CN109872881A - Nickel sulfide/application of the carbon nano tube flexible composite film material in supercapacitor - Google Patents
Nickel sulfide/application of the carbon nano tube flexible composite film material in supercapacitor Download PDFInfo
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Abstract
The invention discloses a kind of nickel sulfide/application of the carbon nano tube flexible composite film material in supercapacitor, it is characterized in that, the nickel sulfide/carbon nano tube flexible composite film material preparation method is placed in ptfe autoclave the following steps are included: weighing 3~4mg silicic acid nickel carbon nano-tube film, it takes dehydrated alcohol to be added in reaction kettle again, makes ethanol solution complete wetting silica/carbon periosteum；1.0~3.0mg/mL sodium sulfide solution, 15~16ml is weighed as sulphur source, the solvent of the vulcanized sodium is the mixture of water and ethyl alcohol, sequentially add ptfe autoclave, in 160 DEG C of reaction 9-24h, after room temperature natural cooling, it washs through deionized water to neutrality, immerse ethyl alcohol, it is sprawled on polytetrafluoroethylene film, it dries at room temperature, nickel sulfide/carbon nanotube membrane material is obtained, the object phase in the nickel sulfide/carbon nano tube flexible composite film material is adjusted by adjusting reaction time and reacting material concentration.
Description
Technical field
The present invention relates to C-base composte material technical fields, compound more particularly to a kind of nickel sulfide/carbon nano tube flexible
Application of the thin-film material in supercapacitor.
Background technique
Metal sulfide especially nickel sulfide relies on its good electric conductivity and cycle performance, resourceful, environmental-friendly
Etc. characteristics and the favor by researchers, cause in recent energy storage system electrode material to be studied modish.Carbon nanotube
Unique texture make it have higher specific surface area, good mechanical performance and electric conductivity, supercapacitor field have
Have and possesses huge application potential.But carbon nanotube is nonpolar molecule, wellability is poor in aqueous solution, and interbank has
Biggish Van der Waals force often mutually tangles reunion.Hydrophobic property is presented in general carbon material surface, is unfavorable for it water-soluble
It is reacted in liquid, reaction is caused only to rest on material macro surface, reaction is uneven, is not thorough, while being also unfavorable for inorganic
The contact and infiltration of electrolyte, which greatly limits the applications of carbon nanotube.
Researchers can be surface-treated electrode material at present, as assisted using concentrated acid processing or plasma
O2-Processing makes Carbon Materials, and charcoal material surface forms surface texture defect and oxygen-containing functional group, the surface of material are in high-energy shape
State, chemical activity is relatively high, improves material surface wetability.But one side process of surface treatment is many and diverse, and may destroy
Original macrostructure；On the other hand the presence of some organo-functional groups will increase the internal resistance of electrode, leakage current can be made to increase, and reduce
The cycle performance of capacitor.Therefore how carbon nano-tube film macro property is not destroyed, change the wetability of carbon nano-tube film,
So that chemical reaction is not only rested on the surface of carbon nanotube membrane material macroscopic view, while improving the knot of active material and carbon nanotube
It closes intensity and load capacity is had got long long way to go.
Summary of the invention
In view of the technical drawbacks of the prior art, it is an object of the present invention to provide a kind of nickel sulfide/carbon nanotubes
Application of the flexible composite film material in supercapacitor.
