CN104966625A - N-doped porous carbon/NiO composite material and preparation method therefor - Google Patents
N-doped porous carbon/NiO composite material and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a N-doped porous carbon/NiO composite material and a preparation method therefor. The preparation method comprises the following steps: first, coal-based polyaniline is prepared through a in-situ polymerization method; second, nickle powder and coal-based polyaniline are mixed uniformly to obtain a mixture, the mixture is subjected to pyrolysis and a N-doped porous carbon/Ni composite material is obtained; third, hydrogen peroxide and sulfuric acid are mixed uniformly and a mixed solution A is obtained; fourth, the N-doped porous carbon/Ni composite material is added in the mixed solution A, after mixing processing is carried out, the pH value is adjusted to 7-8 through ammonium hydroxide, next a urea aqueous solution is added drop by drop, insulation stirring is carried out, pumping filtration is carried out after cooling, a filter cake is washed, the filter cake is calcined, and a N-doped porous carbon/NiO composite material is obtained. N-doped porous carbon in the N-doped porous carbon/NiO composite material prepared through the method shows pore structure characteristics of meso pores as the main and macropores as the part and NiO in the composite material exists in a form of nanosheets or nanospheres.
Description
Technical field
The invention belongs to energy and material, functional material and mineral machining cross technical field, be specifically related to one and mix N porous carbon/NiO composite material and preparation method thereof.
Background technology
Ultracapacitor because in parallelly with storage battery accessory power supply can be made, make up storage battery the startup of electric automobile, braking and climbing time power deficiency, play the effect of balance accumulator load, increasing storage battery service life, and be widely studied.The electrode material of ultracapacitor directly affects the performance of ultracapacitor, and therefore the preparation of the electrode material of high specific capacitance, high-specific-power and specific energy, stable charge/discharge just becomes the key of dealing with problems.At present, the electrode material of ultracapacitor is mainly divided into: material with carbon element, metal oxide and conducting polymer.The former is electric double layer capacitance energy storage mechnism, is fake capacitance energy storage mechnism both rear.Wherein, material with carbon element conductivity and good cycling stability, resistant to chemical media, cheap but ratio capacitance and energy density lower.Metal oxide ratio capacitance is high, but poorly conductive, compact structure, electromotive force window narrows and expensive.If will both compounds, can obtain and have electric double layer capacitance and fake capacitance characteristic concurrently, have more high specific capacitance and energy density, cost is lower, combination property is good nanocarbon/metal oxide combination electrode material.In addition, the element doping such as N, P, B of material with carbon element also can obviously improve its capacitive property.
Current business-like electrode material mainly concentrates on the porous carbon materials of easy suitability for industrialized production, mainly contains active carbon, activated carbon fiber, carbon nano-tube, charcoal-aero gel and template carbon etc.Coal is the mixture containing the large condensed ring organic compound of major part and fraction inorganic mineral, is used for the preparation of material with carbon element because abundance, cost are low by numerous scholar.In the catalytic hydrogenation direct liquefaction technique of coal, meeting association has the coke class byproduct of certain pore structure.If not hydrogenation, directly metal catalytic high temperature pyrolysis is carried out to coal, pore structure can be obtained and slightly improve but still undesirable porous carbon major product.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides one to mix the preparation method of N porous carbon/NiO composite material.The method for raw material, regulates the pore structure of carbon with the Coal-based Polyaniline of in-situ polymerization, and synchronously realizes the doping of N.The doping of mixing N in N porous carbon/NiO composite material adopting the method to prepare is 1.422wt% ~ 2.238wt%, mixes N porous carbon and presents based on mesoporous, and with the pore property of part macropore, NiO exists with the form of nanometer sheet or nanosphere.What adopt the method to prepare mixes N porous carbon/NiO composite material as active electrode material, what prepare mixes N porous carbon/NiO electrode material under the constant current density of 2.5A/g, its one pole ratio capacitance can reach more than 280F/g, energy density can reach more than 98Wh/kg, and power density reaches more than 2056W/kg.
