CN104966625B - One kind mixes N porous carbons/NiO composites and preparation method thereof - Google Patents
One kind mixes N porous carbons/NiO composites and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the preparation method that one kind mixes N porous carbons/NiO composites, comprise the following steps：First, Coal-based Polyaniline is prepared using situ aggregation method；2nd, nickel powder and Coal-based Polyaniline are well mixed and obtain mixture, be pyrolyzed in a nitrogen atmosphere, obtain mixing N porous carbons/Ni composites；3rd, hydrogen peroxide and sulfuric acid are well mixed, obtain mixed solution A；4th, N porous carbons/Ni composites will be mixed to add in mixed solution A, it is 7~8 to adjust pH value with ammoniacal liquor after stir process, and suction filtration after aqueous solution of urea, insulated and stirred, cooling is then added dropwise, and washs filter cake, calcines filter cake, obtains mixing N porous carbons/NiO composites.The N porous carbons of mixing mixed in N porous carbons/NiO composites for using the method for the present invention to prepare are showed based on mesoporous, with the pore property of part macropore, and NiO exists with nanometer sheet or the form of nanosphere.
Description
Technical field
The invention belongs to energy and material, functional material and mineral machining cross technical field, and in particular to it is porous that one kind mixes N
Carbon/NiO composites and preparation method thereof.
Background technology
Ultracapacitor makes up startup, braking of the battery in electric automobile because that in parallel with battery can make accessory power supply
The deficiency of power during with climbing, plays a part of balance battery load, increasing storage battery service life, and is widely studied.
The electrode material of ultracapacitor directly affects the performance of ultracapacitor, therefore high specific capacitance, high-specific-power and specific energy,
The preparation of the electrode material of stable charge/discharge just turns into the key solved the problems, such as.At present, the electrode material of ultracapacitor is main
It is divided into：Carbon material, metal oxide and conducting polymer.The former is electric double layer capacitance energy storage mechnism, and both rear is fake capacitance storage
Can mechanism.Wherein, carbon material electric conductivity and good cycling stability, resistant to chemical media, cheap but specific capacitance and energy density
It is relatively low.Metal oxide specific capacitance is high, but poorly conductive, and compact structure, potential window are narrow and expensive.If both are answered
Close, can obtain and have electric double layer capacitance and fake capacitance characteristic concurrently, have more high specific capacitance and energy density, cost be relatively low, combination property
Good nanocarbon/metal oxide combination electrode material.In addition, the element doping such as N, P, B of carbon material also can obviously improve its electricity
Capacitive energy.
Current commercialized electrode material focuses primarily upon the porous carbon materials of easy industrialized production, main active charcoal,
NACF, CNT, charcoal-aero gel and template carbon etc..Coal is containing most of big condensed ring organic compound and fraction
The mixture of inorganic mineral, due to abundance, cost is low and is used for the preparation of carbon material by numerous scholars.Add in the catalysis of coal
In hydrogen direct liquefaction technique, the coke class byproduct of certain pore structure can be associated with.If not being hydrogenated with, row metal directly is entered to coal and urged
Change high temperature pyrolysis, can obtain pore structure slightly improves but still undesirable porous carbon major product.
The content of the invention
The technical problems to be solved by the invention be for above-mentioned the deficiencies in the prior art there is provided one kind mix N porous carbons/
The preparation method of NiO composites.This method is using the Coal-based Polyaniline of in-situ polymerization as raw material, to adjust the pore structure of carbon, and
Synchronously realize N doping.Use prepared by this method mix the doping of N in N porous carbons/NiO composites for 1.422wt%~
2.238wt%, mixes N porous carbons and shows based on mesoporous, and with the pore property of part macropore, NiO is with nanometer sheet or receives
The form of rice ball is present.N porous carbons/NiO composites are mixed as active electrode material using prepared by this method, are prepared
Mix N porous carbons/NiO electrode materials under 2.5A/g constant current density, its monopole specific capacitance is up to more than 280F/g, energy
Density reaches more than 2056W/kg up to more than 98Wh/kg, power density.