The technical solution adopted to achieve the purpose of the present invention is:
Nickel sulfide/application of the carbon nano tube flexible composite film material in supercapacitor, the vulcanization nickel carbon nanometer
The preparation method of pipe flexible composite film material the following steps are included:
Step 1, it weighs silica/carbon nano-tube film to be placed in dehydrated alcohol, so that aoxidizing without ethanol solution complete wetting
Silicon/carbon periosteum；
Step 2, nickel nitrate solution, urea and deionized water are added into system prepared by step 1, is uniformly mixed to urine
Plain all dissolutions；
Step 3, the resulting system of step 2 is placed in 90-120 DEG C of reaction 6-18h in baking oven, at room temperature after natural cooling,
It washs through deionized water to neutrality, it is spare to obtain silicic acid nickel carbon nano-tube film after dry；
Step 4,3~4mg silicic acid nickel carbon nano-tube film that step 3 obtains is weighed to be placed in ptfe autoclave,
It takes dehydrated alcohol to be added in reaction kettle again, makes ethanol solution complete wetting silica/carbon periosteum；
Step 5,1.0~3.0mg/mL sodium sulfide solution, 15~16ml is weighed as sulphur source, and the solvent of the vulcanized sodium is
The mixture of water and ethyl alcohol, sequentially adds ptfe autoclave, after 160 DEG C of reaction 9-24h, room temperature natural cooling, warp
Deionized water is washed to neutrality, is immersed ethyl alcohol, is sprawled on polytetrafluoroethylene film, dries receive to get to vulcanization nickel carbon at room temperature
Mitron membrane material；
When the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 9-15h, nickel sulfide/carbon nanotube membrane material
Object in material is mutually Ni3S2And Ni3Si2O5(OH)4, and predominantly Ni3Si2O5(OH)4；
When the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nano-tube film
Object in material is mutually Ni3S2And Ni3Si2O5(OH)4, and predominantly Ni3S2；
When the vulcanized sodium in step 5 is 1.7-1.9mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nano-tube film
Object in material is mutually Ni3S2；
When the vulcanized sodium in step 5 is 2.0-2.2mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nano-tube film
Object in material is mutually Ni3S2And NiS；
When the vulcanized sodium in step 5 is 2.3-2.5mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nano-tube film
Object in material is mutually Ni3S4。
Preferably, silica/carbon nano-tube film preparation method in the step 1, comprising the following steps:
S1, according to (95-100): (1.5-2): it is molten that 1 mass ratio weighing ethyl alcohol, ferrocene and thiophene is mixed to get mixing
Liquid, wherein carbon source of the ethyl alcohol as this reaction, for ferrocene as catalyst, thiophene is as promotor, then weighs above-mentioned gross mass
Silicon source of the ethyl orthosilicate (TEOS) of score 1~8% as reaction, is added in the mixed solution, at 40-60 DEG C, holds
Continuous ultrasonic disperse, is transferred to syringe after obtaining uniform dispersion, as precursor solution；
Vertical CVD furnace is fully sealed (water seal or oil sealing), is continually fed into the Ar of 50~200sccm by S2, completely exclusion furnace
Vertical CVD furnace is warming up to 1000~1250 DEG C, keeps the temperature 2~6h by the residual air in son；
S3 closes Ar, the H of 600~900sccm is persistently injected in furnace after the completion2, to H2Full of entire vertical CVD furnace
Thorax, then by precursor solution in the fluid injection rate injection burner hearth of 4~12mL/h；The 10-30min or so after starting is reacted,
Si oxide/carbon nano-tube film of burner hearth bottom collection tubular class.
Preferably, the mass fraction of ethyl orthosilicate is 4% in the step S1.
Preferably, when the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 9-15h, the nickel sulfide/
Carbon nanotube membrane material obtains the specific capacity of 540-550F/g under 10A/g current density.
Preferably, when the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 20-24h, the nickel sulfide/
Carbon nanotube membrane material obtains the specific capacity of 1400-1500F/g under 10A/g current density.
Preferably, when the vulcanized sodium in step 5 is 1.7-1.9mg/mL, and the reaction time is 20-24h, the nickel sulfide/
Carbon nanotube membrane material obtains the specific capacity of 1900-2000F/g under 10A/g current density.
Preferably, when the vulcanized sodium in step 5 is 2.0-2.2mg/mL, and the reaction time is 20-24h, the nickel sulfide/
Carbon nanotube membrane material obtains the specific capacity of 2500-2600F/g under 10A/g current density.
Preferably, when the vulcanized sodium in step 5 is 2.3-2.5mg/mL, and the reaction time is 20-24h, the nickel sulfide/
Carbon nanotube membrane material obtains the specific capacity of 1600-1700F/g under 10A/g current density.
Compared with prior art, the beneficial effects of the present invention are:
1. enabling 4% silica/carbon nanotube more by being added and being firstly added dehydrated alcohol during the reaction
Good is infiltrated, and then chemical reaction is made not only to rest on the surface of carbon nanotube membrane material macroscopic view, and is more goed deep into micro-
Between seeing carbon nanotube, it is finally reached that reaction is more complete, and product is more uniform, active material load capacity is higher and active material
It is combined between carbon nanotube even closer；
2. keeping material manufacture craft easier by optimization reaction condition, greatly shortening material Production Time cost；
3. reaching the microcosmic even crystal form of nickel sulfide diverse microcosmic appearance and adjustability by the adjustment to reaction process；
4. nickel sulfide/carbon nano-tube film material preparation process the stabilization prepared by this method, while preparation cost is low
It is honest and clean, there is biggish commercial application potentiality.
5. nickel sulfide/carbon nanotube membrane material prepared by this method is used for supercapacitor field, obtain high
Chemical property.
