CN111099578B - Nitrogen-doped three-dimensional graphene material - Google Patents
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- 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
- C01B32/184—Preparation
-
- 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
Abstract
A nitrogen-doped three-dimensional graphene material is characterized in that formaldehyde is used as a bridge, the formaldehyde and melamine are subjected to moderate crosslinking to form a nitrogen-doped precursor, then hydrothermal reaction is carried out, the nitrogen-doped precursor and cysteine are reacted to generate three-dimensional aerogel, the nitrogen-doped precursor and graphene are subjected to interaction and uniform fusion, and then solvent-free microwave reaction is carried out to synthesize the high-nitrogen-content doped three-dimensional graphene. According to the nitrogen-doped three-dimensional graphene material, the loss caused by sublimation of a nitrogen-doped precursor in a heating process in the traditional nitrogen-doping process is avoided in the preparation process, the nitrogen-doping efficiency is improved, the reaction conditions are gradually increased from mild to strong, and the nitrogen-doped precursor and graphene are uniformly fused through interaction. The prepared nitrogen-doped three-dimensional graphene material has good stability, is not easy to denature in air, is easy to store, has a large specific surface area, is used as a lithium ion battery cathode material, provides a good channel for lithium ion transmission, and shows large specific capacity and good cycling stability.
Description
Technical Field
The invention relates to a nitrogen-doped three-dimensional graphene material, in particular to a high-nitrogen-content doped graphene lithium battery cathode material and a preparation method thereof, and belongs to the technical field of electrode materials.
Background
Graphene is a carbonaceous material having a two-dimensional honeycomb lattice structure formed by close packing of single-layer carbon atoms, and has received great attention in experimental science and theoretical science since the discovery of Andre K heim (Andre K. Geim) and the like at manchester university in 2004 england. Graphene, which is only one carbon atom thick, is the thinnest of known materials, but is very strong and hard, stronger than diamond, and 100 times stronger than the hardest steel in the world. The nano-composite material has a special nano-structure and excellent performance, and has potential application prospects in the fields of catalysis, lithium storage, composite materials, electrochemistry and the like.
Graphene has hydrophobic properties and is difficult to directly modify and process in practical research. Graphene Oxide (GO), a derivative of the Graphene oxide, has good water-soluble dispersibility due to the fact that oxygen-containing functional groups such as carboxyl, hydroxyl and carbonyl are enriched on the surface, and good operability is provided for further modification of GO. For example, GO can be shrunk to form a three-dimensional hydrogel by adding certain cross-linking agents and providing certain temperature and pressure. The three-dimensional graphene has a high actual specific surface area, a rich pore structure and an excellent electron transmission speed, and good conditions are created for improving the electron transmission and the quality transmission of the catalyst.
The nitrogen-doped three-dimensional structure graphene is further prepared by carrying out nitrogen-doping modification on the three-dimensional structure graphene, so that the defects of the graphene can be overcome, the energy band gap can be opened, the conductivity type can be adjusted, the electronic structure can be changed, the free carrier density of the graphene can be improved, and the conductivity and stability of the graphene can be improved.
At present, a great deal of research is carried out to prepare nitrogen-doped graphene, and the method mainly comprises a high-temperature solid-phase reaction method, chemical vapor deposition, arc discharge, a hydrothermal method, a high-temperature thermal decomposition method and the like. CN 102887502B provides a chemical vapor deposition method for preparing nitrogen-doped graphene material, firstly providing a clean and dry substrate, coating a solution containing a catalyst on the surface of the substrate, and heating the substrate to 500-1300 ℃ in an oxygen-free condition o And C, introducing reducing gas and a reducing catalyst, and then introducing a gaseous organic carbon source compound and a gaseous nitrogen source compound to react to finally obtain the nitrogen-doped graphene. CN 104860308B adopts a solid-phase combustion synthesis method to prepare the nitrogen-doped graphene material, and mainly mixes solid metal powder, a solid carbon source and a solid nitrogen source, and carries out combustion synthesis reaction on the mixed powder, and the reaction product is washed and purified to obtain the nitrogen-doped graphene material. However, the existing methods generally have the problems of multiple steps, long time consumption and difficulty in controlling the nitrogen doping content, and the problem of low nitrogen doping efficiency caused by the loss of a large amount of nitrogen-doped precursors due to strong sublimation of the nitrogen-doped precursors in the heating process in the solid phase reaction causes difficulty in preparing the high-nitrogen-content doped three-dimensional graphene, so that the wide application of the nitrogen-doped three-dimensional graphene is limited.
