CN105225844A - The preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material and application - Google Patents
The preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material and application Download PDFInfo
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Abstract
The present invention disclose a kind of nitrogen-doped graphene/? the preparation method of nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material, concrete steps are: (a) adds potassium permanganate, hydrochloric acid and hydrogen peroxide in graphene oxide, and stirring reaction prepares porous graphene; (b) porous graphene is dialysed 8-12 days after ultrasonic disperse, then add carbon nano-tube, after ultrasonic mixing, suction filtration film forming; After the drying of (c) film, add ammoniacal liquor reaction 24h; D () adds zinc nitrate, cobalt nitrate, urea, ammonium fluoride, absolute ethyl alcohol and distilled water reaction 4h; E mixture is transferred to tube furnace by (), sinter 2h under nitrogen atmosphere, namely obtains described composite material; This composite material has good pliability, after bending to various angle, chemical property change is little, and its ratio capacitance value is the highest can up to 1802F/g, simple Graphene of comparing, carbon nano-tube, and the composite material of most of Graphene and carbon nano-tube all increases significantly.
Description
Technical field
The invention belongs to electrochemical field, the preparation method of particularly a kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material and application.
Background technology
Graphene is that known at present world is the thinnest the hardest
nano material, thickness only has a carbon atom, and specific area is up to 2630m
2/ g, because of using this graphene-supported metal oxide or the sulfide nano composite material electrode material as electrochemical storage device such as lithium ion battery, ultracapacitor, lithium-air batteries, electric charge/the ion transport capability of electrode material can be significantly improved, and then promote the cyclical stability of electrode material.But the metal oxide of current reported graphenic surface institute load or sulfide, mainly exist with the pattern of meticulous nano particle, specific area is relatively low, relative less with the reactivity point of lithium ion, specific capacity is lower, is only 200-300F/g, restricts this material and further develops; Pore-creating is carried out by potassium permanganate, to ensure the course of membrane structure and shortening ion, further increasing specific surface area in practice; Carry out nitrating by ammoniacal liquor in addition, the wettability of electrode material and electrolyte can be improved on the one hand, improve the efficiency of electrochemical reaction, fake capacitance performance can be provided on the other hand, thus improve the chemical property of material; But due to the overlap of graphene sheet layer in actual production process, its resistivity and specific area often do not reach theoretical value, therefore need and carbon nano-tube compound, form three-dimensional hierarchy, the specific area of oneself can be improved on the one hand by the overlap reduced between lamella, the conductivity that carbon nano-tube is higher can also be utilized on the other hand, solve the inflexible shortcoming of battery, for the update of battery industry of future generation lays the foundation, reduce interior resistance when being used as electrode simultaneously, thus the heat release problem produced when reducing charge and discharge cycles.But the nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe existed at present is used as electrochemical capacitance and is limited to the less ratio capacitance value of electric double layer capacitance, therefore need to obtain larger ratio capacitance with fake capacitance compound.
Cobalt acid zinc is the binary oxide of the structure with spinelle, the zinc ion of divalence is in the tetrahedral position of cubic spinel, the cobalt element of trivalent is then on octahedron, its electrode as electrochemical capacitance has better capacitive property than cobaltosic oxide, because it has higher electro-chemical activity, abundanter oxygen reduction reaction, has the nanostructure of suitable porous and layering can improve power density and cycle life.
In the technology of the graphene-supported cobalt acid zinc of current existence, be limited to the stacking between graphene sheet layer, therefore the volume utilization of entirety is lower, as college of science of Xi'an Communications University doctor Gao Guoxin, synthetic method (" graphenic surface Supported Co acid zinc the nanostructure ") material therefor of the graphene-supported ultra-thin cobalt acid nickel nano film of XiongWen (David) the professor Lou research of Ding Shujiang professor and Nanyang Technological University is natrium citricum, it fails to reduce the stacking of Graphene in the process of preparation, and the materials application of its research is in lithium ion battery, in electrochemical capacitance, do not do further research, application number be 201310390188.0 Chinese patent then disclose a kind of method that fused salt casting method prepares nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper material, obtain composite material there is ORR electrocatalysis characteristic, but its preparation methods steps is complicated, higher to operation requirements, be unsuitable for large-scale promotion application, and the document does not relate to super capacitor research equally.At present, Graphene, carbon nano-tube and cobalt acid zinc is carried out compound, the preparation method that formation three-dimensional manometer battle array structure is used as super capacitor material has not yet to see report.