Detailed description of the invention
Fig. 1 is nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 1；
Fig. 2 is nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 2；
Fig. 3 is nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 3；
Fig. 4 is nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 4；
Fig. 5 is nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 5；
Fig. 6 is nickel sulfide/carbon nano-tube film SEM image in embodiment 1；
Fig. 7 is nickel sulfide/carbon nano-tube film SEM image in embodiment 2；
Fig. 8 is nickel sulfide/carbon nano-tube film SEM image in embodiment 3；
Fig. 9 is nickel sulfide/carbon nano-tube film SEM image in embodiment 4；
Figure 10 is nickel sulfide/carbon nano-tube film SEM image in embodiment 5；
Figure 11 is nickel sulfide/carbon nano-tube film cyclic voltammetry curve in embodiment 1；
Figure 12 is nickel sulfide/carbon nano-tube film discharge curve in embodiment 1；
Figure 13 is nickel sulfide/carbon nano-tube film cyclic voltammetry curve in embodiment 2；
Figure 14 is nickel sulfide/carbon nano-tube film discharge curve in embodiment 2；
Figure 15 is nickel sulfide/carbon nano-tube film cyclic voltammetry curve in embodiment 3；
Figure 16 is nickel sulfide/carbon nano-tube film discharge curve in embodiment 3；
Figure 17 is nickel sulfide/carbon nano-tube film cyclic voltammetry curve in embodiment 4；
Figure 18 is nickel sulfide/carbon nano-tube film discharge curve in embodiment 4；
Figure 19 is nickel sulfide/carbon nano-tube film cyclic voltammetry curve in embodiment 5；
Figure 20 is nickel sulfide/carbon nano-tube film discharge curve in embodiment 5；
Specific embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.It should be appreciated that described herein
Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) the 4% silica/carbon nano-tube film for weighing 15mg is placed in 100mL blue bottle cap vial, measure 20mL without
Water-ethanol is added in bottle, jiggles body, makes ethanol solution complete wetting silica/carbon periosteum.
(2) 60mL deionized water is measured, 2.4mL concentration is the nickel nitrate solution of 0.1M, weighs 2g urea and is added sequentially to
It in blue lid bottle, is gently agitated for, until urea all dissolves.
(3) blue lid bottle 105 DEG C of reaction 12h in baking oven are placed in wash through deionized water at room temperature after natural cooling
Property, it is spare that silicic acid nickel carbon nano-tube film is obtained after dry；
(4) it weighs above-mentioned obtained silicic acid nickel carbon nano-tube film 3.5mg and is placed in 20mL ptfe autoclave
In, it measures 4mL dehydrated alcohol and is added in reaction kettle, make ethanol solution complete wetting silica/carbon periosteum.
(5) 12mL deionized water is measured, 1.5mg/mL vulcanized sodium is weighed as sulphur source, sequentially adds polytetrafluoroethyl-ne alkene reaction
Kettle washs to neutrality through deionized water after 160 DEG C of reaction 12h, room temperature natural cooling, ethyl alcohol is immersed, in polytetrafluoroethylene film
On sprawl, dried at room temperature to get to nickel sulfide/carbon nanotube membrane material.
Nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 1 is as shown in Figure 1, as can be seen from the figure this material
Peak value in XRD spectrum is not very sharply to illustrate that the crystallinity of material under this condition is not fine, but main peak position can be distinguished
Not, by being compared with standard PDF card, it can be determined that going out main object in material is mutually Ni3S2And Ni3Si2O5(OH)4, and it is main
For Ni3Si2O5(OH)4, in the above conditions, not exclusively due to time shorter second step vulcanization, also residual is not a large amount of anti-for this explanation
The Ni answered3Si2O5(OH)4.Nickel sulfide/carbon nano-tube film SEM spectrum in embodiment 1 in figure as shown in fig. 6, can be seen that
Curved elongated smooth carbon nanotube, which mutually overlaps, forms network, and the nanometer nickel sulfide piece of thin slice " flowers " shape is evenly distributed
Among carbon nano tube network, on the carbon nanotubes, some is distributed between carbon nanotube some packages, and some is grown in carbon nanometer
On managed network node, nanometer nickel sulfide piece " flowers " is tightly combined with carbon nanotube, and sheet flowers are in open three-dimensional porous
Structure.Electro-chemical test is carried out to the material in embodiment 1, Figure 11 is nickel sulfide in embodiment 1/carbon nano-tube film circulation volt
Pacify curve, scanning voltage range is 0~0.5V, and sweep speed variation is 5~200mV/s.CV curve in figure is clearly distinguishable from
The rectangle of standard, it is possible thereby to judge that its electrode material is mainly based upon faraday's reaction mechanism and carries out storage charge,
There are a pair of of redox peaks between 0.17~0.2V and between 0.35~0.4V, and peak shape has good symmetry,
This corresponds to the redox reaction that nickel ion occurs.Under the sweep speed of 5~200mV/s, CV curve shape is almost without change
Change, or even still there can be apparent redox peaks under the high sweep speed of 200mV/s, cathodic peak current potential change is about
For 0.1V, illustrate that the material is that have good invertibity, while implying that the electrode material has good multiplying power property.Figure 12