Disclosure of Invention
In order to solve the problems of complex equipment, complex process, complex and time-consuming operation, low product utilization rate, difficult raw material acquisition, low nitrogen doping content caused by the loss of a large amount of nitrogen-doped precursors in the nitrogen doping process and the like in the preparation of the nitrogen-doped three-dimensional graphene material in the prior art, the invention provides a method for efficiently, quickly and massively synthesizing the high-nitrogen-content doped three-dimensional graphene material.
In order to achieve the technical purpose, the first aspect of the present invention provides a method for preparing a nitrogen-doped three-dimensional graphene material, comprising the following steps:
(1) dispersing graphene oxide in a formaldehyde aqueous solution, and then adding cysteine to obtain a dispersion liquid A;
(2) dispersing melamine into deionized water to obtain a dispersion liquid B;
(3) mixing the dispersion liquid A and the dispersion liquid B, heating to 50-80 ℃, reacting for 10-60min, adjusting the pH of the reaction liquid to 7-9, then sealing, heating for hydrothermal reaction, and drying the product to obtain aerogel;
(4) and (4) placing the aerogel obtained in the step (3) in a microwave reaction cavity, and heating for 10-60min at the microwave power of 300-1200W to obtain the nitrogen-doped three-dimensional graphene material.
In the above-mentioned production method, the concentration of the aqueous formaldehyde solution in the step (1) is not particularly limited, and in a preferred embodiment of the present invention, the concentration of formaldehyde by mass is 37% to 40%. And mixing the graphene oxide with the formaldehyde aqueous solution according to the solid-to-liquid ratio of 1g (10-100) mL. The mixing mass ratio of the graphene oxide to the cysteine is 1:1-20, preferably 1: 3-8; the cysteine is L-cysteine; the obtained solution is preferably mixed and dispersed uniformly in an ultrasonic mode, and the ultrasonic time is 5-30 min.
In the above production method, the dispersion liquid a and the dispersion liquid B are mixed in the step (3), and the dispersion liquid a is preferably poured into the dispersion liquid B. Mixing the graphene in the dispersion liquid A and the melamine in the dispersion liquid B in a ratio of 1:1-20 by mass. After mixing, the mixture is preferably mixed and dispersed evenly in an ultrasonic mode, and the ultrasonic time is 5-30 min.
In the above preparation method, the pH of the reaction solution in the step (3) may be adjusted by using an organic base or an inorganic base, and as a more specific embodiment, the pH is selected from one or more of triethanolamine, methylamine, ethylamine, ethylenediamine, propylamine, isopropylamine, aniline, cyclohexylamine, o-aminophenol, 2-chlorophenol, potassium carbonate, sodium bicarbonate, potassium hydroxide, and sodium hydroxide.
In the preparation method, the temperature of the hydrothermal reaction in the step (3) is 100-200 ℃, preferably 120-160 ℃, and the reaction time is 8-24 hours, preferably 12-18 hours.
In the above production method, the drying in the step (3) is freeze-drying. The freeze drying can maintain the graphene skeleton structure, effectively relieve the agglomeration phenomenon of graphene materials, and further ensure the characteristics of the interior of graphene.
In the preparation method, the power of the microwave reaction in the step (4) is preferably 600-1000W, and the time is preferably 10-30 min.
In the preparation method, the microwave reaction cavity is purged by nitrogen or inert gas before and during the microwave reaction, and preferably, argon is used for purging.
In the above preparation method, the graphene oxide is selected from among graphene oxides having the following properties: the area of the sheet layer is 100 mu m 2 The conductivity is 3500S/m or more.
In the above preparation method, the graphene oxide is obtained by oxidizing graphite, and the graphene oxide of the present invention is synthesized by Hummers method, and as a more specific embodiment, the present invention discloses a specific preparation method of the graphite oxide as follows: adding natural crystalline flake graphite into ice-bath concentrated sulfuric acid under stirring, cooling to 0-10 ℃, adding sodium nitrate and potassium permanganate, stirring for reaction, adding deionized water, heating to 50-100 ℃, reacting at constant temperature until the reaction solution turns to bright yellow, adding hydrogen peroxide, stirring for reaction, cooling, washing and drying to obtain graphene oxide.