For solving the problems of the technologies described above, the technical solution used in the present invention is: one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, comprises the following steps:
Step one, employing situ aggregation method prepare Coal-based Polyaniline;
Step 2, by the Coal-based Polyaniline of preparation in nickel powder and step one according to 1:(1 ~ 2) mass ratio mix and obtain mixture, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 2h ~ 3h under the condition of 800 DEG C ~ 1000 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 3, be that the sulfuric acid of 3mol/L ~ 4mol/L is according to 1:(1 ~ 2 by hydrogen peroxide and concentration) volume ratio mix, obtain mixed solution A;
Step 4, add in mixed solution A described in step 3 by mixing N porous carbon/Ni composite material described in step 2, stir process 5min ~ 10min at 80 DEG C ~ 90 DEG C, then the pH value of the mixed solution after stir process is regulated to be 7 ~ 8 with ammoniacal liquor, then be to the mixed solution and dripping aqueous solution of urea after adjust ph in temperature under the stirring condition of 80 DEG C ~ 90 DEG C, dropwise follow-up continuous insulated and stirred 3h ~ 4h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 2h ~ 3h under 380 DEG C ~ 420 DEG C conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution A is for mixing 10 ~ 20 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step 2, the mol ratio of nickel powder is (3 ~ 5): 1.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the preparation method of Coal-based Polyaniline described in step one comprises the following steps:
Step 101, aniline, concentrated hydrochloric acid and water mixed obtain mixed solution B, in described mixed solution B, add coal dust, at 25 DEG C ~ 35 DEG C, stir swelling 2h ~ 3h, obtain swelling coal sample; The volume of described concentrated hydrochloric acid is 1.5 ~ 3 times of aniline quality, and the volume of water is 2.5 ~ 6 times of aniline quality, and wherein the unit of volume is mL, and the unit of quality is g; The mass ratio of described coal dust and aniline is 1:(1 ~ 2);
Step 102, in 0 DEG C ~ 5 DEG C ice-water baths, ammonium persulfate aqueous solution is dripped under agitation in coal sample swelling described in step 101, dropwising rear continuation under the ice-water bath condition of 0 DEG C ~ 5 DEG C stirs 6h ~ 8h, suction filtration, the filter cake that washing suction filtration obtains, then grind after the filter cake vacuumize after washing, sieve and obtain Coal-based Polyaniline; In described ammonium persulfate aqueous solution, in ammonium persulfate and step 101, the mol ratio of aniline is 1:1.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the mass concentration of concentrated hydrochloric acid described in step 101 is 37%.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the concentration of ammonium persulfate aqueous solution described in step 102 is 0.30g/mL ~ 0.48g/mL, and the rate of addition of ammonium persulfate aqueous solution is 1mL/min ~ 3mL/min.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, vacuum drying temperature described in step 102 is 50 DEG C ~ 70 DEG C, and the vacuum drying time is 10h ~ 12h.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the sieve number of sieving described in step 102 is 200 orders.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the mass concentration of hydrogen peroxide described in step 3 is 30%.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the mass percent concentration of ammoniacal liquor described in step 4 is 20% ~ 30%.
Above-mentioned one mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the concentration of aqueous solution of urea described in step 4 is 3mol/L ~ 5mol/L.
In addition, present invention also offers a kind of adopt said method to prepare mix N porous carbon/NiO composite material.
The present invention compared with prior art has the following advantages:
1, the present invention is with the Coal-based Polyaniline of in-situ polymerization for raw material, regulates the pore structure of carbon, and synchronously realizes the doping of N.Wherein, polyaniline cracking easier in the large molecule of the condensed ring of coal, and also the gaseous material that its cracking produces can to the further reaming of carbon skeleton.In addition, polyaniline can simultaneously as Carbon and nitrogen sources, and as carbon source, the gas-phase carbon that polyaniline cracking produces or remaining carbon skeleton all have larger contribution to target product porous carbon;-N=in polyaniline molecule chain and-NH-can be used as nitrogenous source, realizes adulterating to the N of porous carbon.
2, the present invention adopts situ aggregation method to prepare Coal-based Polyaniline, first by swelling hole or surface of aniline being introduced coal, the aqueous hydrochloric acid solution of aniline has good swelling action to coal, can by large for even fragrant for the hole of coal synusia support, cause aniline in-situ polymerization again, can obtain the Coal-based Polyaniline of certain inierpeneirating network structure, this porous carbon obtaining hole IPN to follow-up pyrolysis is very favourable.
3, the present invention's method of adopting liquid phase chemical to be oxidized, precipitate after nickel ion further again, in the hole being finally deposited in porous carbon with the form of NiO nano particle or the outer surface of porous carbon, Raney nickel is transformed into the NiO with fake capacitance characteristic, achieves the comprehensive utilization of catalyst.
4, the doping of mixing N in N porous carbon/NiO composite material adopting method of the present invention to prepare is 1.422wt% ~ 2.238wt%, mixing N porous carbon presents based on mesoporous, with the pore property of part macropore, NiO exists with the form of nanometer sheet or nanosphere, NiO nanometer sheet is inserted the macropore of porous carbon or is attached to the outer surface of porous carbon, and NiO nanosphere embeds the macropore, mesoporous or be attached to the outer surface of porous carbon of porous carbon.