In order to solve the above technical problems, the technical solution adopted by the present invention is：One kind mixes N porous carbons/NiO composites
Preparation method, it is characterised in that comprise the following steps：
Step 1: preparing Coal-based Polyaniline using situ aggregation method；
Step 2: by the Coal-based Polyaniline prepared in nickel powder and step one according to 1:The mass ratio of (1~2) is well mixed
To mixture, temperature is pyrolysis 2h~3h, cooling under conditions of 800 DEG C~1000 DEG C by the mixture in a nitrogen atmosphere
After obtain mixing N porous carbons/Ni composites；
Step 3: by hydrogen peroxide and concentration for 3mol/L~4mol/L sulfuric acid according to 1:The volume ratio mixing of (1~2) is equal
It is even, obtain mixed solution A；
Added Step 4: N porous carbons/Ni composites will be mixed described in step 2 described in step 3 in mixed solution A,
Stir process 5min~10min at 80 DEG C~90 DEG C, the pH value for then adjusting the mixed solution after stir process with ammoniacal liquor is 7
~8, then in the mixed solution and dripping aqueous solution of urea under temperature is 80 DEG C~90 DEG C of stirring condition to after adjusting pH value,
The follow-up continuous insulated and stirred 3h~4h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained, then the filter cake after washing is existed
2h~3h is calcined under the conditions of 380 DEG C~420 DEG C, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composites；It is described mixed
The volume for closing solution A is 10~20 times of the quality for mixing N porous carbons/Ni composites, and wherein the unit of quality is g, volume
Unit is mL；The mol ratio of urea and nickel powder in step 2 is (3~5) in the aqueous solution of urea:1.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that coal base described in step one
The preparation method of polyaniline comprises the following steps：
Step 101, obtain mixed solution B by aniline, concentrated hydrochloric acid and water are well mixed, added into the mixed solution B
Coal dust, stirring is swelled 2h~3h at 25 DEG C~35 DEG C, obtains being swelled coal sample；The volume of the concentrated hydrochloric acid is aniline quality
1.5~3 times, the volume of water is 2.5~6 times of aniline quality, and the unit of wherein volume is mL, and the unit of quality is g；Institute
The mass ratio for stating coal dust and aniline is 1:(1~2)；
Step 102, in 0 DEG C~5 DEG C ice-water baths, under agitation to be swelled described in step 101 in coal sample be added dropwise
Continue to stir 6h~8h under the conditions of 0 DEG C~5 DEG C of ice-water bath after ammonium persulfate aqueous solution, completion of dropping, suction filtration washs suction filtration
Obtained filter cake, then will grind, sieving obtains Coal-based Polyaniline after the filter cake vacuum drying after washing；The ammonium persulfate water
The mol ratio of ammonium persulfate and aniline in step 101 is 1 in solution:1.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that dense described in step 101
The mass concentration of hydrochloric acid is 37%.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that mistake described in step 102
The concentration of ammonium sulfate solution is 0.30g/mL~0.48g/mL, the rate of addition of ammonium persulfate aqueous solution for 1mL/min~
3mL/min。
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that true described in step 102
The temperature that sky is dried is 50 DEG C~70 DEG C, and the vacuum drying time is 10h~12h.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that mistake described in step 102
The sieve mesh number of sieve is 200 mesh.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that dioxygen described in step 3
The mass concentration of water is 30%.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that ammoniacal liquor described in step 4
Mass percent concentration be 20%~30%.
Above-mentioned one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that urea described in step 4
The concentration of the aqueous solution is 3mol/L~5mol/L.
In addition, mixing N porous carbons/NiO composites present invention also offers what a kind of use above method was prepared.
The present invention has advantages below compared with prior art：
1st, the present invention to adjust the pore structure of carbon, and synchronously realizes mixing for N using the Coal-based Polyaniline of in-situ polymerization as raw material
It is miscellaneous.Wherein, polyaniline is more easy to cracking than the condensed ring macromolecular of coal, and the gaseous material that its cracking is produced can enter one to carbon skeleton
Walk reaming.In addition, polyaniline can be simultaneously as carbon source and nitrogen source, as carbon source, gas-phase carbon or residue that polyaniline cracking is produced
Carbon skeleton all have larger contribution to target product porous carbon；- N=and-NH- in polyaniline molecule chain can be real as nitrogen source
Now the N of porous carbon is adulterated.
2nd, the present invention prepares Coal-based Polyaniline using situ aggregation method, first by be swelled by aniline introduce coal hole or
Surface, the aqueous hydrochloric acid solution of aniline has good swelling action to coal, the even fragrant synusia of the hole of coal can be supportted into big, then trigger
Aniline in-situ polymerization, can obtain the Coal-based Polyaniline of certain inierpeneirating network structure, and this obtains hole IPN to follow-up pyrolysis
Porous carbon is highly beneficial.
3rd, the method that the present invention is aoxidized using liquid phase chemical, will further be precipitated after nickel ion, finally with NiO nanometers
The form of particle be deposited in the hole of porous carbon or porous carbon outer surface, Raney nickel is transformed into fake capacitance characteristic
NiO, realize the comprehensive utilization of catalyst.