It is the chronopotentiogram under nickel sulfide in embodiment 1/carbon nanotube film composite material difference current density load, has no bright in figure
Aobvious IR drop, illustrates that the resistance of material is smaller, there are discharge platform between 0.2V~0.3V, illustrates have fake capacitance anti-at this
It answers.It calculates it can be concluded that nickel sulfide/carbon nanotube film composite material obtains the specific capacity of 808.2F/g under 1A/g current density,
When sweep speed increases to 2,5,10,20 and 50A/g, specific capacity is respectively 766.3,664.2,548.1,419.7 F/g, is
The 94.8% of initial capacity, 82.2%, 67.8%, 51.9%, illustrate nickel sulfide/carbon nanotube film composite material with great Rong
There is good multiplying power property while amount.In conjunction with its pattern and structural analysis, laminar Ni3S2Greatly increase composite material
Specific surface area, provides sufficient reaction site for electrode reaction, the carbon nano tube network to extend in all direction reduce electronics with from
The transmission distance of son, has not only acted as skeleton function, also provides transmission expressway for electronics, increases leading for metal sulfide
Electrically；Cross one another sheet metal sulfide forms three-dimensional honeycomb shape simultaneously, is conducive to the diffusion of electrolyte, in summary former
Because causing nickel sulfide/carbon nanotube film composite material specific capacity to improve very significantly, and have extraordinary multiplying power special
Property.
Embodiment 2
(1) the 4% silica/carbon nano-tube film for weighing 15mg is placed in 100mL blue bottle cap vial, measure 20mL without
Water-ethanol is added in bottle, jiggles body, makes ethanol solution complete wetting silica/carbon periosteum.
(2) 60mL deionized water is measured, 2.4mL concentration is the nickel nitrate solution of 0.1M, weighs 2g urea and is added sequentially to
It in blue lid bottle, is gently agitated for, until urea all dissolves.
(3) blue lid bottle 105 DEG C of reaction 12h in baking oven are placed in wash through deionized water at room temperature after natural cooling
Property, it is spare that silicic acid nickel carbon nano-tube film is obtained after dry；
(4) it weighs above-mentioned obtained silicic acid nickel carbon nano-tube film 3.5mg and is placed in 20mL ptfe autoclave
In, it measures 4mL dehydrated alcohol and is added in reaction kettle, make ethanol solution complete wetting silica/carbon periosteum.
(5) 12mL deionized water is measured, 1.5mg/mL vulcanized sodium is weighed as sulphur source, sequentially adds polytetrafluoroethyl-ne alkene reaction
Kettle for 24 hours in 160 DEG C of reactions after room temperature natural cooling, washs to neutrality through deionized water, ethyl alcohol is immersed, in polytetrafluoroethylene film
On sprawl, dried at room temperature to get to nickel sulfide/carbon nanotube membrane material.
Nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 2 is as shown in Fig. 2, as can be seen from the figure this material
Peak value in XRD spectrum is more sharp relative to embodiment 1, illustrates that vulcanization can be significantly changed by increasing the hydro-thermal reaction time
The crystal property of nickel carbon nanotube films material.By being compared with standard PDF card, it can be determined that going out main object in material is mutually
Ni3S2And Ni3Si2O5(OH)4, but compare Ni for Fig. 13S2Corresponding peak value is more obvious, this explanation is anti-by increasing hydro-thermal
It is more abundant to can be sulfidation between seasonable, Ni in material3S2Phase accounting greatly increases, but also residual is a small amount of unreacted
Ni3Si2O5(OH)4.Nickel sulfide/carbon nano-tube film SEM spectrum in embodiment 2 is as shown in fig. 7, as can be seen that material in figure
Microscopic appearance is substantially identical as the material in embodiment 1, but compares the SEM figure of embodiment 1 as can be seen that sheet cluster accounting
It is larger, and cluster itself combination is closer, exposed carbon pipe tails off.Electro-chemical test, Figure 13 are carried out to the material in embodiment 2
For nickel sulfide in embodiment 2/carbon nano-tube film cyclic voltammetry curve, scanning voltage range is 0~0.5V, sweep speed variation
For 5~50mV/s.CV curve shape in figure is similar with Figure 11, illustrates it is possible thereby to judge that its electrode material is mainly
Storage charge is carried out based on faraday's reaction mechanism.Compared with Figure 11, the face in same scan rate lower curve besieged city in Figure 13
Product is bigger, illustrates that material has more excellent super electrical property.Figure 14 is nickel sulfide in embodiment 3/carbon nanotube film composite material
Chronopotentiogram under different current density load has no apparent IR drop in figure, illustrates that the resistance of material is smaller, in 0.2V
There are discharge platform between~0.3V, illustrate there is fake capacitance reaction at this.It calculates it can be concluded that nickel sulfide/carbon nano-tube film is compound
Material obtains 1431.2 specific capacity under 10A/g current density, when sweep speed increases to 20,30,40 and 50A/g, than
Capacity is respectively 1269.8,1182.5,1100.5 and 1005.2F/g, is the 88.6% of initial capacity, 82.5%, 76.8%,
70.2%, illustrate that nickel sulfide/carbon nanotube film composite material has good multiplying power property while with large capacity.