What 5, adopt method of the present invention to prepare mixes N porous carbon/NiO composite material as active electrode material, what prepare mixes N porous carbon/NiO electrode material under the constant current density of 2.5A/g, its one pole ratio capacitance can reach more than 280F/g, energy density can reach more than 98Wh/kg, and power density reaches more than 2056W/kg.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the SEM figure mixing N porous carbon/Ni composite material prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM figure mixing N porous carbon/NiO composite material prepared by the embodiment of the present invention 1.
Fig. 3 is that N porous carbon/Ni composite material of mixing prepared by the embodiment of the present invention 1 is schemed with the XRD mixing N porous carbon/NiO composite material.
Fig. 4 is the SEM figure mixing N porous carbon/Ni composite material prepared by the embodiment of the present invention 2.
Fig. 5 is the SEM figure mixing N porous carbon/NiO composite material prepared by the embodiment of the present invention 2, and multiplication factor is 50,000 times.
Fig. 6 is the SEM figure mixing N porous carbon/NiO composite material prepared by the embodiment of the present invention 2, and multiplication factor is 100,000 times.
Fig. 7 is the graph of pore diameter distribution of mixing N porous carbon/NiO composite material prepared by the embodiment of the present invention 2.
Fig. 8 is that N porous carbon/Ni composite material of mixing prepared by the embodiment of the present invention 2 is schemed with the XRD mixing N porous carbon/NiO composite material.
Fig. 9 be prepare with the embodiment of the present invention 1 and embodiment 2 mix the cyclic voltammetry curve that N porous carbon/NiO composite material is electrode material prepared by active electrode material.
Figure 10 is the N porous carbon/NiO composite material of mixing prepared with the embodiment of the present invention 1 and embodiment 2 is the constant current charge-discharge curve of electrode material under 5mA prepared by active electrode material.
Embodiment
Embodiment 1
The preparation method mixing N porous carbon/NiO composite material of the present embodiment comprises:
Step one, employing situ aggregation method prepare Coal-based Polyaniline, specifically comprise the following steps:
Step 101,10g aniline, 30mL concentrated hydrochloric acid (mass concentration is 37%) and 60mL water mixed obtain mixed solution B, in described mixed solution B, add 10g coal dust, at 30 DEG C, stir swelling 3h, obtain swelling coal sample;
Step 102, in 3 DEG C of ice-water baths, the ammonium persulfate aqueous solution that 80mL concentration is 0.30g/mL is dripped under agitation in coal sample swelling described in step 101, rate of addition is 2mL/min, dropwise rear continuation and stir 6h under the ice-water bath condition of 3 DEG C, suction filtration, the filter cake that washing suction filtration obtains, then grinds after the filter cake vacuumize after washing, crosses 200 eye mesh screens and obtains Coal-based Polyaniline; Described vacuum drying temperature is 50 DEG C, and the vacuum drying time is 12h;
Step 2, to be mixed by the Coal-based Polyaniline of preparation in nickel powder and step one obtain mixture according to the mass ratio of 1:2, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 3h under the condition of 1000 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 3, the sulfuric acid being 4.0mol/L by hydrogen peroxide (mass concentration is 30%) and concentration mix according to the volume ratio of 1:1, obtain mixed solution A;
Step 4, add in mixed solution A described in step 3 by mixing N porous carbon/Ni composite material described in step 2, stir process 5min at 90 DEG C, then the pH value of the mixed solution after stir process is regulated to be 8 with the ammoniacal liquor that mass percent concentration is 25%, then in temperature be under the stirring condition of 90 DEG C to the mixed solution and dripping concentration after adjust ph be the aqueous solution of urea of 4mol/L, dropwise follow-up continuous insulated and stirred 4h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 3h under 400 DEG C of conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution A is for mixing 10 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step 2, the mol ratio of nickel powder is 4:1.
Fig. 1 is the SEM figure mixing N porous carbon/Ni composite material prepared by the present embodiment, Fig. 2 is the SEM figure mixing N porous carbon/NiO composite material prepared by the present embodiment, as can be seen from the figure, prepared by the present embodiment N porous carbon of mixing mixed in N porous carbon/Ni composite material presents based on mesoporous, with the pore property of part macropore, NiO exists with the form of nanometer sheet, inserts the macropore of porous carbon, or invests the outer surface of porous carbon.Fig. 3 be the present embodiment prepare mix N porous carbon/Ni composite material (in figure a curve) and mix N porous carbon/NiO composite material (in figure b curve) XRD figure, as can be seen from the figure, the Ni successful transformation mixed in N porous carbon/Ni composite material has become NiO.