4th, use the present invention method prepare mix the doping of N in N porous carbons/NiO composites for 1.422wt%~
2.238wt%, mixes N porous carbons and shows based on mesoporous, and with the pore property of part macropore, NiO is with nanometer sheet or receives
The form of rice ball is present, the macropore of NiO nanometer sheets insertion porous carbon or the outer surface for being attached to porous carbon, the insertion of NiO nanospheres
The macropore of porous carbon, outer surface that is mesoporous or being attached to porous carbon.
5th, N porous carbons/NiO composites are mixed as active electrode material using prepared by the method for the present invention, be prepared into
To mix N porous carbons/NiO electrode materials under 2.5A/g constant current density, its monopole specific capacitance is up to more than 280F/g, energy
Metric density reaches more than 2056W/kg up to more than 98Wh/kg, power density.
With reference to the accompanying drawings and examples, technical scheme is described in further detail.
Brief description of the drawings
Fig. 1 is the SEM for mixing N porous carbons/Ni composites figures prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM for mixing N porous carbons/NiO composites figures prepared by the embodiment of the present invention 1.
Fig. 3 is that the mixing of preparing of the embodiment of the present invention 1 and mixes N porous carbons/NiO composites at N porous carbons/Ni composites
XRD.
Fig. 4 is the SEM for mixing N porous carbons/Ni composites figures prepared by the embodiment of the present invention 2.
Fig. 5 is the SEM for mixing N porous carbons/NiO composites figures prepared by the embodiment of the present invention 2, and multiplication factor is 50,000 times.
Fig. 6 is the SEM for mixing N porous carbons/NiO composites figures 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 for mixing N porous carbons/NiO composites prepared by the embodiment of the present invention 2.
Fig. 8 is that the mixing of preparing of the embodiment of the present invention 2 and mixes N porous carbons/NiO composites at N porous carbons/Ni composites
XRD.
Fig. 9 is to mix N porous carbons/NiO composites as active electrode material using prepared by Example 1 and Example 2 of the present invention
Expect the cyclic voltammetry curve of electrode material prepared.
Figure 10 is to mix N porous carbons/NiO composites as active electrode material using prepared by Example 1 and Example 2 of the present invention
Expect constant current charge-discharge curve of the electrode material prepared under 5mA.
Embodiment
Embodiment 1
The preparation method for mixing N porous carbons/NiO composites of the present embodiment includes：
Step 1: preparing Coal-based Polyaniline using situ aggregation method, following steps are specifically included：
Step 101,10g aniline, 30mL concentrated hydrochloric acids (mass concentration is 37%) and 60mL water mixed
Solution B, 10g coal dusts are added into the mixed solution B, and stirring is swelled 3h at 30 DEG C, obtains being swelled coal sample；
Step 102, in 3 DEG C of ice-water baths, under agitation to be swelled described in step 101 in coal sample be added dropwise 80mL it is dense
Spend the ammonium persulfate aqueous solution for 0.30g/mL, rate of addition is to continue the ice-water bath bar at 3 DEG C after 2mL/min, completion of dropping
6h is stirred under part, then suction filtration, the filter cake that washing suction filtration is obtained will grind after the filter cake vacuum drying after washing, cross 200 mesh sieves
Net obtains Coal-based Polyaniline；The vacuum drying temperature is 50 DEG C, and the vacuum drying time is 12h；
Step 2: by the Coal-based Polyaniline prepared in nickel powder and step one according to 1:2 mass ratio is mixed
Compound, by the mixture in a nitrogen atmosphere, temperature be pyrolyzed after 3h, cooling under conditions of 1000 DEG C obtain mixing N porous carbons/
Ni composites；
Step 3: by hydrogen peroxide (mass concentration is 30%) and concentration for 4.0mol/L sulfuric acid according to 1:1 volume ratio
It is well mixed, obtain mixed solution A；
Added Step 4: N porous carbons/Ni composites will be mixed described in step 2 described in step 3 in mixed solution A,
The stir process 5min at 90 DEG C, is then the mixed solution after 25% ammoniacal liquor regulation stir process with mass percent concentration
PH value be 8, then under temperature is 90 DEG C of stirring condition to regulation pH value after mixed solution and dripping concentration be 4mol/
L aqueous solution of urea, the follow-up continuous insulated and stirred 4h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained, then will washing
Filter cake afterwards calcines 3h under the conditions of 400 DEG C, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composites；The mixing
The volume of solution A is 10 times of the quality for mixing N porous carbons/Ni composites, and the wherein unit of quality is g, and the unit of volume is
mL；The mol ratio of urea and nickel powder in step 2 is 4 in the aqueous solution of urea:1.
