CN102757029B - Nitrogen doped graphene material and preparation method thereof - Google Patents
Nitrogen doped graphene material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of electrochemical materials and discloses a nitrogen doped graphene material and a preparation method thereof. The preparation method of the nitrogen doped graphene material comprises the following steps of: preparing graphite oxidize; preparing graphene oxide solution; preparing mixed solution of graphene oxide and ammonium carbonate; removing solvent in the mixed solution of the graphene oxide and ammonium carbonate; and calcining mixture of graphite oxide and ammonium carbonate, thus obtaining the nitrogen doped graphene oxide material. The nitrogen doped graphene material and preparation method thereof which are disclosed by the invention have the advantages that preparation cost is lower, mass production is easy to realize, product purity is high, ammonium carbonate is completely decomposed into gas at high temperature and no pollution is produced to a product.
Description
Technical field
The present invention relates to grapheme material field, relate in particular to a kind of nitrogen-doped graphene material.The invention still further relates to the preparation method of nitrogen-doped graphene material.
Background technology
The strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because its unique structure and photoelectric property have been subject to people, pay attention to widely.Mono-layer graphite is due to its large specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.As: 1, high strength, Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm
2/ V*s); 4, high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.Up to the present, known to the method for preparing Graphene have multiple, as (1) micromechanics stripping method; This method can only produce the very limited graphene film of quantity, can be used as fundamental research; (2) ultrahigh vacuum(HHV) Graphene epitaxial growth method; The structural limitations of the expensive and sequin of this method its application; (3) chemical Vapor deposition process (CVD); This method can meet the requirement that high-quality graphene is prepared in mass-producing, but cost is higher, complex process.(4) solvent stripping method; This method shortcoming is that productive rate is very low, limits its commercial applications; (5) oxidation-reduction method; This method is the most simply can obtain in a large number a kind of common method of Graphene, and whole process relates to graphite oxidation is become to graphite oxide, and graphite oxide peels off the graphene oxide of generation, then is Graphene by chemical reagent or thermal reduction; The synthetic final oxygen level of Graphene of this method is higher, and purity is inadequate; For Graphene, the voltage as electrode materials has a certain impact in the existence of Sauerstoffatom.
Summary of the invention
The object of the present invention is to provide a kind of low cost, high purity, and be easy to realize the preparation method of the nitrogen-doped graphene material of scale operation.
Technical scheme of the present invention is as follows:
A preparation method for nitrogen-doped graphene material, comprises the steps:
S1, the Graphite Powder 99, Potassium Persulphate and the Vanadium Pentoxide in FLAKES that by mass ratio, are 2:1:1 add in the vitriol oil of 80 ℃, stir, and more than cooling 6h, washing is to neutral, dry; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 35 ℃, keep after 2h, slowly add 920mL deionized water; After 15min, add 2.8L deionized water, then adding 50mL concentration is the hydrogen peroxide solution of 30wt% again, and mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, at 60 ℃ of vacuum-drying 48h, obtain graphite oxide with the hydrochloric acid that 5L concentration is 10%;
S2, the graphite oxide making in step S1 is added to the water, ultrasonic dispersion 0.5～2h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration of graphene oxide is 0.1～2mg/ml, is preferably 1mg/ml;
In S3, the graphene oxide solution that obtains toward step S2, adding mass concentration is 10～50% soluble ammonium salts solution, stirs 10min, and graphene oxide is mixed with soluble ammonium salts solution, obtains the mixing solutions of graphene oxide and solubility ammonium salt; Wherein, soluble ammonium salts solution is sal volatile, ammonium bicarbonate soln, Spirit of Mindererus or ammonium oxalate solution, and the concentration of ammonium salt is 10-50wt%;
Solvent in S4, removal step S3 gained mixing solutions, obtains solid mixture;
S5, the solid mixture in step S4 is placed in to the retort furnace insulation calcining 0.5～5h of 550～1000 ℃; and whole calcination process carries out under non-oxidizing gas (at least one in hydrogen atmosphere, nitrogen atmosphere or argon gas atmosphere) protection; cooling, obtain nitrogen-doped graphene material.
The invention still further relates to a kind of nitrogen-doped graphene material, this material adopts processing step as mentioned above to make.
A kind of nitrogen-doped graphene material preparation method provided by the invention, have preparation cost lower, easily realize scale operation, product purity is high, and is decomposed into gas completely under volatile salt high temperature, can not pollute product; Meanwhile, the method, by the Graphene of preparing under non-oxidizing atmosphere environment, can effectively replace the oxygen in Graphene, thereby reduces the oxygen level in Graphene, has improved the magnitude of voltage of Graphene as electrode materials.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of nitrogen-doped graphene material preparation method of the present invention;
Fig. 2 is that the nitrogen-doped graphene material of the embodiment of the present invention 1 is applied to the constant current charge-discharge graphic representation in ultracapacitor as electrode materials.
