CN109755036A - Nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method and application - Google Patents
Nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method and application Download PDFInfo
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- CN109755036A CN109755036A CN201811579139.0A CN201811579139A CN109755036A CN 109755036 A CN109755036 A CN 109755036A CN 201811579139 A CN201811579139 A CN 201811579139A CN 109755036 A CN109755036 A CN 109755036A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention discloses a kind of nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method of volume contraction, specific steps are as follows: (a) prepares carbon nano-tube solution by pickling reflow treatment single-walled carbon nanotube；(b) polyurethane foam is cleaned, by carbon coated pipe and burns process preparation carbon nanotube foam；(c) carbon nanotube foam is put into the mixed solution of nickel chloride, cobalt chloride, urea, distilled water, methanol, is placed in tube furnace and is heat-treated after hydro-thermal reaction and drying, obtains cobalt acid nickel foam；(d) cobalt acid nickel foam is placed in sodium sulfide solution and obtains the composite material after hydro-thermal process；Composite material quality capacitor after vulcanizing treatment greatly improves, and volume-diminished is 1/10th originally, so that its area capacitance and volumetric capacitance for obtaining superelevation；The composite material can be adapted for current wearable, portable energy-storing equipment.
Description
Technical field
The present invention relates to electrochemical field, nickel sulfide/sulphur cobalt nickel carbon nanotube foam of especially a kind of volume contraction
Preparation method and application.
Background technique
Carbon nanotube was found in the Iijima doctor by Japan Electronics Corporation (NEC) in 1991, because its is light-weight and has excellent
Different mechanics, electricity, chemical property and receive significant attention.In electrochemical field, it is whole to improve material to be commonly incorporated into carbon nanotube
The electric conductivity of body.Three dimensional carbon nanotubes foam have high density, high resiliency, high conductivity and be widely used in electrochemical energy storage
The self-supporting electrode basement of device, the intrinsic hole of the material provide express passway for the transport of electronic and ionic, it is ensured that electricity
The good high rate performance of pole material.
The transition metal oxide of transient metal sulfide corresponding thereto is compared with higher electro-chemical activity and is led
Electrical property and be easy to by oxide convert preparation and by extensive concern.Ni-Co-S has very as ternary transition metal sulfide
Good capacitive property, compared with binary transition metal sulfide and ternary transition metal oxide, it has richer oxidation
Reduction reaction and higher capacitor.
Wearable at present, portable device is grown rapidly, therefore electrode material is required to have miniaturization, and high resilience
Etc. features.
The substrate surfaces such as carbon cloth, nickel screen product is big or without elasticity, and which limits them towards miniaturization, portable hair
Exhibition, and low area specific capacitance and volumetric capacitance is also one limiting factor.The Yang Quan Red Sect of Lamaism of University Of Tianjin, which awards, to endeavour
In evaporation drying method preparation volume contraction Graphene gel (Y.Tao, X.Xie, W.Lv, D.M.Tang, D.Kong,
Z.Huang,H.Nishihara,T.Ishii,B.Li,D.Golberg,F.Kang,T.Kyotani and Q.H.Yang,Sci
Rep 2013,3,2975.), volumetric capacitance reaches 376F cm-3, due to without the fake capacitance material knot with high specific capacitance
It closes, limits further increasing for its capacitor.It is at present that three dimensional carbon nanotubes foam and Ni-Co-S is compound, to prepare with body
There is not been reported for the method for the small electrode material for super capacitor of product.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of first that carbon nanotube foam and cobalt acid nickel is compound, then pass through vulcanized sodium
One step of cobalt acid nickel is vulcanized and prepares nickel sulfide/sulphur cobalt nickel carbon nanotube foam electrode side for nickel sulfide/sulphur cobalt nickel method
Method.This method is vulcanized using vulcanized sodium, forms carbon-sulfur bond in the process and the active force between carbon pipe is enhanced, thus carbon
Nanotube foam volume is shunk significantly, to achieve the purpose that prepare electrode material small in size.