Embodiment 2
The preparation method mixing N porous carbon/NiO composite material of the present embodiment comprises:
Step one, employing situ aggregation method prepare Coal-based Polyaniline, specifically comprise the following steps:
Step 101,20g aniline, 30mL concentrated hydrochloric acid (mass concentration is 37%) and 50mL water mixed obtain mixed solution B, in described mixed solution B, add 10g coal dust, at 35 DEG C, stir swelling 2h, obtain swelling coal sample;
Step 102, in 0 DEG C of ice-water bath, the ammonium persulfate aqueous solution that 100mL concentration is 0.48g/mL is dripped under agitation in coal sample swelling described in step 101, rate of addition is 3mL/min, dropwise rear continuation and stir 8h under the ice-water bath condition of 0 DEG C, suction filtration, the filter cake that washing suction filtration obtains, then grinds after the filter cake vacuumize after washing, crosses 200 eye mesh screens and obtains Coal-based Polyaniline; Described vacuum drying temperature is 70 DEG C, and the vacuum drying time is 10h;
Step 2, to be mixed by the Coal-based Polyaniline of preparation in nickel powder and step one obtain mixture according to the mass ratio of 1:2, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 3h under the condition of 1000 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 3, the sulfuric acid being 3mol/L by hydrogen peroxide (mass concentration is 30%) and concentration mix according to the volume ratio of 1:2, obtain mixed solution A;
Step 4, add in mixed solution A described in step 3 by mixing N porous carbon/Ni composite material described in step 2, stir process 8min at 85 DEG C, then the pH value of the mixed solution after stir process is regulated to be 7 with the ammoniacal liquor that mass percent concentration is 20%, then in temperature be under the stirring condition of 85 DEG C to the mixed solution and dripping concentration after adjust ph be the aqueous solution of urea of 3mol/L, dropwise follow-up continuous insulated and stirred 3h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 2h under 420 DEG C of conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution A is for mixing 20 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step 2, the mol ratio of nickel powder is 3:1.
Fig. 4 is the SEM figure mixing N porous carbon/Ni composite material prepared by the present embodiment, Fig. 5 is the SEM figure mixing N porous carbon/NiO composite material prepared by the present embodiment, multiplication factor is 50,000 times, Fig. 6 is the SEM figure mixing N porous carbon/NiO composite material of preparation, multiplication factor is 100,000 times, as can be seen from the figure, prepared by the present embodiment N porous carbon of mixing mixed in N porous carbon/Ni composite material presents based on mesoporous, hole is abundant and orderly, with the pore property of part macropore, NiO exists with the form of nanosphere, embed porous carbon macropore in and mesoporous in, or be attached to the outer surface of porous carbon.Fig. 7 is the graph of pore diameter distribution of mixing N porous carbon/NiO composite material prepared by the present embodiment, can draw from the data figure, preparation mix N porous carbon to be less than the mesoporous of 50nm and micropore.By the initial data of specific surface test through theory calculate, show that the BET average pore size of mixing N porous carbon be 19.8nm, BET specific surface is 627.5m
2/ g, t-Plot Micropore volume reaches 0.253cm
3/ g, what confirm preparation further mixes N porous carbon based on mesoporous, and its specific surface is larger.Fig. 8 be the present embodiment prepare mix N porous carbon/Ni composite material (in figure a curve) and mix N porous carbon/NiO composite material (in figure b curve) XRD figure, as can be seen from the figure, the Ni successful transformation mixed in N porous carbon/Ni composite material has become NiO.