Embodiment
The object of the present invention is to provide a kind of low cost, high purity, and be easy to realize the preparation method of the nitrogen-doped graphene material of scale operation, first by improved Hummers legal system for graphite oxide, change graphite oxide ultrasonic dispersion in water into graphene oxide again, adding volatile salt (can be also bicarbonate of ammonia again, ammonium acetate, ammonium oxalate, methane amide or ethanamide etc.) solution mixes, by solvent evaporates, obtain graphene oxide and volatile salt solid mixture, finally solid mixture being put into retort furnace calcines, solubility ammonium salt or organic amine are decomposed into ammonia and carbon dioxide, graphene oxide adulterates and reduction reaction under the condition of ammonia simultaneously, obtain nitrogen-doped graphene material.
A preparation method for nitrogen-doped graphene material, as shown in Figure 1, comprises the steps:
S1, according to Hummers method (Hummers W S, Offeman R E.[J] .J Am Chem Soc, 1958,80:133921339) prepare graphite oxide: 50 order Graphite Powder 99s, 10g Potassium Persulphate and the 10g Vanadium Pentoxide in FLAKES of 20g purity 99.5% are added in the vitriol oil of 80 ℃, stir, more than cooling 6h, washing is to neutral, dry; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 35 ℃, keep after 2h, slowly add 920mL deionized water; After 15min, add 2.8L deionized water, then adding 50mL concentration is the hydrogen peroxide solution of 30wt% again, and mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, at 60 ℃ of vacuum-drying 48h, obtain graphite oxide with the hydrochloric acid that 5L concentration is 10%;
S2, the graphite oxide making in step S1 is added to the water, ultrasonic dispersion 0.5～2h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration of graphene oxide is 0.1～2mg/ml, is preferably 1mg/ml;
In S3, the graphene oxide solution that obtains toward step S2, adding mass concentration is 10～50%(preferably 40%) soluble ammonium salts solution, stir 10min, graphene oxide is mixed with soluble ammonium salts solution, obtain the mixing solutions of graphene oxide and solubility ammonium salt; Wherein, soluble ammonium salts solution is sal volatile, ammonium bicarbonate soln, Spirit of Mindererus or ammonium oxalate solution, and the concentration of ammonium salt is 10-50wt%;
Solvent in S4, removal step S3 gained mixing solutions, obtains solid mixture;
S5, the solid mixture in step S4 is placed in to the retort furnace insulation calcining 0.5～5h of 550～1000 ℃; and whole calcination process carries out under non-oxidizing gas (at least one in hydrogen atmosphere, nitrogen atmosphere or argon gas atmosphere) protection; cooling, obtain nitrogen-doped graphene material.
The invention still further relates to a kind of nitrogen-doped graphene material, this material adopts processing step as mentioned above to make, and this nitrogen-doped graphene material has good conductivity, can be applied to the electrode of ultracapacitor.
A kind of nitrogen-doped graphene material preparation method provided by the invention, have preparation cost lower, easily realize scale operation, product purity is high, and is decomposed into gas completely under volatile salt high temperature, can not pollute product; Meanwhile, the method, by the Graphene of preparing under non-oxidizing atmosphere environment, can effectively replace the oxygen in Graphene, thereby reduces the oxygen level in Graphene, has improved the magnitude of voltage of Graphene as electrode materials.
Below preferred embodiment of the present invention is described in further detail.
Embodiment 1
(1) graphite oxide: 50 order Graphite Powder 99s, 10g Potassium Persulphate and the 10g Vanadium Pentoxide in FLAKES of 20g purity 99.5% are added in the vitriol oil of 80 ℃, stir, more than cooling 6h, washing is to neutral, dry; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 35 ℃, keep after 2h, slowly add 920mL deionized water; After 15min, add 2.8L deionized water, then adding 50mL concentration is the hydrogen peroxide solution of 30wt% again, and thing color to be mixed becomes glassy yellow, suction filtration while hot, then wash, suction filtration, at 60 ℃ of vacuum-drying 48h, obtain graphite oxide with the hydrochloric acid that 5L concentration is 10%;
(2) graphite oxide preparing in (1) is added to the water ultrasonic dispersion 0.5h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration that makes graphene oxide is 1mg/ml;
(3) toward the graphene oxide solution in (2), adding concentration is the sal volatile of 40wt%, stirs 10min, and both are mixed, and obtains graphene oxide and volatile salt mixing solutions;
(4), by the mixing solutions evaporating solvent of (3) gained, obtain solid mixture;
(5) first retort furnace is warmed up to 1000 ℃, the mixture then (4) being obtained is put into retort furnace, and under hydrogen atmosphere protection, insulation calcining 0.5h, cooling, obtains nitrogen-doped graphene material.