The present invention is achieved through the following technical solutions:
A kind of preparation method of the nickel sulfide of volume contraction/sulphur cobalt nickel carbon nanotube foam, the specific steps of which are as follows:
(a) single-walled carbon nanotube is dissolved in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, flow back 2h at 70 DEG C, is added and steams
It is filtered after distilled water and (constantly uses distilled water flushing during filtering), and cleaning to filter residue is neutrality, adds distilled water and obtains acid
Change single-walled carbon nanotube dispersion liquid；
(b) dry after cleaning polyurethane foam, it is then immersed in the acidification single-walled carbon nanotube dispersion of step (a) acquisition
In liquid, and squeezing 3-5s with tweezers makes carbon nano-tube solution sufficiently be coated on foam surface, and taking-up is placed in 70 DEG C of baking ovens, dry
12h repeats above-mentioned submergence drying steps twice, finally obtains the polyurethane foam for being coated with carbon pipe；By the poly- ammonia of carbon coated pipe
Ester foam, which is placed on alcolhol burner, burns 15-20s, and (minimum 15s guarantees that polyurethane can completely remove to burning-off polyurethane, and the time is more than
20s can generate destruction to carbon nanotube foam), obtain carbon nanotube foam.Above-mentioned carbon coated pipe and baked wheaten cake specific steps can also
Referring to Chinese patent CN108163837A disclosure of that.
(c) nickel chloride, cobalt chloride, urea are dissolved in methanol aqueous solution (volume ratio of methanol and water is 6:1), and filled
Divide stirring, obtains pink colour solution；In the pink colour solution, nickel chloride, cobalt chloride, urea concentration be followed successively by 0.005mol L-1、
0.01mol L-1、0.4mol L-1；Above-mentioned pink colour solution is transferred in 50mL ptfe autoclave, and by carbon nanotube
Foam is immersed, 120 DEG C of hydro-thermal reaction 6h, after being then cooled to room temperature, take out sample distilled water and dehydrated alcohol according to
Sample drying is placed in tubular type and is rapidly heated in furnace by secondary washing, and calcining at constant temperature 2h is under 300 DEG C of air to get to being supported on carbon
Cobalt acid nickel on nanotube foam；
(d) vulcanized sodium is dissolved in distilled water, being made into concentration range is 0.003-0.012mol L-1Solution and transfer
Enter in 50mL ptfe autoclave, the cobalt acid nickel being supported on carbon nanotube foam that step (c) is obtained immerses solution
In, 120 DEG C of hydro-thermal reaction 8h after being cooled to room temperature, take out dry at a temperature of sample is washed with distilled water 2~3 times, 60 DEG C
12h is to get the nickel sulfide/sulphur cobalt nickel carbon nanotube foam for arriving the volume contraction.
Further, in the nickel sulfide of above-mentioned volume contraction/sulphur cobalt nickel carbon nanotube foam preparation method, step (a)
In, the body of the concentrated sulfuric acid (mass fraction 95.0-98.0%) and concentrated nitric acid (mass fraction 65.0-68.0%) in the mixed solution
Product is than being 3:1；The concentration of single-walled carbon nanotube solution obtained is about 1mg mL-1(concentration is too low, subsequent in polyurethane foam
The step of upper carbon coated pipe, needs were repeated as many times, and wasted time；Concentration is too high, and it is uneven to will lead to cladding) acidification single wall carbon
Nanotube dispersion liquid.
Further, in the nickel sulfide of above-mentioned volume contraction/sulphur cobalt nickel carbon nanotube foam preparation method, in step (b)
It is described by polyurethane foam clean after drying refer to: polyurethane foam is cut to 1cm-3Square size, successively with washing powder, steaming
After distilled water, dehydrated alcohol are cleaned, it is placed in 60 DEG C of dry 12h.
Use nickel sulfide/sulphur cobalt nickel carbon nanotube foam of above-mentioned volume contraction as super secondly, the present invention goes back body
The application of electrode for capacitors.
The nickel sulfide of volume contraction prepared by the method for the present invention/sulphur cobalt nickel carbon nanotube foamed composite, in structure
It is to load nickel sulfide/sulphur cobalt nickel three-dimensional manometer array in top using carbon nanotube foam as skeleton, is cross-linked with each other and part collapses
The nickel sulfide to collapse/sulphur cobalt nickel array increases the contact area with foam substrate, improves the electric conductivity of material, furthermore vulcanizes
Hole on nickel/sulphur cobalt nickel nano film increases the contact between active material and electrolyte, facilitates the transfer of electronics and ion, can
To guarantee the relatively good high rate performance of material.
Vulcanisation step can convert cobalt acid nickel nano film to nickel sulfide/sulphur cobalt nickel nano film, form carbon-sulfur bond in the process
So that the active force enhancing between carbon pipe realizes the miniaturization of electrode, greatly improves electricity to make its volume shrink significantly
The area specific capacitance and volumetric capacitance of pole material.In addition, also creating the certain destruction of nickel sulfide/sulphur cobalt nickel nano film, increase
Its big contact with substrate, increases the electric conductivity of material entirety, the hole in nanometer sheet caused by sulfidation increases
Contact of the active material with electrolyte, facilitates the transmission of electronic and ionic.