Embodiment 3
(1) the 4% silica/carbon nano-tube film for weighing 15mg is placed in 100mL blue bottle cap vial, measure 20mL without
Water-ethanol is added in bottle, jiggles body, makes ethanol solution complete wetting silica/carbon periosteum.
(2) 60mL deionized water is measured, 1.0~2.5mL concentration is the nickel nitrate solution of 0.1M, weighs 2g urea and successively adds
Enter into blue lid bottle, be gently agitated for, until urea all dissolves.
(3) blue lid bottle 105 DEG C of reaction 12h in baking oven are placed in wash through deionized water at room temperature after natural cooling
Property, it is spare that silicic acid nickel carbon nano-tube film is obtained after dry；
(4) it weighs above-mentioned obtained silicic acid nickel carbon nano-tube film 3.5mg and is placed in 20mL ptfe autoclave
In, it measures 4mL dehydrated alcohol and is added in reaction kettle, make ethanol solution complete wetting silica/carbon periosteum.
(5) 12mL deionized water is measured, 1.8mg/mL vulcanized sodium is weighed as sulphur source, sequentially adds polytetrafluoroethyl-ne alkene reaction
Kettle for 24 hours in 160 DEG C of reactions after room temperature natural cooling, washs to neutrality through deionized water, ethyl alcohol is immersed, in polytetrafluoroethylene film
On sprawl, dried at room temperature to get to nickel sulfide/carbon nanotube membrane material.
Nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 3 is as shown in figure 3, as can be seen from the figure this material
Peak value in XRD spectrum is more sharp relative to Fig. 1,2, illustrates that vulcanization can be significantly changed by increasing the hydro-thermal reaction time
The crystal property of nickel carbon nanotube films material.By being compared with standard PDF card, it can be determined that go out main object phase base in material
Originally it is fully converted to Ni3S2Almost without residual Ni3Si2O5(OH)4, this explanation, which passes through increase the hydro-thermal reaction time, can make sulphur
Change process is more abundant.Nickel sulfide/carbon nano-tube film SEM spectrum in embodiment 3 is as shown in figure 8, as can be seen that material in figure
Expect that microscopic appearance is substantially identical as the material in embodiment 1, but compares the SEM figure of embodiment 1 as can be seen that sheet nickel sulfide
Load capacity becomes larger, and exposed carbon pipe tails off.Electro-chemical test is carried out to the material in embodiment 3, Figure 15 is to vulcanize in embodiment 3
Nickel carbon nano-tube film cyclic voltammetry curve, scanning voltage range are 0~0.5V, and sweep speed variation is 5~100mV/s.Figure
In CV curve shape it is similar with Figure 11, illustrate it is possible thereby to judge that its electrode material is mainly based upon faraday's reaction
Mechanism carries out storage charge.Compared with Figure 11, the area that same scan rate lower curve is encircled a city in Figure 15 is bigger, illustrates material
There is more excellent super electrical property.Figure 16 is nickel sulfide in embodiment 3/carbon nanotube film composite material difference current density load
Under chronopotentiogram, apparent IR drop is had no in figure, illustrates that the resistance of material is smaller, exists between 0.2V~0.3V and put
Level platform illustrates there is fake capacitance reaction at this.It calculates it can be concluded that nickel sulfide/carbon nanotube film composite material is in 10A/g electric current
The specific capacity of 1994.7F/g is obtained under density, when sweep speed increases to 20,30,40 and 50A/g, specific capacity is respectively
1734.0,1500.0,1356.3 and 1351.1F/g is the 86.9%, 75.2%, 67.8%, 67.7% of initial capacity, explanation
Nickel sulfide/carbon nanotube film composite material has good multiplying power property while with large capacity.