The specification of the natural crystalline flake graphite is 100-500 meshes. After the reaction is finished, the post-treatment is carried out by repeatedly settling with deionized water to remove unreacted graphite particles, then centrifuging with hydrochloric acid, cleaning, removing Cl ions in the reaction solution, washing with deionized water until the pH value is close to neutral, drying and grinding.
The stripping efficiency of the Hummers method is more than 93%, the yield is more than 90%, the structural integrity of the obtained graphene oxide sheet layer is high, and the crystal lattice is complete after thermal reduction.
The technical purpose of the second aspect of the invention is to provide the nitrogen-doped three-dimensional graphene material prepared by the method. In the preparation process of the method, formaldehyde and melamine are mixed firstly to generate moderate crosslinking reaction to form a water-soluble nitrogen-doped precursor, and then hydrothermal reaction is carried out to carry out graphene nitrogen doping to obtain the three-dimensional graphene aerogel coated by the nitrogen-doped precursor, so that the nitrogen-doped precursor and graphene components are easy to interact, conditions are created for uniformly fusing composite materials, and the nitrogen-doped process is facilitated; subsequent microwave reaction heating rate is fast, the heating is even, and graphite oxide is reduced into graphite alkene by heat rapidly, and the nitrogen-doped precursor is heated and is decomposed simultaneously, because graphite oxide and nitrogen-doped precursor evenly fuse together in the preparation process before, make graphite alkene nitrogen doping more even, are favorable to synthesizing high content nitrogen doping graphite alkene more.
The technical purpose of the third aspect of the invention is to provide application of the nitrogen-doped three-dimensional graphene material, and the material can be used as a lithium ion battery cathode material and shows good cycle stability and rate capability.
Compared with the prior art, the invention has the following advantages:
(1) according to the preparation method, formaldehyde is used as a bridge in the preparation process of the nitrogen-doped three-dimensional graphene material, and the formaldehyde and melamine are appropriately crosslinked to form the nitrogen-doped precursor, so that the problem of low nitrogen-doping efficiency caused by large loss of the nitrogen-doped precursor due to strong sublimation of the nitrogen-doped precursor in the heating process in the traditional solid nitrogen-doping reaction is solved.
(2) In the preparation process, the formaldehyde and the melamine are subjected to a cross-linking reaction to form a water-soluble nitrogen-doped precursor, so that the nitrogen-doped precursor and the three-dimensional graphene framework are interacted and uniformly fused in the subsequent hydrothermal reaction, and the preparation of the high-nitrogen-content doped graphene material is realized.
(3) The microwave reaction stage in the preparation process, the heating rate is fast, the heating is even, can avoid the loss that the sublimation of the nitrogen-doped precursor that slowly heaies up in traditional reaction caused causes on the one hand, on the other hand, under the microwave condition, the oxidation graphite alkene is rapidly by thermal reduction for graphite alkene, the nitrogen-doped precursor is heated simultaneously and decomposes, because oxidation graphite alkene and nitrogen-doped precursor homogeneous fusion in the hydrothermal reaction process in the past are in the same place, make graphite alkene nitrogen doping more even, be more favorable to synthesizing high nitrogen content doping graphite alkene, effectively alleviate long-time heat treatment in-process nanoparticle's the gathering pile up.
(4) The microwave reaction in the preparation process adopts a solvent-free treatment mode, so that the post-treatment processes of washing, separating, drying and the like of the product are omitted, and the production process is simplified.
