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and preparation method thereof | |
CN112421008B (en) | Preparation method of carbon-coated silicon monoxide material for lithium ion battery cathode, product and application thereof | |
CN112652757B (en) | Modified silicon-carbon negative electrode material and preparation method and application thereof | |
CN109449411B (en) | Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain | |
CN113611855B (en) | Water-soluble inorganic salt modified graphite material and preparation method and application thereof | |
CN104091952A (en) | Novel negative electrode material for lithium ion battery and preparation method of negative electrode material | |
CN113078320B (en) | Melamine modified graphite negative electrode material and preparation method and application thereof | |
CN114122354B (en) | Silicon-based composite anode material and preparation method thereof | |
CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
CN111268671B (en) | Graphene-loaded tin-doped cobalt disulfide composite material and preparation method and application thereof | |
CN111509230B (en) | Tin disulfide composite flexible carbon cloth electrode material and preparation method thereof | |
CN114388738B (en) | Silicon-based anode material and preparation method and application thereof | |
CN111916741A (en) | Preparation method and application of sodium titanium phosphate/carbon composite material | |
CN111564618A (en) | High-capacity lithium ion battery cathode material capable of being industrially produced | |
CN111313012A (en) | Multiwalled carbon nanotube graphite lithium ion battery negative electrode material and preparation method thereof | |
CN112980436B (en) | Carbon quantum dot derived carbon nano sheet composite silicon dioxide anode material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210105 |