Embodiment 3
The preparation method mixing N porous carbon/NiO composite material of the present embodiment comprises:
Step one, employing situ aggregation method prepare Coal-based Polyaniline, specifically comprise the following steps:
Step 101,10g aniline, 25mL concentrated hydrochloric acid (mass concentration is 37%) and 55mL water mixed obtain mixed solution B, in described mixed solution B, add 8g coal dust, at 25 DEG C, stir swelling 2.5h, obtain swelling coal sample;
Step 102, in 5 DEG C of ice-water baths, the ammonium persulfate aqueous solution that 60mL concentration is 0.40g/mL is dripped under agitation in coal sample swelling described in step 101, rate of addition is 1mL/min, dropwise rear continuation and stir 7h under the ice-water bath condition of 5 DEG C, suction filtration, the filter cake that washing suction filtration obtains, then grinds after the filter cake vacuumize after washing, crosses 200 eye mesh screens and obtains Coal-based Polyaniline; Described vacuum drying temperature is 60 DEG C, and the vacuum drying time is 11h;
Step 2, to be mixed by the Coal-based Polyaniline of preparation in nickel powder and step one obtain mixture according to the mass ratio of 1:1.5, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 3h under the condition of 800 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 3, the sulfuric acid being 4mol/L by hydrogen peroxide (mass concentration is 30%) and concentration mix according to the volume ratio of 1:1.5, obtain mixed solution A;
Step 4, add in mixed solution A described in step 3 by mixing N porous carbon/Ni composite material described in step 2, stir process 10min at 80 DEG C, then the pH value of the mixed solution after stir process is regulated to be 7.5 with the ammoniacal liquor that mass percent concentration is 30%, then in temperature be under the stirring condition of 80 DEG C to the mixed solution and dripping concentration after adjust ph be the aqueous solution of urea of 5mol/L, dropwise follow-up continuous insulated and stirred 3.5h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 2.5h under 380 DEG C of conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution A is for mixing 15 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step 2, the mol ratio of nickel powder is 5:1.
Prepared by the present embodiment mix, and N porous carbon/NiO composite material SEM schemes and XRD schemes similar to embodiment 1, mixes N porous carbon and presents based on mesoporous, with the pore property of part macropore; NiO exists with the form of nanometer sheet, and NiO nanometer sheet is inserted in macropore, or is attached to porous carbon outer surface.
Embodiment 4
The preparation method mixing N porous carbon/NiO composite material of the present embodiment comprises:
Step one, employing situ aggregation method prepare Coal-based Polyaniline, specifically comprise the following steps:
Step 101,10g aniline, 25mL concentrated hydrochloric acid (mass concentration is 37%) and 55mL water mixed obtain mixed solution B, in described mixed solution B, add 6g coal dust, at 30 DEG C, stir swelling 2.5h, obtain swelling coal sample;
Step 102, in 2 DEG C of ice-water baths, the ammonium persulfate aqueous solution that 60mL concentration is 0.40g/mL is dripped under agitation in coal sample swelling described in step 101, rate of addition is 1mL/min, dropwise rear continuation and stir 6h under the ice-water bath condition of 2 DEG C, suction filtration, the filter cake that washing suction filtration obtains, then grinds after the filter cake vacuumize after washing, crosses 200 eye mesh screens and obtains Coal-based Polyaniline; Described vacuum drying temperature is 70 DEG C, and the vacuum drying time is 12h;
Step 2, to be mixed by the Coal-based Polyaniline of preparation in nickel powder and step one obtain mixture according to the mass ratio of 1:1, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 2.5h under the condition of 900 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 3, the sulfuric acid being 3.8mol/L by hydrogen peroxide (mass concentration is 30%) and concentration mix according to the volume ratio of 1:1.6, obtain mixed solution A;
Step 4, add in mixed solution A described in step 3 by mixing N porous carbon/Ni composite material described in step 2, stir process 10min at 85 DEG C, then the pH value of the mixed solution after stir process is regulated to be 7 with the ammoniacal liquor that mass percent concentration is 25%, then in temperature be under the stirring condition of 85 DEG C to the mixed solution and dripping concentration after adjust ph be the aqueous solution of urea of 5mol/L, dropwise follow-up continuous insulated and stirred 3.5h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 2h under 400 DEG C of conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution A is for mixing 18 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step 2, the mol ratio of nickel powder is 4:1.
Prepared by the present embodiment mix, and N porous carbon/NiO composite material SEM schemes and XRD schemes similar to embodiment 2, mixes N porous carbon and presents based on mesoporous, with the pore property of part macropore; NiO exists with the form of nanosphere, NiO nanosphere to embed in macropore and mesoporous in, or be attached to the outer surface of porous carbon.
Comparative example 1
Employing polyaniline is Carbon and nitrogen sources, and N porous carbon/NiO composite material is mixed in preparation, and concrete grammar is:
Step one, nickel powder and polyaniline to be mixed according to the mass ratio of 1:2 and obtain mixture, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 3h under the condition of 1000 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 2, the sulfuric acid being 4mol/L by hydrogen peroxide (mass concentration is 30%) and concentration mix according to the volume ratio of 1:1, obtain mixed solution;
Step 3, add in mixed solution described in step 2 by mixing N porous carbon/Ni composite material described in step one, stir process 5min at 90 DEG C, then the pH value of the mixed solution after stir process is regulated to be 8 with the ammoniacal liquor that mass percent concentration is 25%, then in temperature be under the stirring condition of 90 DEG C to the mixed solution and dripping concentration after adjust ph be the aqueous solution of urea of 4mol/L, dropwise follow-up continuous insulated and stirred 4h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 3h under 400 DEG C of conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution is for mixing 10 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step one, the mol ratio of nickel powder is 4:1.