Embodiment 2
(1) preparation of graphite oxide is in the same manner as in Example 1;
(2) graphite oxide preparing in (1) is added to the water ultrasonic dispersion 1h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration that makes graphene oxide is 0.1mg/ml;
(3) toward the graphene oxide solution in (2), adding mass concentration is 10% ammonium bicarbonate soln, stirs 10min, and both are mixed, and obtains graphene oxide and volatile salt mixing solutions;
(4), by the mixing solutions evaporating solvent of (3) gained, obtain solid mixture;
(5) first retort furnace is warmed up to 550 ℃, the mixture then (4) being obtained is put into retort furnace, and under nitrogen atmosphere protection, insulation calcining 1h, cooling, obtains nitrogen-doped graphene material.
Embodiment 3
(1) preparation of graphite oxide is in the same manner as in Example 1;
(2) graphite oxide preparing in (1) is added to the water ultrasonic dispersion 2h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration that makes graphene oxide is 2mg/ml;
(3) toward the graphene oxide solution in (2), adding mass concentration is 50% Spirit of Mindererus, stirs 10min, and both are mixed, and obtains graphene oxide and volatile salt mixing solutions;
(4), by the mixing solutions evaporating solvent of (3) gained, obtain solid mixture;
(5) first retort furnace is warmed up to 1000 ℃, the mixture then (4) being obtained is put into retort furnace, and under argon gas atmosphere protection, insulation calcining 5h, cooling, obtains nitrogen-doped graphene material.
Embodiment 4
(1) preparation of graphite oxide is in the same manner as in Example 1;
(2) graphite oxide preparing in (1) is added to the water ultrasonic dispersion 1h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration that makes graphene oxide is 1.5mg/ml;
(3) toward the graphene oxide solution in (2), adding mass concentration is 30% ammonium oxalate solution, stirs 10min, and both are mixed, and obtains graphene oxide and volatile salt mixing solutions;
(4), by the mixing solutions evaporating solvent of (3) gained, obtain solid mixture;
(5) first retort furnace is warmed up to 800 ℃, the mixture then (4) being obtained is put into retort furnace, and under hydrogen and the protection of nitrogen mixture atmosphere, insulation calcining 2h, cooling, obtains nitrogen-doped graphene material.
Embodiment 5
(1) preparation of graphite oxide is in the same manner as in Example 1;
(2) graphite oxide preparing in (1) is added to the water ultrasonic dispersion 1.5h, forms with the homodisperse graphene oxide solution of monolithic layer, and the concentration that makes graphene oxide is 1mg/ml;
(3) toward the graphene oxide solution in (2), adding mass concentration is 40% sal volatile, stirs 10min, and both are mixed, and obtains graphene oxide and volatile salt mixing solutions;
(4), by the mixing solutions evaporating solvent of (3) gained, obtain solid mixture;
(5) first retort furnace is warmed up to 1000 ℃, the mixture then (4) being obtained is put into retort furnace, and under hydrogen and the protection of argon gas mixed atmosphere, insulation calcining 4h, cooling, obtains nitrogen-doped graphene material.
In order to test boron for the capacitive property of graphene oxide electrode, the present invention will test boron and become battery or electrode for capacitors for graphene oxide electrode fabrication, carry out charge-discharge test.
Ultracapacitor below, i.e. battery charging and discharging graphic representation, as shown in Figure 2, the electrode materials of this ultracapacitor adopts the embodiment of the present invention 1 to make Graphene/polythiophene derivant composite materials.
1, the preparation of pole piece: take Graphene/polythiophene derivant composite materials 4.5g, acetylene black 0.25g, PVDF0.25g, dripping NMP makes said mixture become pulpous state, fully stirring is coated on metal aluminum foil after making it to mix, coating thickness is 200 μ m, then after 100 ℃ of dry 12h of vacuum, take out, form the roll-in of described pole piece pole piece: the pole piece of gained is carried out to roll extrusion with roller mill, and the thickness after roll-in is 165 μ m; Cut-parts: the pole piece of roll-in is broken into the circular pole piece that diameter is 15mm with punch tool, accurately weigh;
2, the assembling of battery: in glove box by pole piece, barrier film and electrolytic solution are assembled into ultracapacitor according to cell making process, its septation is celgard2000(U.S. Nader company product), electrolytic solution is the 1-ethyl-3-methylimidazole Tetrafluoroboric acid salts solution of 1mol/L, assembled and within latter standing one day, carried out constant current charge-discharge test, wherein, test voltage scope is 0-2.5V, and test current is that 1A/g carries out constant current charge-discharge.