Fig. 1 is the SEM figures manufactured in the present embodiment for mixing N porous carbons/Ni composites, and Fig. 2 mixes N to be manufactured in the present embodiment
The SEM figures of porous carbon/NiO composites, it can be seen that manufactured in the present embodiment mix in N porous carbons/Ni composites
N porous carbons of mixing show based on mesoporous, with the pore property of part macropore, NiO exists with the form of nanometer sheet, inserts
Enter the macropore of porous carbon, or invest the outer surface of porous carbon.Fig. 3 mixes N porous carbons/Ni composites to be manufactured in the present embodiment
(a curves in figure) and the XRD for mixing N porous carbons/NiO composites (b curves in figure), it can be seen that it is porous to mix N
Ni successful transformations in carbon/Ni composites are into NiO.
Embodiment 2
The preparation method for mixing N porous carbons/NiO composites of the present embodiment includes：
Step 1: preparing Coal-based Polyaniline using situ aggregation method, following steps are specifically included：
Step 101,20g aniline, 30mL concentrated hydrochloric acids (mass concentration is 37%) and 50mL water mixed
Solution B, 10g coal dusts are added into the mixed solution B, and stirring is swelled 2h at 35 DEG C, obtains being swelled coal sample；
Step 102, in 0 DEG C of ice-water bath, 100mL is added dropwise to being swelled described in step 101 in coal sample under agitation
Concentration is 0.48g/mL ammonium persulfate aqueous solution, and rate of addition is to continue the ice-water bath at 0 DEG C after 3mL/min, completion of dropping
Under the conditions of stir 8h, then suction filtration, the filter cake that washing suction filtration is obtained will grind after the filter cake vacuum drying after washing, crosses 200 mesh
Screen cloth obtains Coal-based Polyaniline；The vacuum drying temperature is 70 DEG C, and the vacuum drying time is 10h；
Step 2: by the Coal-based Polyaniline prepared in nickel powder and step one according to 1:2 mass ratio is mixed
Compound, by the mixture in a nitrogen atmosphere, temperature be pyrolyzed after 3h, cooling under conditions of 1000 DEG C obtain mixing N porous carbons/
Ni composites；
Step 3: by hydrogen peroxide (mass concentration is 30%) and concentration for 3mol/L sulfuric acid according to 1:2 volume ratio is mixed
Close uniform, obtain mixed solution A；
Added Step 4: N porous carbons/Ni composites will be mixed described in step 2 described in step 3 in mixed solution A,
The stir process 8min at 85 DEG C, is then the mixed solution after 20% ammoniacal liquor regulation stir process with mass percent concentration
PH value be 7, then under temperature is 85 DEG C of stirring condition to regulation pH value after mixed solution and dripping concentration be 3mol/
L aqueous solution of urea, the follow-up continuous insulated and stirred 3h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained, then will washing
Filter cake afterwards calcines 2h under the conditions of 420 DEG C, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composites；The mixing
The volume of solution A is 20 times of the quality for mixing N porous carbons/Ni composites, and the wherein unit of quality is g, and the unit of volume is
mL；The mol ratio of urea and nickel powder in step 2 is 3 in the aqueous solution of urea:1.
Fig. 4 is the SEM figures manufactured in the present embodiment for mixing N porous carbons/Ni composites, and Fig. 5 mixes N to be manufactured in the present embodiment
The SEM figures of porous carbon/NiO composites, multiplication factor is 50,000 times, and Fig. 6 mixes N porous carbons/NiO composites for what is prepared
SEM schemes, and multiplication factor is 100,000 times, it can be seen that manufactured in the present embodiment mix in N porous carbons/Ni composites
Mix N porous carbons to show based on mesoporous, hole is abundant and orderly, and with the pore property of part macropore, NiO is with nanosphere
Form exist, in the macropore of embedded porous carbon and it is mesoporous in, or be attached to the outer surface of porous carbon.Fig. 7 is the present embodiment system
The standby graph of pore diameter distribution for mixing N porous carbons/NiO composites, can draw from the data in figure, preparation mix N porous carbons with
Based on mesoporous and micropore less than 50nm.By the initial data than surface test through theoretical calculation, the BET for mixing N porous carbons is drawn
Average pore size is 19.8nm, and BET is 627.5m than surface2/ g, t-Plot Micropore volume reach 0.253cm3/ g, is further confirmed
The N porous carbons of mixing prepared are that based on mesoporous, it is more larger than surface.To mix N porous carbons/Ni multiple to be manufactured in the present embodiment by Fig. 8
Condensation material (a curves in figure) and the XRD for mixing N porous carbons/NiO composites (b curves in figure), it can be seen that mixing N
Ni successful transformations in porous carbon/Ni composites are into NiO.