Comparative example 2
Employing coal dust is Carbon and nitrogen sources, and N porous carbon/NiO composite material is mixed in preparation, and concrete grammar is:
Step one, nickel powder and coal dust to be mixed according to the mass ratio of 1:2 and obtain mixture, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 3h under the condition of 1000 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 2, the sulfuric acid being 4mol/L by hydrogen peroxide (mass concentration is 30%) and concentration mix according to the volume ratio of 1:1, obtain mixed solution;
Step 3, add in mixed solution described in step 2 by mixing N porous carbon/Ni composite material described in step one, stir process 5min at 90 DEG C, then the pH value of the mixed solution after stir process is regulated to be 8 with the ammoniacal liquor that mass percent concentration is 25%, then in temperature be under the stirring condition of 90 DEG C to the mixed solution and dripping concentration after adjust ph be the aqueous solution of urea of 4mol/L, dropwise follow-up continuous insulated and stirred 4h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 3h under 400 DEG C of conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution is for mixing 10 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step one, the mol ratio of nickel powder is 4:1.
The nitrogen element content mixing N porous carbon/NiO composite material of table 1 elemental analyser test
As can be seen from Table 1, the N doping of mixing N porous carbon/NiO composite material adopting method of the present invention to prepare is 1.422wt% ~ 2.238wt%, illustrates that N element is successfully mixed in composite material.Its doping increases along with the increase of polyaniline content in Coal-based Polyaniline, low than comparative example 1, than the height of comparative example 2.
Electrode material prepared by the N porous carbon/NiO composite material of mixing adopting the embodiment of the present invention 1 to embodiment 4 and comparative example 1 and comparative example 2 to prepare, and carries out electrochemical property test to the electrode material of preparation:
The preparation method of electrode material: by active electrode material, conductive agent and bonding agent mass ratio be 80:15:5 make electrode slice, N porous carbon/NiO composite material of mixing prepared by the embodiment of the present invention 1 to embodiment 4 and comparative example 1 and comparative example 2 is ground rear mistake 200 mesh sieve respectively, using screenings as active electrode material, granule conductive black Supper-p is conductive agent, Kynoar (PVDF) is bonding agent, N, dinethylformamide (DMF) is solvent, disperses after mixing N porous carbon/NiO composite material and conductive agent Homogeneous phase mixing with DMF; Then in the material after dispersion, add the DMF solution of PVDF, stir into pasty mixture; Again by pasty mixture even application on the graphite paper of 1cm × 1.5cm; Naturally after drying, at 60 DEG C, vacuumize is to constant weight, obtains mixing N porous carbon/NiO electrode material.
Electrochemical property test: adopt three-electrode system, respectively to mix N porous carbon/NiO electrode material for work electrode, Ag/AgCl (saturated KCl solution) is reference electrode, Pt sheet is auxiliary electrode, the 6mol/L KOH aqueous solution is electrolyte, and AUTOLAB PGSTAT 302N type electrochemical workstation carries out cyclic voltammetric and constant current charge-discharge test.The potential range of cyclic voltammetry is-1.0V ~ 0.4V, sweeps speed for 50mV/s; Constant current charge-discharge measuring current is constant in 5mA, potential range-1.4V ~ 0.4V.Fig. 9 mixes for what prepare with embodiment 1 (in figure a curve) and embodiment 2 (in figure b curve) the cyclic voltammetry curve that N porous carbon/NiO composite material is electrode material prepared by active electrode material, as can be seen from the figure, two kinds of rectangular characteristic of mixing the cyclic voltammetry curve of N porous carbon/NiO composite material are obvious, all show obvious electric double layer capacitance feature, this mixes the contribution of N porous carbon to electric capacity.In addition, two cyclic voltammetry curves all have an oxidation peak near-0.8V, have a reduction peak, correspond to the oxidation of NiO, reduction process respectively near 0.1V, reflect the fake capacitance feature of NiO and the contribution to electric capacity thereof.Figure 10 for the N porous carbon/NiO composite material of mixing prepared with embodiment 1 (in figure a curve) and embodiment 2 (in figure b curve) be the constant current charge-discharge curve of electrode material under 5mA prepared by active electrode material, as can be seen from the figure, article two, constant current charge-discharge curve all has an oxidation peak near-0.8V, a reduction peak is had near 0.1V, correspond to the oxidation of NiO, reduction process respectively, this is consistent with cyclic voltammetry result.Reflect the contribution of the fake capacitance feature of NiO and the electric capacity to composite material thereof.In addition, the charging process of two curves and discharge process have certain symmetry, reflect and mix the electric double layer capacitance feature of N porous carbon and the contribution to electric capacity thereof.