Embodiment 4
(1) the 4% silica/carbon nano-tube film for weighing 15mg is placed in 100mL blue bottle cap vial, measure 20mL without
Water-ethanol is added in bottle, jiggles body, makes ethanol solution complete wetting silica/carbon periosteum.
(2) 60mL deionized water is measured, 2.4mL concentration is the nickel nitrate solution of 0.1M, weighs 2g urea and is added sequentially to
It in blue lid bottle, is gently agitated for, until urea all dissolves.
(3) blue lid bottle 105 DEG C of reaction 12h in baking oven are placed in wash through deionized water at room temperature after natural cooling
Property, it is spare that silicic acid nickel carbon nano-tube film is obtained after dry；
(4) it weighs above-mentioned obtained silicic acid nickel carbon nano-tube film 3.5mg and is placed in 20mL ptfe autoclave
In, it measures 4mL dehydrated alcohol and is added in reaction kettle, make ethanol solution complete wetting silica/carbon periosteum.
(5) 12mL deionized water is measured, 2.1mg/mL vulcanized sodium is weighed as sulphur source, sequentially adds polytetrafluoroethyl-ne alkene reaction
Kettle for 24 hours in 160 DEG C of reactions after room temperature natural cooling, washs to neutrality through deionized water, ethyl alcohol is immersed, in polytetrafluoroethylene film
On sprawl, dried at room temperature to get to nickel sulfide/carbon nanotube membrane material.
Nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 4 is as shown in figure 4, as can be seen from the figure this material
Peak value in XRD spectrum is more sharp relative to Fig. 1,2 and 3, illustrates that sulphur can be significantly changed by increasing the hydro-thermal reaction time
Change the crystal property of nickel carbon nanotube films material.By being compared with standard PDF card, it can be determined that go out main object phase in material
Substantially completely it is converted into Ni3S2And NiS, absolutely not residual Ni3Si2O5(OH)4, this explanation can by increasing the hydro-thermal reaction time
To be that sulfidation is more abundant, while increasing vulcanization concentration and can change the type for ultimately producing object.Vulcanize in embodiment 4
The SEM spectrum of nickel carbon nano-tube film is as shown in figure 9, as can be seen that material microscopic appearance is substantially and in embodiment 1 in figure
Material is identical, but compares the SEM figure of embodiment 1 as can be seen that sheet vulcanization nickel loading becomes larger, and exposed carbon pipe tails off,
Lamella becomes bended and " softness " is even closer in conjunction with carbon pipe.Electro-chemical test, Figure 17 are carried out to the material in embodiment 4
For nickel sulfide in embodiment 2/carbon nano-tube film cyclic voltammetry curve, scanning voltage range is 0~0.5V, sweep speed variation
For 5~100mV/s.CV curve shape in figure is similar with Figure 11, illustrates it is possible thereby to judge that its electrode material is main
It is that storage charge is carried out based on faraday's reaction mechanism.Compared with Figure 11, same scan rate lower curve is surrounded in Figure 17
Area is bigger, illustrates that material has more excellent super electrical property.Figure 18 is nickel sulfide in embodiment 2/carbon nano-tube film composite wood
Expect the chronopotentiogram under different current density load, apparent IR drop is had no in figure, illustrates that the resistance of material is smaller,
There are discharge platform between 0.2V~0.3V, illustrate there is fake capacitance reaction at this.It calculates it can be concluded that nickel sulfide/carbon nano-tube film
Composite material obtains the specific capacity of 2540.5F/g under 10A/g current density, when sweep speed increases to 20,30,40 and 50A/
When g, specific capacity is respectively 2318.9,2213.5,2108.1.3 and 2027.0F/g, be initial capacity 91.2%, 87.1%,
82.9%, 79.8%, illustrate that nickel sulfide/carbon nanotube film composite material has good multiplying power while with very big capacity
Characteristic.
Embodiment 5
(1) the 4% silica/carbon nano-tube film for weighing 15mg is placed in 100mL blue bottle cap vial, measure 20mL without
Water-ethanol is added in bottle, jiggles body, makes ethanol solution complete wetting silica/carbon periosteum.
(2) 60mL deionized water is measured, 2.4mL concentration is the nickel nitrate solution of 0.1M, weighs 2g urea and is added sequentially to
It in blue lid bottle, is gently agitated for, until urea all dissolves.