Embodiment 3
The preparation method for mixing N porous carbons/NiO composites of the present embodiment includes：
Step 1: preparing Coal-based Polyaniline using situ aggregation method, following steps are specifically included：
Step 101,10g aniline, 25mL concentrated hydrochloric acids (mass concentration is 37%) and 55mL water mixed
Solution B, 8g coal dusts are added into the mixed solution B, and stirring is swelled 2.5h at 25 DEG C, obtains being swelled coal sample；
Step 102, in 5 DEG C of ice-water baths, under agitation to be swelled described in step 101 in coal sample be added dropwise 60mL it is dense
Spend the ammonium persulfate aqueous solution for 0.40g/mL, rate of addition is to continue the ice-water bath bar at 5 DEG C after 1mL/min, completion of dropping
7h is stirred under part, then suction filtration, the filter cake that washing suction filtration is obtained will grind after the filter cake vacuum drying after washing, cross 200 mesh sieves
Net obtains Coal-based Polyaniline；The vacuum drying temperature is 60 DEG C, and the vacuum drying time is 11h；
Step 2: by the Coal-based Polyaniline prepared in nickel powder and step one according to 1:1.5 mass ratio is well mixed to be obtained
Mixture, temperature are to be pyrolyzed after 3h, cooling under conditions of 800 DEG C to obtain mixing N porous by the mixture in a nitrogen atmosphere
Carbon/Ni composites；
Step 3: by hydrogen peroxide (mass concentration is 30%) and concentration for 4mol/L sulfuric acid according to 1:1.5 volume ratio
It is well mixed, obtain mixed solution A；
Added Step 4: N porous carbons/Ni composites will be mixed described in step 2 described in step 3 in mixed solution A,
The stir process 10min at 80 DEG C, it is then molten for the mixing after 30% ammoniacal liquor regulation stir process with mass percent concentration
The pH value of liquid is 7.5, is then being to the mixed solution and dripping concentration after regulation pH value under temperature is 80 DEG C of stirring condition
5mol/L aqueous solution of urea, the follow-up continuous insulated and stirred 3.5h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained,
The filter cake after washing is calcined into 2.5h under the conditions of 380 DEG C again, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composite woods
Material；The volume of the mixed solution A is 15 times of the quality for mixing N porous carbons/Ni composites, and wherein the unit of quality is g, body
Long-pending unit is mL；The mol ratio of urea and nickel powder in step 2 is 5 in the aqueous solution of urea:1.
N porous carbons/NiO composites SEM figures manufactured in the present embodiment of mixing are similar to Example 1 with XRD, mix N porous
Carbon is showed based on mesoporous, with the pore property of part macropore；NiO exists with the form of nanometer sheet, and NiO nanometer sheets are inserted
Enter in macropore, or be attached to porous carbon outer surface.
Embodiment 4
The preparation method for mixing N porous carbons/NiO composites of the present embodiment includes：
Step 1: preparing Coal-based Polyaniline using situ aggregation method, following steps are specifically included：
Step 101,10g aniline, 25mL concentrated hydrochloric acids (mass concentration is 37%) and 55mL water mixed
Solution B, 6g coal dusts are added into the mixed solution B, and stirring is swelled 2.5h at 30 DEG C, obtains being swelled coal sample；
Step 102, in 2 DEG C of ice-water baths, under agitation to be swelled described in step 101 in coal sample be added dropwise 60mL it is dense
Spend the ammonium persulfate aqueous solution for 0.40g/mL, rate of addition is to continue the ice-water bath bar at 2 DEG C after 1mL/min, completion of dropping
6h is stirred under part, then suction filtration, the filter cake that washing suction filtration is obtained will grind after the filter cake vacuum drying after washing, cross 200 mesh sieves
Net obtains Coal-based Polyaniline；The vacuum drying temperature is 70 DEG C, and the vacuum drying time is 12h；
Step 2: by the Coal-based Polyaniline prepared in nickel powder and step one according to 1:1 mass ratio is mixed
Compound, temperature are to be pyrolyzed after 2.5h, cooling under conditions of 900 DEG C to obtain mixing N porous by the mixture in a nitrogen atmosphere
Carbon/Ni composites；
Step 3: by hydrogen peroxide (mass concentration is 30%) and concentration for 3.8mol/L sulfuric acid according to 1:1.6 volume
Than well mixed, mixed solution A is obtained；
Added Step 4: N porous carbons/Ni composites will be mixed described in step 2 described in step 3 in mixed solution A,
The stir process 10min at 85 DEG C, it is then molten for the mixing after 25% ammoniacal liquor regulation stir process with mass percent concentration
The pH value of liquid is 7, is then being to the mixed solution and dripping concentration after regulation pH value under temperature is 85 DEG C of stirring condition
5mol/L aqueous solution of urea, the follow-up continuous insulated and stirred 3.5h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained,
The filter cake after washing is calcined into 2h under the conditions of 400 DEG C again, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composites；
The volume of the mixed solution A is 18 times of the quality for mixing N porous carbons/Ni composites, and wherein the unit of quality is g, volume
Unit be mL；The mol ratio of urea and nickel powder in step 2 is 4 in the aqueous solution of urea:1.