Summary of the invention
For the problems referred to above, the invention provides a kind of utilize Graphene, carbon nano-tube and cobalt acid zinc to take out film after carry out hydro-thermal and be compounded to form the method that three-dimensional manometer battle array structure prepares super capacitor material, the lifting of specific area and space availability ratio is realized between the lamella that carbon nano-tube is joined Graphene by the method, the super capacitor material obtained has good conductivity and toughness, and higher ratio capacitance and good cycle charge discharge electrical stability, the present invention is achieved in that
A preparation method for nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material, concrete steps are as follows:
A () is add 1.5g potassium permanganate in the graphene oxide of 0.5mg/ml to 100ml concentration, stirring reaction 2h, then add the hydrochloric acid stirring reaction 3h that 250ml mass fraction is 36.5%, then add the hydrogen peroxide stirring reaction 3h that 20ml mass fraction is 30%, obtain porous graphene;
B porous graphene is placed in bag filter by (), dialyse 8-12 days in distilled water, ultrasonic disperse 1h after taking out; Then add carbon nano-tube, add carbon nano-tube and porous graphene mass ratio be 1:5-15, after continuing ultrasonic 2h, suction filtration film forming;
C () gets film dry 48h under normal temperature that suction filtration obtains, add the ammoniacal liquor that 35ml concentration is 25%, 180 DEG C of reaction 24h, and products therefrom is nitrating graphene/carbon nano-tube blend films;
D nitrating Graphene, carbon nanotube mixture film are inserted 45ml and are contained zinc nitrate 0.1mmol, cobalt nitrate 0.1mmol, urea 0.1mmol, ammonium fluoride 0.1mmol by (), in the distilled water of absolute ethyl alcohol 30ml, in 120-140 DEG C of reaction 4h;
E the mixture obtained after () step (d) reaction is transferred to tube furnace, under nitrogen atmosphere, 300-400 DEG C of sintering 2h, namely obtains described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material.
2, according to the preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe according to claim 1/cobalt acid zinc composite material, it is characterized in that, in step (b), add carbon nano-tube and porous graphene mass ratio be 1:10.
The preparation method of 3, nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe according to claim 2/cobalt acid zinc composite material, it is characterized in that, in step e, tube furnace heating rate is 2 DEG C/min,
4, according to the preparation method of the nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe one of claim 1-3 Suo Shu/cobalt acid zinc composite material, it is characterized in that, described graphene oxide obtains like this:
3g natural flake graphite is scattered in the sulfuric acid that 70ml mass fraction is 98%, under condition of ice bath, adds sodium nitrate 1.5g, potassium permanganate 9g, keep temperature lower than 20 DEG C of stirring reaction 1.5h; Then reactant is placed in 38-40 DEG C of hot bath stirring reaction 30min; And then be placed in ice-water bath, add 500ml distilled water and at least leave standstill 2h, discard after supernatant liquor with the centrifugal 10min of the speed of 13000rpm, then by the dark solution ultrasonic disperse 10min of centrifugal acquisition, ultrasonic power is 20kHz, with the centrifugal 10min of the speed of 4000rpm after dispersion, centrifugal rear obtained upper strata yellow transparent liquid is graphene oxide solution.
Nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe as described herein/cobalt acid zinc composite material is as the application of flexible electrode.
According to the composite material that the inventive method obtains, structure is with porous nitrating Graphene and carbon nano-tube for skeleton, the three-dimensional manometer array of Supported Co acid zinc oxide on skeleton.The nanometer sheet that heap sum separately grows can not only reduce the empty area in Graphene and carbon nano-tube, the real contact area between electrode and electrolyte can also be promoted, so just can improve the utilization rate of active material, cobalt acid zinc is directly long on Graphene and carbon nano-tube, not only can keep pattern in long cyclic process, contact resistance can also be reduced, the nanometer sheet of mesopore not only can improve a large amount of pore volumes to store electrolyte, improve more avtive spot to carry out faraday's reaction, and the distance of hydroxide ion diffusion can be shortened, dynamics faster can be caused, thus raising electrical property.