Can quantitatively calculate ratio capacitance, energy density and power density by constant current charge-discharge curve, computing formula is:
C
s＝I△t/m△E (1)
E
s＝1000C
s(△E
2)/7200 (2)
P
s＝3600E
s/△t (3)
Wherein, C
sfor ratio capacitance, unit is F/g; I is discharging current, and unit is A; M is the quality of the active material on electrode, and unit is g; △ E is the difference of charge cutoff voltage and discharge cut-off voltage, and unit is V; △ t is discharge time, and unit is s; E
sfor energy density, unit is Wh/kg; P
sfor power density, unit is W/kg.
Result of calculation sees the following form 2.
The result of calculation (constant current density is 2.5A/g) of table 2 constant current charge-discharge test
| Mix N porous carbon/NiO composite material | Ratio capacitance (F/g) | Energy density (Wh/kg) | Power density (W/kg) |
| Embodiment 1 | 312.3 | 125.6 | 3479.1 |
| Embodiment 2 | 286.3 | 112.2 | 2868.9 |
| Embodiment 3 | 280.5 | 106.0 | 2086.7 |
| Embodiment 4 | 283.0 | 98.6 | 2056.6 |
| Comparative example 1 | 173.4 | 72.1 | 1754.8 |
| Comparative example 2 | 145.1 | 58.3 | 1256.0 |
As can be seen from Table 2, what adopt method of the present invention to prepare mixes N porous carbon/NiO composite material as active electrode material, what prepare mixes N porous carbon/NiO electrode material under the constant current density of 2.5A/g, its one pole ratio capacitance can reach more than 280F/g, energy density can reach more than 98Wh/kg, and power density reaches more than 2056W/kg.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent structure change, all still belong in the protection range of technical solution of the present invention.
Claims (10)
1. mix a preparation method for N porous carbon/NiO composite material, it is characterized in that, comprise the following steps:
Step one, employing situ aggregation method prepare Coal-based Polyaniline;
Step 2, by the Coal-based Polyaniline of preparation in nickel powder and step one according to 1:(1 ~ 2) mass ratio mix and obtain mixture, by described mixture in a nitrogen atmosphere, temperature is pyrolysis 2h ~ 3h under the condition of 800 DEG C ~ 1000 DEG C, obtains mixing N porous carbon/Ni composite material after cooling;
Step 3, be that the sulfuric acid of 3mol/L ~ 4mol/L is according to 1:(1 ~ 2 by hydrogen peroxide and concentration) volume ratio mix, obtain mixed solution A;
Step 4, add in mixed solution A described in step 3 by mixing N porous carbon/Ni composite material described in step 2, stir process 5min ~ 10min at 80 DEG C ~ 90 DEG C, then the pH value of the mixed solution after stir process is regulated to be 7 ~ 8 with ammoniacal liquor, then be to the mixed solution and dripping aqueous solution of urea after adjust ph in temperature under the stirring condition of 80 DEG C ~ 90 DEG C, dropwise follow-up continuous insulated and stirred 3h ~ 4h, suction filtration after cooling, the filter cake that washing suction filtration obtains, again the filter cake after washing is calcined 2h ~ 3h under 380 DEG C ~ 420 DEG C conditions, take out with after stove cooling, obtain mixing N porous carbon/NiO composite material, the volume of described mixed solution A is for mixing 10 ~ 20 times of the quality of N porous carbon/Ni composite material, and wherein the unit of quality is g, and the unit of volume is mL, in described aqueous solution of urea, in urea and step 2, the mol ratio of nickel powder is (3 ~ 5): 1.