(3) blue lid bottle 105 DEG C of reaction 12h in baking oven are placed in wash through deionized water at room temperature after natural cooling
Property, it is spare that silicic acid nickel carbon nano-tube film is obtained after dry；
(4) it weighs above-mentioned obtained silicic acid nickel carbon nano-tube film 3.5mg and is placed in 20mL ptfe autoclave
In, it measures 4mL dehydrated alcohol and is added in reaction kettle, make ethanol solution complete wetting silica/carbon periosteum.
(5) 12mL deionized water is measured, 2.4mg/mL vulcanized sodium is weighed as sulphur source, sequentially adds polytetrafluoroethyl-ne alkene reaction
Kettle for 24 hours in 160 DEG C of reactions after room temperature natural cooling, washs to neutrality through deionized water, ethyl alcohol is immersed, in polytetrafluoroethylene film
On sprawl, dried at room temperature to get to nickel sulfide/carbon nanotube membrane material.
Nickel sulfide/carbon nano-tube film XRD spectrum in embodiment 5 as shown in figure 5, by being compared with standard PDF card,
It may determine that main object is mutually substantially completely converted into Ni in material3S4, this different explanation of substance, which is generated, from Fig. 1~4 passes through increasing
Adding the hydro-thermal reaction time can be, sulfidation is more abundant, while increasing vulcanization concentration and can change the kind for ultimately producing object
Class.Nickel sulfide/carbon nano-tube film SEM spectrum is as shown in Figure 10 in embodiment 5, as can be seen that material microscopic appearance in figure
It is substantially different with Examples 1 to 4, but the SEM figure of Examples 1 to 4 is compared as can be seen that nickel sulfide is filled in carbon nanotube
In film gap, laminar nickel sulfide is significantly reduced, and crystalline particulate occurs.It is described above to can change by increasing vulcanization concentration
Ultimately produce object microscopic appearance.Electro-chemical test is carried out to the material in embodiment 5, Figure 19 is that vulcanization nickel carbon is received in embodiment 2
Mitron film cyclic voltammetry curve, scanning voltage range are 0~0.5V, and sweep speed variation is 5~100mV/s.CV in figure
Curve shape is similar with Figure 11, illustrate it is possible thereby to judge its electrode material be mainly based upon faraday's reaction mechanism into
Row storage charge.Compared with Figure 11, the area that same scan rate lower curve is encircled a city in Figure 19 is bigger, illustrates that material has more
Excellent super electrical property.Figure 20 is the meter under nickel sulfide in embodiment 2/carbon nanotube film composite material difference current density load
When potential diagram, apparent IR drop is had no in figure, illustrates that the resistance of material is smaller, it is flat to there is electric discharge between 0.2V~0.3V
Platform illustrates there is fake capacitance reaction at this.It calculates it can be concluded that nickel sulfide/carbon nanotube film composite material is in 10A/g current density
The lower specific capacity for obtaining 1656.9F/g, when sweep speed increases to 20,30,40 and 50A/g, specific capacity is respectively 1626.3,
1507.8,1410.5 and 1315.7F/g, be initial capacity 98.1%, 90.9%, 85.1%, 79.4%, illustrate nickel sulfide/
Carbon nanotube film composite material has good multiplying power property while with very big capacity.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (8)
1. nickel sulfide/application of the carbon nano tube flexible composite film material in supercapacitor, which is characterized in that the vulcanization
The preparation method of nickel carbon nanotube flexible composite film material the following steps are included:
Step 1, it weighs silica/carbon nano-tube film to be placed in dehydrated alcohol, so that without ethanol solution complete wetting silica/carbon
Periosteum；
Step 2, nickel nitrate solution, urea and deionized water are added into system prepared by step 1, is uniformly mixed complete to urea
Portion's dissolution；
Step 3, the resulting system of step 2 is placed in 90-120 DEG C of reaction 6-18h in baking oven, at room temperature after natural cooling, through going
It is spare to obtain silicic acid nickel carbon nano-tube film after dry to neutrality for ion water washing；
Step 4, it weighs 3~4mg silicic acid nickel carbon nano-tube film that step 3 obtains to be placed in ptfe autoclave, then takes
Dehydrated alcohol is added in reaction kettle, makes ethanol solution complete wetting silica/carbon periosteum；
Step 5, weigh 1.0~3.0mg/mL sodium sulfide solution, 15~16ml as sulphur source, the solvent of the vulcanized sodium be water and
The mixture of ethyl alcohol, sequentially adds ptfe autoclave, after 160 DEG C of reaction 9-24h, room temperature natural cooling, gone from
Sub- water washing immerses ethyl alcohol, sprawls on polytetrafluoroethylene film, dried at room temperature to get nickel sulfide/carbon nanotube is arrived to neutrality