(5) The nitrogen-doped three-dimensional graphene material prepared by the method has good stability, is not easy to denature in air, is easy to store, has a large specific surface area, is used as a lithium ion battery cathode material, provides a good channel for lithium ion transmission, and shows a large specific capacity and a good cycling stability performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XRD pattern of graphene oxide prepared according to the present invention;
fig. 2 is an SEM image of the nitrogen-doped three-dimensional graphene material prepared in example 8;
FIG. 3 shows the current density of 100mA g of the nitrogen-doped three-dimensional graphene material in example 8 -1 Time charge and discharge cycle curve.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The graphene oxide used in the following examples was prepared by the following method:
100mL of 98% concentrated sulfuric acid was slowly added to a 500mL dry three-necked flask, and the three-necked flask was placed on a magnetic stirrer with ice-bath cooling. 2.0g of natural crystalline flake graphite (180 mesh) was added with rapid stirring until the temperature of the reaction mixture was reduced to aboutAt 0 deg.C, 4.0g of sodium nitrate was slowly added and stirring was continued for 2 h. Then slowly adding 10g of potassium permanganate in batches within 1h, continuously stirring for 2h, and controlling the reaction temperature below 10 ℃. The three-necked flask is transferred into a water bath at 40 ℃, and the reaction is continuously stirred for 2 hours. Subsequently, 200mL of warm deionized water was added slowly and the reaction solution was kept at a temperature within 100 ℃. The reaction was carried out at a constant temperature of 98 ℃ until the reaction solution became bright yellow. 20mL of 30% hydrogen peroxide was added to the reaction solution, and the mixture was stirred continuously to allow the mixture to react sufficiently. And after cooling, replacing deionized water with the obtained solution for repeated sedimentation, removing unreacted graphite particles, centrifugally cleaning with hydrochloric acid to remove Cl ions in the reaction solution, and then washing with deionized water until the pH value is close to neutral. And finally, vacuum drying for 12h at 80 ℃ to obtain graphene oxide, and grinding the graphene oxide into powder for later use. Its XRD pattern is shown in FIG. 1 and is located at 11 o To the left and right is the typical 001 diffraction peak of graphene oxide, which is mainly due to the intercalation of a large number of oxygen-containing functional groups between graphene sheets. The distance between graphite oxide sheets can be calculated to be 0.7 nm through the Sherle formula, and is obviously larger than the interlayer spacing 0.3254 nm of graphite. The increased interlayer spacing is primarily due to oxygen-containing functional groups intercalated between graphene sheets.
The nitrogen-doped three-dimensional graphene material is prepared in the embodiments 1-8:
example 1
(1) 1.0g of graphene oxide and 3.0g L-cysteine were weighed and dispersed in 20mL of 37% formaldehyde aqueous solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 3.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating to 60 ℃ in a water bath, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated by the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 10min at 600W of microwave power to obtain the nitrogen-doped three-dimensional graphene material.
Example 2
(1) 1.0g of graphene oxide and 3.0g L-cysteine were weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 5.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 60 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated by the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 10min at 600W of microwave power to obtain the nitrogen-doped three-dimensional graphene material.
Example 3
(1) 1.0g of graphene oxide and 4.0g L-cysteine were weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument and is uniformly dispersed by ultrasound to be marked as dispersion B.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 10 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 8.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated with the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 20min at the microwave power of 600W to obtain the nitrogen-doped three-dimensional graphene material.
Example 4
(1) 1.0g of graphene oxide and 5.0g of 5.0g L-cysteine were weighed out and dispersed in 30mL of 37% formaldehyde aqueous solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating to 70 ℃ in a water bath, and stirring for 20 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated by the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 30min at 600W of microwave power to obtain the nitrogen-doped three-dimensional graphene material.
Example 5
(1) 1.0g of graphene oxide and 6.0g L-cysteine were weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 70 ℃, and stirring for 20 min. And then adding potassium hydroxide into the reaction liquid, adjusting the pH value of a reaction liquid system to 9.0, carrying out ultrasonic mixing uniformly, then pouring the reaction liquid into a high-pressure reaction kettle, and heating to 120 ℃ for reaction for 12 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated by the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 10min at the microwave power of 800W to obtain the nitrogen-doped three-dimensional graphene material.
Example 6
(1) 1.0g of graphene oxide and 7.0g L-cysteine are weighed and dispersed in 30mL of 37% formaldehyde aqueous solution, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed and is marked as a dispersion liquid A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And then adding potassium hydroxide into the reaction liquid, adjusting the pH value of a reaction liquid system to 9.0, carrying out ultrasonic mixing uniformly, then pouring the reaction liquid into a high-pressure reaction kettle, and heating to 140 ℃ for reaction for 15 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated with the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 10min at the microwave power of 800W to obtain the nitrogen-doped three-dimensional graphene material.
Example 7
(1) 1.0g of graphene oxide and 8.0g of 8.0g L-cysteine were weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating to 80 ℃ in a water bath, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of the reaction solution system to 9.0, uniformly mixing by ultrasonic waves, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reaction for 15 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated by the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 10min at the microwave power of 800W to obtain the nitrogen-doped three-dimensional graphene material.
Example 8
(1) 1.0g of graphene oxide and 8.0g of 8.0g L-cysteine were weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. And freeze-drying the obtained product to obtain the three-dimensional graphene material coated by the nitrogen-doped precursor.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. And heating for 30min at the microwave power of 1000W to obtain the nitrogen-doped three-dimensional graphene material.