N porous carbons/NiO composites SEM figures manufactured in the present embodiment of mixing are similar to Example 2 with XRD, mix N porous
Carbon is showed based on mesoporous, with the pore property of part macropore；NiO exists with the form of nanosphere, and NiO nanospheres are embedding
In entering in macropore and being mesoporous, or it is attached to the outer surface of porous carbon.
Comparative example 1
Polyaniline is used for carbon source and nitrogen source, N porous carbons/NiO composites are mixed in preparation, and specific method is：
Step 1: by nickel powder and polyaniline according to 1:2 mass ratio is well mixed to obtain mixture, and the mixture is existed
Under nitrogen atmosphere, temperature obtains mixing N porous carbons/Ni composites to be pyrolyzed after 3h, cooling under conditions of 1000 DEG C；
Step 2: by hydrogen peroxide (mass concentration is 30%) and concentration for 4mol/L sulfuric acid according to 1:1 volume ratio is mixed
Close uniform, obtain mixed solution；
Added Step 3: N porous carbons/Ni composites will be mixed described in step one described in step 2 in mixed solution,
The stir process 5min at 90 DEG C, is then the mixed solution after 25% ammoniacal liquor regulation stir process with mass percent concentration
PH value be 8, then under temperature is 90 DEG C of stirring condition to regulation pH value after mixed solution and dripping concentration be 4mol/
L aqueous solution of urea, the follow-up continuous insulated and stirred 4h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained, then will washing
Filter cake afterwards calcines 3h under the conditions of 400 DEG C, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composites；The mixing
The volume of solution is 10 times of the quality for mixing N porous carbons/Ni composites, and the wherein unit of quality is g, and the unit of volume is
mL；The mol ratio of urea and nickel powder in step one is 4 in the aqueous solution of urea:1.
Comparative example 2
Coal dust is used for carbon source and nitrogen source, N porous carbons/NiO composites are mixed in preparation, and specific method is：
Step 1: by nickel powder and coal dust according to 1:2 mass ratio is well mixed to obtain mixture, by the mixture in nitrogen
Under gas atmosphere, temperature obtains mixing N porous carbons/Ni composites to be pyrolyzed after 3h, cooling under conditions of 1000 DEG C；
Step 2: by hydrogen peroxide (mass concentration is 30%) and concentration for 4mol/L sulfuric acid according to 1:1 volume ratio is mixed
Close uniform, obtain mixed solution；
Added Step 3: N porous carbons/Ni composites will be mixed described in step one described in step 2 in mixed solution,
The stir process 5min at 90 DEG C, is then the mixed solution after 25% ammoniacal liquor regulation stir process with mass percent concentration
PH value be 8, then under temperature is 90 DEG C of stirring condition to regulation pH value after mixed solution and dripping concentration be 4mol/
L aqueous solution of urea, the follow-up continuous insulated and stirred 4h of completion of dropping, suction filtration after cooling, the filter cake that washing suction filtration is obtained, then will washing
Filter cake afterwards calcines 3h under the conditions of 400 DEG C, is taken out after furnace cooling, obtains mixing N porous carbons/NiO composites；The mixing
The volume of solution is 10 times of the quality for mixing N porous carbons/Ni composites, and the wherein unit of quality is g, and the unit of volume is
mL；The mol ratio of urea and nickel powder in step one is 4 in the aqueous solution of urea:1.
The nitrogen element content for mixing N porous carbons/NiO composites of the elemental analyser of table 1 test
From table 1 it follows that the N dopings for mixing N porous carbons/NiO composites prepared using the method for the present invention
For 1.422wt%~2.238wt%, illustrate that N element is successfully mixed in composite.Its doping is with Coal-based Polyaniline
The increase of polyphenyl amine content and increase, it is lower than comparative example 1, it is higher than comparative example 2.