2. one according to claim 1 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the preparation method of Coal-based Polyaniline described in step one comprises the following steps:
Step 101, aniline, concentrated hydrochloric acid and water mixed obtain mixed solution B, in described mixed solution B, add coal dust, at 25 DEG C ~ 35 DEG C, stir swelling 2h ~ 3h, obtain swelling coal sample; The volume of described concentrated hydrochloric acid is 1.5 ~ 3 times of aniline quality, and the volume of water is 2.5 ~ 6 times of aniline quality, and wherein the unit of volume is mL, and the unit of quality is g; The mass ratio of described coal dust and aniline is 1:(1 ~ 2);
Step 102, in 0 DEG C ~ 5 DEG C ice-water baths, ammonium persulfate aqueous solution is dripped under agitation in coal sample swelling described in step 101, dropwising rear continuation under the ice-water bath condition of 0 DEG C ~ 5 DEG C stirs 6h ~ 8h, suction filtration, the filter cake that washing suction filtration obtains, then grind after the filter cake vacuumize after washing, sieve and obtain Coal-based Polyaniline; In described ammonium persulfate aqueous solution, in ammonium persulfate and step 101, the mol ratio of aniline is 1:1.
3. one according to claim 2 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the mass concentration of concentrated hydrochloric acid described in step 101 is 37%.
4. one according to claim 2 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the concentration of ammonium persulfate aqueous solution described in step 102 is 0.30g/mL ~ 0.48g/mL, and the rate of addition of ammonium persulfate aqueous solution is 1mL/min ~ 3mL/min.
5. one according to claim 2 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, vacuum drying temperature described in step 102 is 50 DEG C ~ 70 DEG C, and the vacuum drying time is 10h ~ 12h.
6. one according to claim 2 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the sieve number of sieving described in step 102 is 200 orders.
7. one according to claim 1 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the mass concentration of hydrogen peroxide described in step 3 is 30%.
8. one according to claim 1 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the mass percent concentration of ammoniacal liquor described in step 4 is 20% ~ 30%.
9. one according to claim 1 mixes the preparation method of N porous carbon/NiO composite material, it is characterized in that, the concentration of aqueous solution of urea described in step 4 is 3mol/L ~ 5mol/L.
10. what employing method as described in claim arbitrary in claim 1 to 9 prepared mixes N porous carbon/NiO composite material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845454A (en) * | 2016-03-28 | 2016-08-10 | 西安科技大学 | Method for preparing N-doped porous carbon/ferric oxide compound powder |
| CN106348276A (en) * | 2016-08-23 | 2017-01-25 | 西安科技大学 | Combined preparation method of carbon micro-nanotubes and N-doped porous carbon/nickel manganese oxide |
| CN108172413A (en) * | 2017-12-25 | 2018-06-15 | 温州大学新材料与产业技术研究院 | The preparation method and purposes of a kind of three-dimensional globular nitrogen-doped porous carbon material and nickel nickel composite material |
| CN108538610A (en) * | 2018-02-06 | 2018-09-14 | 温州大学新材料与产业技术研究院 | A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material |
| CN110342492A (en) * | 2019-06-13 | 2019-10-18 | 兰溪市立顺生物有限公司 | A kind of preparation method of nitrating oxygen carbon nanotube/porous charcoal |
| CN111850600A (en) * | 2020-07-17 | 2020-10-30 | 西安怡速安智能科技有限公司 | Formula of anode coating for removing peculiar smell of electrochemical electrode |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201008A (en) * | 2014-09-02 | 2014-12-10 | 中物院成都科学技术发展中心 | Nickel oxide and nitrogen doped carbon nanotube composite electrode materials for super capacitor and production method thereof |
| CN104530646A (en) * | 2014-12-24 | 2015-04-22 | 神华集团有限责任公司 | Coal-based polyaniline antistatic board and preparation method thereof |
-
2015
- 2015-07-31 CN CN201510464778.2A patent/CN104966625B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201008A (en) * | 2014-09-02 | 2014-12-10 | 中物院成都科学技术发展中心 | Nickel oxide and nitrogen doped carbon nanotube composite electrode materials for super capacitor and production method thereof |
| CN104530646A (en) * | 2014-12-24 | 2015-04-22 | 神华集团有限责任公司 | Coal-based polyaniline antistatic board and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| NEMANJA GAVRILOV等: "High-performance charge storage by N-containing nanostructured carbon derived from polyaniline", 《CARBON》 * |
| 汪晓芹等: "煤/聚苯胺导电复合材料导电性能的研究", 《煤炭转化》 * |
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| CN108172413A (en) * | 2017-12-25 | 2018-06-15 | 温州大学新材料与产业技术研究院 | The preparation method and purposes of a kind of three-dimensional globular nitrogen-doped porous carbon material and nickel nickel composite material |
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| CN108538610A (en) * | 2018-02-06 | 2018-09-14 | 温州大学新材料与产业技术研究院 | A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material |
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