CN103864010B - A kind of nitrogen-doped graphene/cobalt ferrite nano composite material and preparation thereof - Google Patents
A kind of nitrogen-doped graphene/cobalt ferrite nano composite material and preparation thereof Download PDFInfo
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Abstract
The invention discloses a kind of nitrogen-doped graphene/cobalt ferrite nano composite material and preparation thereof.Graphite oxide is placed in absolute ethyl alcohol to carry out ultrasonic; Subsequently cobalt nitrate and ferric nitrate are joined absolute ethyl alcohol; The metal salt solution of dissolving is joined in graphene oxide solution, again ultrasonic disperse; Joined by urea in above-mentioned finely dispersed mixed solution, stirring and dissolving, finally carries out hydrothermal synthesis reaction by mixed solution, and after reaction terminates, product, after centrifuge washing and drying, obtains composite.The present invention adopts urea to reduce to graphene oxide, while reduction, at the surface doping nitrogen-atoms of Graphene, the doping of nitrogen-atoms changes graphenic surface chemical property, compensate for chemical method and prepare the blemish of Graphene existence simultaneously, the alkalescence that urea provides, makes cobalt ferrite be formed on the surface of nitrogen-doped graphene, cobalt ferrite nano particle can stop Graphene accumulation between layers to be reunited further, improves the chemical property of composite.
Description
Technical field
The invention belongs to Nano-composite materials field, specifically relate to a kind of nitrogen-doped graphene/cobalt ferrite nano composite material and preparation thereof.
Background technology
Since 2004, the birth of new carbon Graphene, the structure (larger specific area) of its uniqueness and photoelectric property (excellent electric conductivity) receive people and pay attention to widely, current Graphene has been widely used at energy storage device (ultracapacitor, lithium ion battery, fuel cell etc.) and other field.At present, the preparation method of Graphene has a variety of, and wherein the chemical method of oxidationreduction prepares Graphene, and because of it, to prepare output high and apply comparatively extensive, but the method obtains Graphene existing defects, easily reunites, the application of restriction Graphene.Some researchers are by dopant impurity atoms or load conducting polymer, and metal oxide etc. overcome the agglomeration traits between Graphene interface, wherein boron, nitrogen, and the application of sulfur doping Graphene is at the early-stage.
The people such as KlausM ü llen are doped with nitrogen, boron (Three-DimensionalNitrogenandBoronCo-dopedGrapheneforHigh-PerformanceAll-Solid-StateSupercapacitors.AdvancedMateri als2012,24 (37): 5130-5135.) by hydro-thermal method on the surface of Graphene simultaneously; Chinese patent (CN103274393A, CN102760866A, CN103359708A, CN103359711A and CN102167310A etc.) introduces nitrogenous source by different chemical methodes, prepared nitrogen-doped graphene, wherein a lot of preparation method is faced with that production cost is high, reaction equipment needed thereby complexity, severe reaction conditions, the problem such as yield poorly; Although the nitrogen-doped graphene obtained, compared with Graphene, improves its electric conductivity, as it can be used as the electrode material of ultracapacitor, its chemical property (as ratio capacitance) cannot meet the requirement of practical application far away.
Cobalt ferrite is the one in ferrite metal composite, and the theoretical ratio capacitance higher due to it and causing greatly is paid close attention to.But its poor cyclicity limits its application in energy storage material, the people such as xia improve its cycle performance by cobalt ferrite and Graphene being combined with each other, (CoFe2O4-graphenenanocompositeasahigh-capacityanodemateri alforlithium-ionbatteries.ElectrochimicaActa, 2012,83,166-174.), but its chemical property (ratio capacitance and cycle performance) is still undesirable.
At present, N doping graphite/cobalt ferrite bielement nano composite be have not been reported.
Summary of the invention
For the problem of currently available technology, the object of this invention is to provide a kind of simple one pot process nitrogen-doped graphene/cobalt ferrite nano composite material and preparation method thereof, this preparation method's synthesis technique is simple, and lower cost, is suitable for large-scale industrial production.
The technical solution realizing the object of the invention is: a kind of nitrogen-doped graphene/cobalt ferrite nano composite material, described composite is made up of matrix material nitrogen-doped graphene and cobalt ferrite, wherein, the mass ratio of matrix material nitrogen-doped graphene and cobalt ferrite is 1:3 ~ 1:10; In described matrix material nitrogen-doped graphene, the doping of nitrogen is 1 ~ 2%.