N porous carbons/the NiO that mixes prepared using the embodiment of the present invention 1 to embodiment 4 and comparative example 1 and comparative example 2 is combined
Material prepares electrode material, and carries out electrochemical property test to the electrode material of preparation：
The preparation method of electrode material：It is 80 by active electrode material, conductive agent and bonding agent mass ratio:15:5 make electricity
Pole piece, N porous carbons/NiO composites are mixed by prepared by the embodiment of the present invention 1 to embodiment 4 and comparative example 1 and comparative example 2
200 mesh sieves are crossed after grinding respectively, using screenings as active electrode material, little particle conductive black Supper-p is conductive agent,
Kynoar (PVDF) is bonding agent, and DMF (DMF) is solvent, will mix N porous carbons/NiO composites
It is scattered with DMF after uniformly being mixed with conductive agent；Then PVDF DMF solution is added in the material to after disperseing, pasty state is stirred into
Mixture；Again by the graphite paper of pasty mixture even application to 1cm × 1.5cm；Naturally after drying, vacuum is done at 60 DEG C
It is dry to constant weight, obtain mixing N porous carbons/NiO electrode materials.
Electrochemical property test：Using three-electrode system, respectively to mix N porous carbons/NiO electrode materials as working electrode,
Ag/AgCl (saturation KCl solution) is reference electrode, and Pt pieces are auxiliary electrode, and the 6mol/L KOH aqueous solution is electrolyte,
Cyclic voltammetric and constant current charge-discharge test are carried out on AUTOLAB PGSTAT 302N type electrochemical workstations.Cyclic voltammetry
Potential range be -1.0V~0.4V, sweep speed be 50mV/s；Constant current charge-discharge test electric current is constant in 5mA, and potential range-
1.4V~0.4V.Fig. 9 be with embodiment 1 (a curves in figure) and embodiment 2 (b curves in figure) preparation to mix N porous carbons/NiO multiple
Condensation material is the cyclic voltammetry curve of electrode material prepared by active electrode material, it can be seen that two kinds to mix N porous
The rectangular characteristic of the cyclic voltammetry curve of carbon/NiO composites substantially, shows obvious electric double layer capacitance feature, this is
Mix contribution of the N porous carbons to electric capacity.In addition, two cyclic voltammetry curves have an oxidation peak near -0.8V, it is attached in 0.1V
Closely there is a reduction peak, NiO oxidation, reduction process is correspond to respectively, reflect NiO fake capacitance feature and its to electric capacity
Contribution.Figure 10 is to mix N porous carbons/NiO composite woods with prepared by embodiment 1 (a curves in figure) and embodiment 2 (b curves in figure)
Constant current charge-discharge curve of the electrode material under 5mA prepared for active electrode material is expected, it can be seen that two constant currents
Charging and discharging curve has an oxidation peak near -0.8V, has a reduction peak near 0.1V, NiO oxygen is correspond to respectively
Change, reduction process, this is consistent with cyclic voltammetry result.Reflect NiO fake capacitance feature and its electricity to composite
The contribution of appearance.In addition, the charging process and discharge process of two curves have certain symmetry, reflect and mix the double of N porous carbons
Electric layer capacitive characteristics and its contribution to electric capacity.
It can be quantified by constant current charge-discharge curve and calculate specific capacitance, energy density and power density, calculation formula is：
Cs=I △ t/m △ E (1)
Es=1000Cs(△E2)/7200 (2)
Ps=3600Es/△t (3)
Wherein, CsFor specific capacitance, unit is F/g；I is discharge current, and unit is A；M is the matter of the active material on electrode
Amount, unit is g；△ E are the difference of charge cutoff voltage and discharge cut-off voltage, and unit is V；△ t are discharge time, and unit is s；
EsFor energy density, unit is Wh/kg；PsFor power density, unit is W/kg.
Result of calculation see the table below 2.
The result of calculation of the constant current charge-discharge test of table 2 (constant current density is 2.5A/g)
| Mix N porous carbons/NiO composites | Specific 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 |
From Table 2, it can be seen that mixing N porous carbons/NiO composites as active electricity using prepared by the method for the present invention
Pole material, what is prepared mixes N porous carbons/NiO electrode materials under 2.5A/g constant current density, and its monopole specific capacitance is reachable
More than 280F/g, energy density reaches more than 2056W/kg up to more than 98Wh/kg, power density.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent structure change that technical spirit is made to above example, still fall within skill of the present invention
In the protection domain of art scheme.