Membrane material；
When the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 9-15h, in nickel sulfide/carbon nanotube membrane material
Object be mutually Ni3S2And Ni3Si2O5(OH)4, and predominantly Ni3Si2O5(OH)4；
When the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nanotube membrane material
In object be mutually Ni3S2And Ni3Si2O5(OH)4, and predominantly Ni3S2；
When the vulcanized sodium in step 5 is 1.7-1.9mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nanotube membrane material
In object be mutually Ni3S2；
When the vulcanized sodium in step 5 is 2.0-2.2mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nanotube membrane material
In object be mutually Ni3S2And NiS；
When the vulcanized sodium in step 5 is 2.3-2.5mg/mL, and the reaction time is 20-24h, nickel sulfide/carbon nanotube membrane material
In object be mutually Ni3S4。
2. nickel sulfide as described in claim 1/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, silica/carbon nano-tube film preparation method in the step 1, comprising the following steps:
S1, according to (95-100): (1.5-2): 1 mass ratio weighs ethyl alcohol, ferrocene and thiophene and is mixed to get mixed solution,
In, carbon source of the ethyl alcohol as this reaction, for ferrocene as catalyst, thiophene is as promotor, then weighs above-mentioned total mass fraction 1
Silicon source of~8% ethyl orthosilicate (TEOS) as reaction, is added in the mixed solution, at 40-60 DEG C, continual ultrasonic
Dispersion, is transferred to syringe after obtaining uniform dispersion, as precursor solution；
Vertical CVD furnace is fully sealed (water seal or oil sealing), is continually fed into the Ar of 50~200sccm by S2, is excluded in stove completely
Residual air, vertical CVD furnace is warming up to 1000~1250 DEG C, keeps the temperature 2~6h；
S3 closes Ar, the H of 600~900sccm is persistently injected in furnace after the completion2, to H2Full of entire vertical CVD burner hearth, then
By precursor solution in the fluid injection rate injection burner hearth of 4~12mL/h；The 10-30min or so after starting is reacted, at burner hearth bottom
Si oxide/carbon nano-tube film of portion's collection tubular class.
3. nickel sulfide as claimed in claim 2/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, the mass fraction of ethyl orthosilicate is 4% in the step S1.
4. nickel sulfide as described in claim 1/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, when the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 9-15h, the vulcanization nickel carbon nanometer
Periosteum material obtains the specific capacity of 540-550F/g under 10A/g current density.
5. nickel sulfide as described in claim 1/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, when the vulcanized sodium in step 5 is 1.4-1.6mg/mL, and the reaction time is 20-24h, the vulcanization nickel carbon nanometer
Periosteum material obtains the specific capacity of 1400-1500F/g under 10A/g current density.
6. nickel sulfide as described in claim 1/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, when the vulcanized sodium in step 5 is 1.7-1.9mg/mL, and the reaction time is 20-24h, the vulcanization nickel carbon nanometer
Periosteum material obtains the specific capacity of 1900-2000F/g under 10A/g current density.
7. nickel sulfide as described in claim 1/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, when the vulcanized sodium in step 5 is 2.0-2.2mg/mL, and the reaction time is 20-24h, the vulcanization nickel carbon nanometer
Periosteum material obtains the specific capacity of 2500-2600F/g under 10A/g current density.
8. nickel sulfide as described in claim 1/application of the carbon nano tube flexible composite film material in supercapacitor,
It is characterized in that, when the vulcanized sodium in step 5 is 2.3-2.5mg/mL, and the reaction time is 20-24h, the vulcanization nickel carbon nanometer
Periosteum material obtains the specific capacity of 1600-1700F/g under 10A/g current density.
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| CN110534354A (en) * | 2019-08-12 | 2019-12-03 | 江苏大学 | Carbon nanotube is interspersed in the composite film electrode preparation method and applications in CuS nano particle |
| CN111939942A (en) * | 2020-07-17 | 2020-11-17 | 清华大学 | Carbon nano tube composite catalytic film and preparation method thereof |
| EP3961667A1 (en) * | 2020-08-26 | 2022-03-02 | Jozef Stefan Institute | Method for manufacturing hybrid binder-free electrodes for electrochemical energy storage devices |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110534354A (en) * | 2019-08-12 | 2019-12-03 | 江苏大学 | Carbon nanotube is interspersed in the composite film electrode preparation method and applications in CuS nano particle |
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| EP3961667A1 (en) * | 2020-08-26 | 2022-03-02 | Jozef Stefan Institute | Method for manufacturing hybrid binder-free electrodes for electrochemical energy storage devices |
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