An SEM image of the nitrogen-doped three-dimensional graphene material obtained in example 8 is shown in fig. 2, and a three-dimensional graphene skeleton structure can be clearly seen, and the surface has some wrinkles.
Comparative example 1
In the step (1), the formaldehyde aqueous solution is not used, and deionized water is used for replacing:
(1) 1.0g of graphene oxide and 8.0g of 8.0g L-cysteine are weighed and dispersed in 30mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed and is marked as a dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) Mixing the dispersion A and the dispersion B, heating in water bath to 80 ℃, and stirring for 30 min. And adding triethanolamine into the reaction solution, adjusting the pH value of a reaction solution system to 9.0, ultrasonically mixing uniformly, pouring the reaction solution into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. The resulting product was freeze-dried.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by 100mL/min argon. Heating for 30min with 1000W of microwave power to obtain the comparative graphene material.
Comparative example 2
And (3) adjusting the pH value of the reaction solution without adding alkali liquor, and directly carrying out hydrothermal reaction after uniformly mixing the dispersion solution A and the dispersion solution B:
(1) 1.0g of graphene oxide and 8.0g of 8.0g L-cysteine were weighed and dispersed in 30mL of 37% aqueous formaldehyde solution, and the mixture was placed in an ultrasonic instrument and uniformly dispersed to obtain dispersion A.
(2) 10.0g of melamine is weighed and added into 40mL of deionized water, and the mixture is placed in an ultrasonic instrument to be uniformly dispersed by ultrasonic, and the dispersion liquid B is marked.
(3) And mixing the dispersion liquid A and the dispersion liquid B, uniformly mixing by ultrasonic waves, pouring the reaction liquid into a high-pressure reaction kettle, and heating to 160 ℃ for reacting for 18 hours. The resulting product was freeze-dried.
(4) And (4) placing the product obtained in the step (3) in a microwave reaction cavity, and purging for 1h by argon gas at 100 mL/min. Heating for 30min with 1000W of microwave power to obtain the comparative graphene material.
The materials of examples 1-8, comparative example 1 and comparative example 2 were used as negative electrode materials for lithium ion batteries. Taking the synthesized nitrogen-doped graphene as an active component, selecting a 2016 type battery shell, a metal lithium sheet (phi 16 mm multiplied by 1mm), and 1.0M LiPF 6 The mixed solution of Ethylene Carbonate (EC)/diethyl carbonate (DEC) (volume ratio is 1:1) is used as electrolyte, and Celgard2300 microporous polypropylene coal membrane is used as battery diaphragm. The materials are assembled into a button cell in a glove box filled with Ar gas, and the test is carried out after the working electrode is fully soaked by the electrolyte. The method comprises the following five steps:
(1) size mixing
The material used has a large specific surface and is easy to adsorb moisture in the air, so the material for preparing the electrode is fully dried in a vacuum drying oven at 120 ℃ to remove the moisture on the surface. Then adding an active substance, a conductive additive (acetylene black) and a binder (PVDF) into the dispersant according to the mass percentage of 80:10:10N-methylpyrrolidone (NMP) to mix and grind the materials to mix uniformly and make a viscous slurry.
(2) Coating film
The resulting viscous paste was uniformly coated on a copper foil (thickness of about 100 μm). The specific operation is as follows: 1) the copper foil of moderate size is cut and laid flat on a table top. 2) Removing stains on the surface of the copper foil. 3) The slurry was dispersed on a copper foil and uniformly spread on the copper foil using a die. 4) The copper foil coated with the slurry was dried in a vacuum drying oven at 120 ℃ for 12 hours.
(3) Roller compaction
After the completion of drying, the copper foil coated with the slurry was rolled with a small-sized rolling machine to prevent the electrode material from falling off from the surface of the copper foil.
(4) Tabletting
And cutting the rolled film into a plurality of circular electrode slices with the diameter of 12mm by using a manual slicer. In order to prevent the coating film from falling off during charge and discharge cycles, it was pressed into a sheet by an oil press. And taking out and weighing after drying, and waiting for battery loading.
(5) Assembled battery
The process of assembling the button cells was carried out in a glove box filled with Ar gas. The battery is assembled according to the sequence of negative battery shell/electrolyte/working electrode plate/electrolyte/diaphragm/lithium plate/positive battery shell. And standing for 24 hours, and carrying out electrochemical test after the electrolyte is fully soaked.