A preparation method for nitrogen-doped graphene/cobalt ferrite nano composite material, comprises the steps:
The first step: graphite oxide is carried out in absolute ethyl alcohol ultrasonic disperse and obtain finely dispersed graphene oxide solution;
Second step: a certain amount of ferric nitrate and cobalt nitrate are dissolved in absolute ethyl alcohol, and stir and cause it and dissolve completely;
3rd step: the mixed salt solution of dissolving is poured in the graphene oxide solution that the first step obtains, and stir and make it mix;
4th step: urea is joined the 3rd step and obtain in mixed system, again stir, make it be uniformly dispersed, wherein the mass ratio of urea and graphite oxide is 100:1 ~ 200:1;
5th step: the above-mentioned mixed solution mixed is transferred in water heating kettle, carries out hydro-thermal reaction at 120 ~ 200 DEG C;
6th step: the 5th step product is carried out centrifugation, and after repeatedly spending deionized water, drying, obtain nitrogen-doped graphene/cobalt ferrite nano composite material.
The ultrasonic disperse time described in step one is 1 ~ 3h.
The mol ratio of the ferric nitrate described in step 2 and cobalt nitrate is 2:1, and described graphite oxide and the mass ratio of cobalt ferrite are 1:3 ~ 1:10, and the dispersed with stirring time is 10 ~ 60min.
The dispersed with stirring time described in step 3 is 10 ~ 60min.
Mixing time described in step 4 is 30 ~ 90min.
The hydro-thermal reaction time described in step 5 is 12 ~ 20h.
Compared with prior art, tool of the present invention has the following advantages in the present invention: (1) synthesis technique of the present invention is simple, and production cost is low, and be beneficial to the large-scale production of low cost, and reaction reagent is nontoxic, environmental pollution is little, (2) urea is adopted to reduce to graphene oxide, while reduction, at the surface doping nitrogen-atoms of Graphene, the doping of nitrogen-atoms changes graphenic surface chemical property, compensate for chemical method and prepare the blemish of Graphene existence simultaneously, the alkalescence that urea provides, cobalt ferrite is formed on the surface of nitrogen-doped graphene, cobalt ferrite nano particle can stop Graphene accumulation between layers to be reunited further, improve the chemical property of composite (if ratio capacitance is by 259 and 128F/g of original one-component electrode, bring up to 318F/g, after circulation 5000 circle, its decay about about 10%).So nitrogen-doped graphene and cobalt ferrite are combined with each other, give full play to both advantages, improve respective defect, thus obtain the electrode material of electrochemical performance.
Accompanying drawing explanation
Accompanying drawing 1 and be the XPS(a of nitrogen-doped graphene/cobalt ferrite nano composite material prepared by the embodiment of the present invention 1) and XRD collection of illustrative plates (b).
Accompanying drawing 2 is TEM photo (a) and Raman collection of illustrative plates (b) of nitrogen-doped graphene/cobalt ferrite nano composite material prepared by the embodiment of the present invention 2.
Accompanying drawing 3 is the cyclic voltammetry curve figure under the electrochemical Characterization figure of nitrogen-doped graphene/cobalt ferrite nano composite material prepared by the embodiment of the present invention 3 different scanning rates in acidic electrolyte bath.
Detailed description of the invention
The mass ratio being mainly 1 ~ 2% to nitrogen content in conjunction with specific embodiments is below that the preparation method of the nitrogen-doped graphene/cobalt ferrite nano composite material of 1:3 ~ 1:10 is described in further detail.