Testing apparatus is the blue electric CT-2001A8 in the Wuhan battery test system of filling enamel, and glove box is German Braun glove box.
From Fig. 2, charging and discharging curve can be found out, battery under 1A/g current density, the charging and discharging curve shape that charging and discharging curve is near the mark, and charging curve and discharge curve present good symmetry, voltage is linear variation in time, has embodied good capacitance characteristic; Therefore, this battery has good charge-discharge performance.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (7)
1. a preparation method for nitrogen-doped graphene material, is characterized in that, the method comprises the steps:
S21, graphite oxide is added to the water, ultrasonic dispersion 0.5～2h, obtains graphene oxide solution;
In S22, the graphene oxide solution that obtains toward step S21, add soluble ammonium salts solution, stir, obtain mixing solutions;
Solvent in S23, removal step S22 gained mixing solutions, obtains solid mixture;
S24, the solid mixture in step S23 is placed at 550～1000 ℃ to insulation calcining 0.5～5h, cooling, obtain described nitrogen-doped graphene material;
In described solubility solution, the concentration of ammonium salt is 10-50wt%;
In described step S24, described solid mixture is incubated calcining in oxygen-free atmosphere.
2. preparation method according to claim 1, is characterized in that, in described step S21, described graphite oxide is to adopt following steps to make:
S211, the Graphite Powder 99, Potassium Persulphate and the Vanadium Pentoxide in FLAKES that by mass ratio, are 2:1:1 add in the vitriol oil of 80 ℃, stir, and more than cooling 6h, washing is to neutral, dry, obtains mixture;
S212, the mixture that step S211 is obtained join in 0 ℃, the vitriol oil of 230mL, add again potassium permanganate, and in the oil bath of 35 ℃ after insulation reaction 2h, slowly add deionized water, adding subsequently concentration is the hydrogen peroxide solution of 30wt%, then carry out suction filtration, washing, suction filtration and drying treatment again, obtain graphite oxide.
3. preparation method according to claim 2, is characterized in that, in described step S212, the quality add-on of described potassium permanganate is Graphite Powder 99 3 times.
4. preparation method according to claim 1 and 2, is characterized in that, in described step S21, in described graphene oxide solution, the concentration of graphene oxide is 0.1～2mg/ml.
5. preparation method according to claim 4, is characterized in that, in described graphene oxide solution, the concentration of graphene oxide is 1mg/ml.
6. preparation method according to claim 1 and 2, is characterized in that, in described step S22, described soluble ammonium salts solution is sal volatile, ammonium bicarbonate soln, Spirit of Mindererus or ammonium oxalate solution.
7. preparation method according to claim 1, is characterized in that, described oxygen-free atmosphere comprises at least one in hydrogen atmosphere, nitrogen atmosphere or argon gas atmosphere.
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| CN103864057B (en) * | 2012-12-07 | 2015-12-02 | 北京大学 | Phosphorus doping Graphene and its preparation method and application |
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| CN104261388B (en) * | 2014-09-17 | 2016-01-13 | 北京理工大学 | A kind of method of shock wave treatment manufacture of carbonates nitrogen-doped graphene |
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| CN104280447A (en) * | 2014-10-14 | 2015-01-14 | 广州盈思传感科技有限公司 | Method for detecting benzenediol-type substances in water |
| CN105084351A (en) * | 2015-07-03 | 2015-11-25 | 北京交通大学 | Preparation method for nitrogen-doped graphene hydrogel |
| CN105632783B (en) * | 2016-01-11 | 2018-02-09 | 河南师范大学 | A kind of nitrogen-doped graphene ultracapacitor preparation method based on redox active electrolyte |
| CN109095463B (en) * | 2018-05-09 | 2020-09-04 | 东莞理工学院 | Improved preparation method of graphene oxide/nano copper oxide composite material |
| CN108914251B (en) * | 2018-07-09 | 2020-10-30 | 杭州高烯科技有限公司 | Nitrogen-doped graphite fiber and preparation method thereof |
| CN110697785A (en) * | 2019-10-16 | 2020-01-17 | 蚌埠学院 | Preparation of manganese oxide-nitrogen modified graphene composite material and lithium battery application |
| CN114212778A (en) * | 2021-12-29 | 2022-03-22 | 杭州嘉悦智能设备有限公司 | Preparation method of nitrogen-doped graphene film and nitrogen-doped graphene film |
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