Adding of carbon nano-tube ensure that electrode has good conductivity, and the stability of Graphene ensure that this electrode has good charge and discharge cycles stability, the mixture of cobalt and zinc is then for electrode material provides larger electric capacity, the synergy of three makes it can be used as flexible electrode in electrochemical capacitance, compared with prior art:
(1) this composite material has good pliability, and after bending to various angle, chemical property change is little.
(2) design feature of this composite material is that carbon nano-tube is interted between graphene layer, make it not easily overlapping, simultaneously, the avtive spot of the carried out faraday hydrogen reduction that it is had is a large amount of of cobalt acid zinc, thus improve ratio capacitance, its ratio capacitance value is the highest can up to 1802F/g, simple Graphene of comparing, carbon nano-tube, and the composite material of most of Graphene and carbon nano-tube all increases significantly.
(3) this composite material is when as electrode material, has superior cycle charge discharge electrical property, after 4000 circles that circulated, still has 1320F/g, has exceeded 200% than initial value.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of flexible electrode composite material prepared by the embodiment of the present invention 1.
Fig. 2 is the projection Electronic Speculum figure (TEM) of flexible electrode composite material prepared by the embodiment of the present invention 1.
Fig. 3 is the X-ray diffraction (XRD) of flexible electrode composite material prepared by the embodiment of the present invention 1.
Fig. 4 is the cyclic voltammogram (cv) of flexible electrode composite material prepared by the embodiment of the present invention 1.
Fig. 5 is the chronopotentiogram of flexible electrode composite material prepared by the embodiment of the present invention 1.
Fig. 6 is the charge and discharge circulation life figure of flexible electrode composite material prepared by the embodiment of the present invention 1.
Specific embodiments
The carbon nano-tube used in embodiment is provided by ShenZhenNanoport, LTD, and purity is 95%, and diameter is 10-20nm, 100-160g/m
2.
Embodiment 1
(1) 3g natural flake graphite being scattered in 70ml mass fraction is in the concentrated sulfuric acid of 98%, adds the cooling of 0.1g sodium nitrate, then add 9g potassium permanganate under condition of ice bath, keeps temperature lower than 20 DEG C, with the speed stirring reaction 1.5 hours of 300-500rpm; Then reactant is placed in the hot bath of 38-40 DEG C, with the speed stirring reaction 30min of 300-500rpm; Then take out reactant, be again placed in ice-water bath, in reactant, add distilled water, leave standstill at least 2 hours, after solution layering, centrifugal after discarding supernatant liquor (13000rpm) 10min, gets the dark solution of centrifugal acquisition, ultrasonic (20kHz) 10min; And then centrifugal (4000rpm) 10min, the upper strata yellow transparent liquid of centrifugal rear acquisition is graphene oxide;
(2) the graphene oxide concentration that set-up procedure (1) obtains is 0.5mg/ml, get 100 milliliters of graphene oxides in beaker, add the potassium permanganate of 1.5g, with the speed stirring reaction 2h of 300-500rpm, then the concentrated hydrochloric acid that 250ml mass fraction is 36.5% is added, with 300-500rpm stirring reaction 3h, then add the hydrogen peroxide stirring reaction 3 hours that 20ml mass fraction is 30%, obtain porous graphene;
(3) porous graphene step (2) obtained loads in bag filter, be placed in distilled water to dialyse 8-12 days, get the porous graphene after dialysis ultrasonic (20kHz) 1h, then adding with porous graphene mass ratio is the carbon nano-tube of 1:10, the ultrasonic mixing of 20kHz is after 2 hours, by solution suction filtration film forming;
(4) dry 48h under the film that suction filtration obtains being placed in normal temperature, the concentration then adding 35ml be the ammoniacal liquor of 25% in reactor, react 24h at 180 DEG C of temperature, obtain product and be nitrating Graphene, carbon nanotube mixture film;
(5) hydro-thermal reaction: nitrating Graphene, carbon nanotube mixture film are placed in reactor, then add 45ml mixed solution, 140 DEG C of reaction 4h;
Described mixed solution is: the zinc nitrate of 0.1mmol, 0.1mmol cobalt nitrate, the absolute ethyl alcohol of 0.1mmol urea, 0.1mmol ammonium fluoride, 30ml, and surplus is distilled water;
(6) calcination reaction: be transferred in tube furnace by reacted mixture, under nitrogen atmosphere protection, with the heating rate of 2 DEG C/min, in 350 DEG C of reactions 2 hours, namely obtains nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material;
In specific operation process, step (6) sintering temperature all can realize the object of invention within the scope of 300-400 DEG C.