And carrying out charge and discharge tests on the assembled button type simulation battery. The material of example 8 was used at a voltage in the range of 0.01 to 3.0V and at a current of 100mA g -1 The results of the cycle stability test at the current density of (a) are shown in fig. 3. The first charge and discharge capacity and the discharge capacity after 100 charge and discharge tests of examples 1 to 8 and comparative examples 1 to 2 are shown in table 1. Wherein the content of nitrogen element is determined by element analysis.
According to test data, the content of nitrogen doped in the graphene is improved, and the nitrogen content can reach 10.1% at most. Secondly, the specific first discharge capacity of the button cell is increased, and the maximum first discharge capacity of the button cell in example 8 can reach 442.8 mAh.g -1 Compared with the comparative example 1, the reversible capacity retention rate is improved by about 10.0%, and the reversible capacity is still kept higher after 100 times of circulation, the reversible capacity retention rate exceeds 80.0% and reaches 90.8% at most, which shows that the material prepared by the invention has higher reversible capacity and good cycle performance.
TABLE 1
Claims (15)
1. A preparation method of a nitrogen-doped three-dimensional graphene material for a lithium ion battery cathode material comprises the following steps:
(1) dispersing graphene oxide in a formaldehyde solution, and then adding cysteine to obtain a dispersion liquid A;
(2) dispersing melamine into deionized water to obtain a dispersion liquid B;
(3) mixing the dispersion liquid A and the dispersion liquid B, heating to 50-80 ℃, reacting for 10-30min, adjusting the pH of the reaction liquid to 7-9, then heating in a sealed environment to carry out hydrothermal reaction at the temperature of 100 ℃ and 200 ℃ for 8-24 h, and drying the product to obtain aerogel;
(4) and (4) placing the aerogel obtained in the step (3) in a microwave reaction cavity, and heating for 10-60min at the microwave power of 300-1200W to obtain the nitrogen-doped three-dimensional graphene material.
2. The preparation method according to claim 1, wherein in the step (1), the graphene oxide is mixed with the formaldehyde solution according to a solid-to-liquid ratio of 1g to 10-100 mL.
3. The preparation method according to claim 1, wherein the mixing mass ratio of the graphene oxide to the cysteine in the step (1) is 1:1-20, and the cysteine is L-cysteine.
4. The preparation method according to claim 3, wherein the mixing mass ratio of the graphene oxide to the cysteine in the step (1) is 1: 3-8.
5. The method according to claim 1, wherein the dispersion A and the dispersion B are mixed in the step (3) by pouring the dispersion A into the dispersion B.
6. The preparation method according to claim 1, wherein the dispersion liquid A and the dispersion liquid B are mixed in the step (3), and the ratio of graphene in the dispersion liquid A to melamine in the dispersion liquid B is 1:1-20 by mass.
7. The production method according to claim 1, wherein an organic base or an inorganic base is used for adjusting the pH of the reaction solution in the step (3).
8. The method according to claim 7, wherein the organic or inorganic base is selected from one or more of triethanolamine, methylamine, ethylamine, ethylenediamine, propylamine, isopropylamine, aniline, cyclohexylamine, o-aminophenol, 2-chlorophenol, potassium carbonate, sodium bicarbonate, potassium hydroxide, and sodium hydroxide.
9. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 120 to 160 ℃ for 12 to 18 hours.
10. The preparation method according to claim 1, wherein the microwave reaction in the step (4) has a power of 600-1000W and a time of 10-30 min.
11. The preparation method according to claim 1, characterized in that the graphene oxide is chosen in particular from graphene oxides having the following properties: the area of the lamella is 100 μm 2 The conductivity is 3500S/m or more.
12. The preparation method according to claim 11, wherein the graphene oxide is obtained by oxidizing graphite.
13. The preparation method according to claim 12, wherein the graphene oxide is synthesized by a Hummers method, and the preparation method comprises the following steps: adding natural crystalline flake graphite into ice-bath concentrated sulfuric acid under the condition of stirring, cooling to 0-10 ℃, adding sodium nitrate and potassium permanganate, stirring for reaction, adding deionized water, heating to 50-100 ℃, reacting at constant temperature until the reaction solution turns bright yellow, adding hydrogen peroxide, stirring for reaction, cooling, washing and drying to obtain the graphene oxide.
14. The nitrogen-doped three-dimensional graphene material prepared by the method of any one of claims 1 to 13.
15. The use of the nitrogen-doped three-dimensional graphene material of claim 14 as a negative electrode material for a lithium ion battery.
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