Embodiment 1: nitrogen content is nitrogen-doped graphene/cobalt ferrite nano composite material (graphite oxide and cobalt ferrite mass ratio the are 1:3) preparation method of 1%, comprises the following steps:
The first step, be that graphite oxide ultrasonic disperse in 50mL absolute ethyl alcohol of 100mg obtains uniform graphene oxide solution by content, ultrasonic time is 1h;
Second step, is dissolved in 1.0333g ferric nitrate and 0.3722g cobalt nitrate in 20mL ethanol and stirs 10min;
3rd step, pours into the mixed salt solution of above-mentioned dissolving in the graphene oxide solution that the first step obtains, and stirs 10min, make it mix;
4th step, joins the 3rd step and obtains in mixed system, again stir 30min, make it be uniformly dispersed by the urea of 10g;
5th step, be transferred in water heating kettle by the above-mentioned mixed solution mixed and carry out hydro-thermal reaction, reaction temperature is 120 DEG C, and the reaction time is 20h;
6th step, carries out centrifugation by the 5th step product, and obtains nitrogen-doped graphene/cobalt ferrite nano composite material after repeatedly spending deionized water, drying.
As shown in Fig. 1 (a) XPS, containing there being carbon in figure, oxygen, nitrogen and iron and cobalt five kinds of elements, describe the successful doping of nitrogen element, and the existence of cobalt ferrite, and wherein the content of nitrogen element is 1%, characterize through figure (b) X-ray powder diffraction (XRD), its characteristic diffraction peak can belong to cobalt ferrite nano particle, therefore obtained product is nitrogen-doped graphene/cobalt ferrite nano composite material.
Embodiment 2: nitrogen content is nitrogen-doped graphene/cobalt ferrite nano composite material (graphite oxide and cobalt ferrite mass ratio the are 1:5) preparation method of 1.5%, comprises the following steps:
The first step, be that graphite oxide ultrasonic disperse in 50mL absolute ethyl alcohol of 100mg obtains uniform graphene oxide solution by content, ultrasonic time is 2h;
Second step, is dissolved in 1.7222g ferric nitrate and 0.6203g cobalt nitrate in 20mL ethanol and stirs 30min;
3rd step, pours into the mixed salt solution of above-mentioned dissolving in the graphene oxide solution that the first step obtains, and stirs 30min, make it mix;
4th step, joins the 3rd step and obtains in mixed system, again stir 60min, make it be uniformly dispersed by the urea of 15g;
5th step, be transferred in water heating kettle by the above-mentioned mixed solution mixed and carry out hydro-thermal reaction, reaction temperature is 180 DEG C, and the reaction time is 18h;
6th step, carries out centrifugation by the 5th step product, and obtains nitrogen-doped graphene/cobalt ferrite nano composite material after repeatedly spending deionized water, drying.
Its TEM photo is as accompanying drawing 2(a) shown in, cobalt ferrite nano particle is evenly distributed on the surface of nitrogen-doped graphene.The simultaneously Raman peaks of obvious visible cobalt ferrite in Fig. 2 (b) Raman spectrogram, can be clear and definite show that prepared product is nitrogen-doped graphene/cobalt ferrite nano composite material.
Embodiment 3: nitrogen content is nitrogen-doped graphene/cobalt ferrite nano composite material (graphite oxide and cobalt ferrite mass ratio the are 1:10) preparation method of 2%, comprises the following steps:
The first step, be that graphite oxide ultrasonic disperse in 50mL absolute ethyl alcohol of 100mg obtains uniform graphene oxide solution by content, ultrasonic time is 3h;
Second step, is dissolved in 3.4443g ferric nitrate and 1.2406g cobalt nitrate in 20mL ethanol and stirs 60min;
3rd step, pours into the mixed salt solution of above-mentioned dissolving in the graphene oxide solution that the first step obtains, and stirs 60min, make it mix;
4th step, joins the 3rd step and obtains in mixed system, again stir 90min, make it be uniformly dispersed by the urea of 20g;
5th step, be transferred in water heating kettle by the above-mentioned mixed solution mixed and carry out hydro-thermal reaction, reaction temperature is 200 DEG C, and the reaction time is 12h;
6th step, carries out centrifugation by the 5th step product, and obtains nitrogen-doped graphene/cobalt ferrite nano composite material after repeatedly spending deionized water, drying.
Prepared nitrogen-doped graphene/cobalt ferrite Nano-composite materials becomes electrode material, electro-chemical test is carried out to it, Fig. 3 is the cyclic voltammetry figure of its sweep speed in acidity from 1 ~ 100mV/s, when sweeping speed for 1mV/s, its ratio capacitance, up to 318F/g, is greatly increased compared with the electrode material of one-component, and it is when current density is 100mA/g, circulation 5000 circle, coulombic efficiency maintains about 100% always, and ratio capacitance sustainment rate remains on about 90%.