Fig. 1 is the SEM figure of this composite material, in figure, the flower-shaped thing of white is cobalt acid zinc, substrate is nitrating graphene/carbon nano-tube film, as seen from Figure 1, the size of cobalt acid zinc is in 100 nanometers, wherein the petal size of needle-like is less than 10 nanometers, is conducive to the raising of specific area, for electrolyte ion provides more reactivity site;
Fig. 2 is the XRD figure of this composite material, can find out that the place of light color is Graphene in figure, and black is cobalt acid zinc nano flower, and bar-shaped be carbon nano-tube, the tight compound of visible three;
Fig. 3 is the XRD figure of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material, in figure, ordinate is labeled as the standard P DF card into cobalt acid zinc, as seen from Figure 2, the characteristic peak of compound cobalt acid zinc gone up substantially by this composite material, and deviation slightly may be machine or substrate impact;
Fig. 4 is the cv figure of this composite material, visible symmetrical hydrogen reduction peak in 4 in figure, and along with the increase of sweeping speed, cv figure does not have greatly changed, and shows good high rate performance, and the electric current of its correspondence is comparatively large simultaneously, and capacitance will be larger;
Fig. 5 is the chronopotentiogram of this composite material under different current density, as can be seen from the figure has the platform of an obvious discharge and recharge, and this is produced by cobalt acid zinc fake capacitance;
Fig. 6 is that thin-film material is under the current density of 5A/g, the change of the ratio capacitance value after nearly 4000 circles that circulates, can find out that ratio capacitance loss is little, this composite material machinery good stability is described, in the process of long discharge and recharge, the dilation effectively caused cobalt acid zinc serves the effect of buffering.
Embodiment 2 hydrothermal temperature is on composite material impact test
With embodiment 1 step (5) hydrothermal temperature (120 DEG C, 130 DEG C, 140 DEG C) for variable, test different Graphene, carbon nano-tube ratio to the impact of composite property, test divides following several groups:
Group 1: porous graphene and carbon nanotube mass are than being 5:1;
Group 2: porous graphene and carbon nanotube mass are than being 10:1;
Group 3: porous graphene and carbon nanotube mass are than being 15:1;
Group 4: do not add carbon nano-tube;
Group 5: Graphene not pore-creating;
Group 1-4 in, except add in step (3) porous graphene different from carbon nano-tube ratio and step (5) hydrothermal temperature except, all the other steps are all identical with embodiment 1;
Group 5 is except lacking step (2) (i.e. Graphene not pore-creating) and step (5) hydrothermal temperature difference, and all the other are identical with embodiment 1 step.
Detect above-mentioned each group of ratio capacitance value under current density is 1A/g, unit F/g, result is as shown in table 1:
The different hydrothermal temperature testing result of table 1
From table 1, compare in the scope of 5-15:1, along with the rising of temperature at (porous) Graphene and carbon nanotube mass, when 1A/g, ratio capacitance value, in the trend increased, illustrates when temperature raises, cobalt acid zinc nano flower petal becomes elongated gradually, and specific area is in increase; When (porous) Graphene and carbon nanotube mass are than when being 10:1, ratio capacitance value is maximum, because carbon nano-tube is very little to the contribution of electric capacity, so in time increasing the ratio of carbon nano-tube and Graphene, capacitance can reduce to some extent, but carbon nano-tube can increase the spacing between porous graphene lamella, thus reduction stacking in increase its specific area, therefore the ratio of Graphene and carbon nano-tube is 10:1 be the best; Meanwhile, when carbon nano-tube and Graphene (non-pore-creating, group 5) compound tense, ratio capacitance value is less, and comprehensive explanation composite material specific area of the present invention is to the improve of the utilance of active material.