Claims (9)
1. one kind mixes the preparation method of N porous carbons/NiO composites, it is characterised in that comprise the following steps：
Step 1: preparing Coal-based Polyaniline using situ aggregation method；
Step 2: by the Coal-based Polyaniline prepared in nickel powder and step one according to 1:The mass ratio of (1~2) is mixed
Compound, temperature are pyrolysis 2h~3h under conditions of 800 DEG C~1000 DEG C by the mixture in a nitrogen atmosphere, after cooling
To mixing N porous carbons/Ni composites；
Step 3: by hydrogen peroxide and concentration for 3mol/L~4mol/L sulfuric acid according to 1:The volume ratio of (1~2) is well mixed,
Obtain mixed solution A；
Added Step 4: N porous carbons/Ni composites will be mixed described in step 2 described in step 3 in mixed solution A, 80
DEG C~90 DEG C at stir process 5min~10min, then with ammoniacal liquor adjust stir process after mixed solution pH value be 7~8,
Then, to the mixed solution and dripping aqueous solution of urea after regulation pH value, it is being added dropwise under temperature is 80 DEG C~90 DEG C of stirring condition
Follow-up continuous insulated and stirred 3h~4h is finished, suction filtration after cooling washs the filter cake that suction filtration is obtained, then by the filter cake after washing 380
DEG C~420 DEG C under the conditions of calcine 2h~3h, after furnace cooling take out, obtain mixing N porous carbons/NiO composites；The mixing is molten
Liquid A volume is 10~20 times of the quality for mixing N porous carbons/Ni composites, and wherein the unit of quality is g, the unit of volume
For mL；The mol ratio of urea and nickel powder in step 2 is (3~5) in the aqueous solution of urea:1；
The preparation method of Coal-based Polyaniline described in step one comprises the following steps：
Step 101, obtain mixed solution B by aniline, concentrated hydrochloric acid and water are well mixed, coal dust added into the mixed solution B,
Stirring is swelled 2h~3h at 25 DEG C~35 DEG C, obtains being swelled coal sample；The volume of the concentrated hydrochloric acid is the 1.5~3 of aniline quality
Times, the volume of water is 2.5~6 times of aniline quality, and the unit of wherein volume is mL, and the unit of quality is g；The coal dust
Mass ratio with aniline is 1:(1~2)；
Step 102, in 0 DEG C~5 DEG C ice-water baths, over cure is added dropwise to being swelled described in step 101 in coal sample under agitation
Continue to stir 6h~8h under the conditions of 0 DEG C~5 DEG C of ice-water bath after sour aqueous ammonium, completion of dropping, suction filtration, washing suction filtration is obtained
Filter cake, then by after washing filter cake vacuum drying after grind, sieving obtain Coal-based Polyaniline；The ammonium persulfate aqueous solution
The mol ratio of middle ammonium persulfate and aniline in step 101 is 1:1.
2. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
The mass concentration of concentrated hydrochloric acid described in 101 is 37%.
3. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
The concentration of ammonium persulfate aqueous solution described in 102 is 0.30g/mL~0.48g/mL, and the rate of addition of ammonium persulfate aqueous solution is
1mL/min~3mL/min.
4. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
Vacuum drying temperature described in 102 is 50 DEG C~70 DEG C, and the vacuum drying time is 10h~12h.
5. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
The sieve mesh number sieved described in 102 is 200 mesh.
6. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
The mass concentration of hydrogen peroxide described in three is 30%.
7. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
The mass percent concentration of ammoniacal liquor described in four is 20%~30%.
8. one kind according to claim 1 mixes the preparation method of N porous carbons/NiO composites, it is characterised in that step
The concentration of aqueous solution of urea described in four is 3mol/L~5mol/L.
9. a kind of N porous carbons/NiO that mixes using as any claim methods described is prepared in claim 1 to 8 is combined
Material.
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| CN105845454B (en) * | 2016-03-28 | 2017-08-22 | 西安科技大学 | A kind of preparation method for mixing N porous carbons/iron oxide composite granule |
| CN106348276B (en) * | 2016-08-23 | 2017-08-25 | 西安科技大学 | It is a kind of to combine the method for preparing carbon micro-nano mitron and mixing N porous carbons/nickel manganese oxide |
| CN108172413B (en) * | 2017-12-25 | 2020-04-14 | 温州大学新材料与产业技术研究院 | Preparation method and application of three-dimensional spherical nitrogen-doped porous carbon material and nickel/nickel oxide 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 |
| CN110342492B (en) * | 2019-06-13 | 2021-03-09 | 陕西浦士达环保科技有限公司 | Preparation method of nitrogen-oxygen doped carbon nano tube/porous carbon |
| 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 |
| CN112320786A (en) * | 2020-11-17 | 2021-02-05 | 绥化学院 | Ganoderma applanatum-based nitrogen-doped mesoporous carbon and NiO-CoS2Preparation method of composite electrode material |
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