Comparative example: compared with embodiment 3, hydrothermal temperature just in the 5th step changes 80 DEG C into, and through centrifuge washing, the amount of gained nitrogen-doped graphene/cobalt ferrite composite is less, without obvious crystal formation in XRD collection of illustrative plates, chemical property is embodiment 3 poor (ratio capacitance only has 207F/g) comparatively.Because reaction temperature is too low, graphite oxide is not completely reduced, and N doping is incomplete, and cobalt ferrite is not also successfully prepared.
Claims (7)
1. nitrogen-doped graphene/cobalt ferrite nano composite material, is characterized in that described composite is made up of matrix material nitrogen-doped graphene and cobalt ferrite, and wherein, the mass ratio of matrix material nitrogen-doped graphene and cobalt ferrite is 1:3 ~ 1:10; In described matrix material nitrogen-doped graphene, the doping of nitrogen is 1 ~ 2%, and described composite is prepared by following steps:
The first step: graphite oxide is carried out in absolute ethyl alcohol ultrasonic disperse and obtain finely dispersed graphene oxide solution;
Second step: ferric nitrate and cobalt nitrate are dissolved in absolute ethyl alcohol, and stir and cause it and dissolve completely;
3rd step: the mixed salt solution of dissolving is poured in the graphene oxide solution that the first step obtains, and stir and make it mix;
4th step: urea is joined the 3rd step and obtain in mixed system, again stir, make it be uniformly dispersed, wherein, the mass ratio of urea and graphite oxide is 100:1 ~ 200:1;
5th step: finely dispersed mixed solution in above-mentioned 4th step is transferred in water heating kettle, carries out hydro-thermal reaction at 120 ~ 200 DEG C;
6th step: the 5th step product is carried out centrifugation, and after repeatedly spending deionized water, drying, obtain nitrogen-doped graphene/cobalt ferrite nano composite material.
2. a preparation method for nitrogen-doped graphene/cobalt ferrite nano composite material, is characterized in that comprising the steps:
The first step: graphite oxide is carried out in absolute ethyl alcohol ultrasonic disperse and obtain finely dispersed graphene oxide solution;
Second step: ferric nitrate and cobalt nitrate are dissolved in absolute ethyl alcohol, and stir and cause it and dissolve completely;
3rd step: the mixed salt solution of dissolving is poured in the graphene oxide solution that the first step obtains, and stir and make it mix;
4th step: urea is joined the 3rd step and obtain in mixed system, again stir, make it be uniformly dispersed, wherein, the mass ratio of urea and graphite oxide is 100:1 ~ 200:1;
5th step: finely dispersed mixed solution in above-mentioned 4th step is transferred in water heating kettle, carries out hydro-thermal reaction at 120 ~ 200 DEG C;
6th step: the 5th step product is carried out centrifugation, and after repeatedly spending deionized water, drying, obtain nitrogen-doped graphene/cobalt ferrite nano composite material.
3. the preparation method of nitrogen-doped graphene according to claim 2/cobalt ferrite nano composite material, is characterized in that the ultrasonic disperse time described in the first step is 1 ~ 3h.
4. the preparation method of nitrogen-doped graphene according to claim 2/cobalt ferrite nano composite material, it is characterized in that the mol ratio of the ferric nitrate described in second step and cobalt nitrate is 2:1, described graphite oxide and the mass ratio of cobalt ferrite are 1:3 ~ 1:10, and the dispersed with stirring time is 10 ~ 60min.
5. the preparation method of nitrogen-doped graphene according to claim 2/cobalt ferrite nano composite material, is characterized in that the dispersed with stirring time described in the 3rd step is 10 ~ 60min.
6. the preparation method of nitrogen-doped graphene according to claim 2/cobalt ferrite nano composite material, is characterized in that the mixing time described in the 4th step is 30 ~ 90min.
7. the preparation method of nitrogen-doped graphene according to claim 2/cobalt ferrite nano composite material, is characterized in that the hydro-thermal reaction time described in the 5th step is 12 ~ 20h.
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| CN105565307A (en) * | 2016-01-12 | 2016-05-11 | 山东佳星环保科技有限公司 | Nitrogen doped graphene material and preparation method thereof |
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