The different calcining heat of embodiment 3 is on composite property impact test
With embodiment 1 step (6) calcination reaction temperature (300 DEG C, 350 DEG C, 400 DEG C) for variable, test different Graphene, carbon nano-tube ratio to the impact of composite property, test is divided into:
Group 1: porous graphene and carbon nanotube mass are than being 5:1;
Group 2: porous graphene and carbon nanotube mass are than being 10:1;
Group 3: porous graphene and carbon nanotube mass are than being 15:1;
Group 4: do not add carbon nano-tube;
Group 5: Graphene not pore-creating;
Group 1-4 in, except add in step (3) porous graphene different from carbon nano-tube ratio and step (6) calcination reaction temperature except, all the other steps are all identical with embodiment 1;
Group 5 is except lacking step (2) (i.e. Graphene pore-creating) and step (6) calcination reaction temperature difference, and all the other are identical with embodiment 1 step.
Detect above-mentioned each group of ratio capacitance value under current density is 1A/g, unit F/g, result is as shown in table 2:
The different calcination reaction temperature detection result of table 2
As can be seen from Table 2 in the elevation process of temperature, ratio capacitance value experienced by first high rear low process, the rising describing temperature facilitates growth and the plastotype of crystal formation on the one hand, temperature can impact the regularity of Graphene and carbon nano-tube film on the other hand, in 350 DEG C, substantially optimal value can be reached.
As seen from the above-described embodiment, nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that the present invention obtains/cobalt acid zinc composite material has good conductivity and toughness, and namely the flexible electrode prepared with this material has higher ratio capacitance and good cycle charge discharge electrical stability.
Above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (5)
1. a preparation method for nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material, it is characterized in that, concrete steps are as follows:
A () is add 1.5g potassium permanganate in the graphene oxide of 0.5mg/ml to 100ml concentration, stirring reaction 2h, then add the hydrochloric acid stirring reaction 3h that 250ml mass fraction is 36.5%, then add the hydrogen peroxide stirring reaction 3h that 20ml mass fraction is 30%, obtain porous graphene;
B porous graphene is placed in bag filter by (), dialyse 8-12 days in distilled water, ultrasonic disperse 1h after taking out; Then add carbon nano-tube, add carbon nano-tube and porous graphene mass ratio be 1:5-15, after continuing ultrasonic 2h, suction filtration film forming;
C () gets film dry 48h under normal temperature that suction filtration obtains, add the ammoniacal liquor that 35ml concentration is 25%, 180 DEG C of reaction 24h, and products therefrom is nitrating graphene/carbon nano-tube blend films;
D nitrating Graphene, carbon nanotube mixture film are inserted containing zinc nitrate 0.1mmol, cobalt nitrate 0.1mmol, urea 0.1mmol, ammonium fluoride 0.1mmol by (), in the 45ml distilled water of absolute ethyl alcohol 30ml, in 120-140 DEG C of reaction 4h;
E the mixture obtained after () step (d) reaction is transferred to tube furnace, under nitrogen atmosphere, 300-400 DEG C of sintering 2h, namely obtains described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material.
2. the preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe according to claim 1/cobalt acid zinc composite material, is characterized in that, in step (b), add carbon nano-tube and porous graphene mass ratio be 1:10.
3. the preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe according to claim 2/cobalt acid zinc composite material, it is characterized in that, in step e, tube furnace heating rate is 2 DEG C/min.
4., according to the preparation method of the nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe one of claim 1-3 Suo Shu/cobalt acid zinc composite material, it is characterized in that, described graphene oxide obtains like this:
3g natural flake graphite is scattered in the sulfuric acid that 70ml mass fraction is 98%, under condition of ice bath, adds sodium nitrate 1.5g, potassium permanganate 9g, keep temperature lower than 20 DEG C of stirring reaction 1.5h; Then reactant is placed in 38-40 DEG C of hot bath stirring reaction 30min; And then be placed in ice-water bath, add 500ml distilled water and at least leave standstill 2h, discard after supernatant liquor with the centrifugal 10min of the speed of 13000rpm, then by the dark solution ultrasonic disperse 10min of centrifugal acquisition, ultrasonic power is 20kHz, with the centrifugal 10min of the speed of 4000rpm after dispersion, centrifugal rear obtained upper strata yellow transparent liquid is graphene oxide solution.
5. as described in one of claim 1-3 nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material as the application of flexible electrode.
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