The composite material that the present invention obtains shows fabulous chemical property and good cyclicity as electrode material
Can, in 1A g-1Quality specific capacitance, area specific capacitance, volumetric capacitance under current density are respectively 2905F g-1、10.46F
cm-2、1307.25F cm-3；In 10A g-1Current density under circulation 10000 circle, capacity retention is still 83%.
Detailed description of the invention
Fig. 1 is volume vs' figure of electrode composite material vulcanization front and back prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD diagram of electrode composite material prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM figure of electrode composite material prepared by the embodiment of the present invention 1.
Fig. 4 is the cyclic voltammogram of electrode composite material prepared by the embodiment of the present invention 1.
Fig. 5 is the chronopotentiogram of electrode composite material prepared by the embodiment of the present invention 1.
Fig. 6 is the cycle life figure of electrode composite material prepared by the embodiment of the present invention 1.
Specific embodiment
The purchase of single-walled carbon nanotube used in embodiment is in Shenzhen nanometer port limited liability company (SWNT-2)；
Polyurethane foam used in embodiment is bought in Nantong great Gong sponge Co., Ltd.
It if not remaining reagent and material illustrate, is bought by commercial sources.
Embodiment 1
(1) by 200mg single-walled carbon nanotube ultrasonic disperse volume ratio be 3:1 the concentrated sulfuric acid (mass fraction 98.0%) and
In the mixed liquor of concentrated nitric acid (mass fraction 68.0%), flow back 2h at 70 DEG C, be added distilled water dilute and stirs, filter and with steaming
Distilled water is washed till neutrality, and being finally in control concentration with distilled water dilution carbon is 1mg mL-1Acidification single-walled carbon nanotube dispersion liquid.
(2) polyurethane foam is cut into 1 × 1 × 1cm3Cube (in the specific implementation process, can be according to requiring to steep
Size and shape required for foam is cut into), successively through washing powder, distilled water, EtOH Sonicate washing, (ultrasonic power is all
500W, time are 20min) after 70 DEG C of dry 12h, it is immersed into the acidification single-walled carbon nanotube dispersion liquid of step (1) acquisition,
And squeezing 3-5s with tweezers makes carbon nano-tube solution sufficiently be coated on foam surface, taking-up sponge, which is placed in 70 DEG C of baking oven, to do
Then dry 12h is immersed into again in the acidification single-walled carbon nanotube dispersion liquid, repetition above-mentioned submergence-drying steps 1 time (i.e. total
Infiltration-drying 2 times) obtain coated single-walled carbon nano tube polyurethane foam；
By the foam composite after above-mentioned drying, as polyurethane is burnt up on alcolhol burner flame, (about 15s or so is embodied
In, calcination time controls within the scope of 15s-20s, can burn up polyurethane), that is, form flexible nitrogen-doped carbon nanometer pipe
Foam, calculating its density according to quality weighing and volume is 1.5mg cm3。
(3) nickel chloride, cobalt chloride, urea are dissolved in methanol aqueous solution to (methanol and water volume ratio be 6:1), sufficiently stirred
Mix to form pink colour solution, in the pink colour solution, nickel chloride, cobalt chloride, urea concentration be followed successively by 0.005mol L-1、0.01mol
L-1、0.4mol L-1；The nitrogen that above-mentioned pink colour solution is transferred in 50mL ptfe autoclave, and step (2) are obtained
Doped carbon nanometer pipe foam is immersed, 120 DEG C of hydro-thermal reaction 6h；After being cooled to room temperature, sample distilled water and nothing are taken out
Sample, is put into 60 DEG C of baking oven 12h drying and is placed in tubular type and be rapidly heated in furnace by water-ethanol washing, with 1 DEG C of min-1Liter
Warm rate, calcining at constant temperature 2h under 300 DEG C of air, obtains the cobalt acid nickel being supported on carbon nanotube foam.
(4) 0.006mol L is prepared-1Sodium sulfide solution and be transferred in 50mL ptfe autoclave, by step
(3) the cobalt acid nickel being supported on carbon nanotube foam obtained immerses in solution, 120 DEG C of hydro-thermal reaction 8h；It is cooled to room temperature
Afterwards, it takes out sample to be washed with distilled water 2-3 times, dry 12h is under the conditions of 60 DEG C to get the nickel sulfide/sulphur cobalt for arriving volume contraction
Nickel carbon nanotube foam.
Fig. 1 is nickel sulfide/sulphur cobalt nickel carbon nanotube foam vulcanization front and back body of the volume contraction manufactured in the present embodiment
Product comparison pictorial diagram, in Fig. 1, a be it is in kind before vulcanization, b is in kind after vulcanization；From figure 1 it appears that the vulcanization after vulcanization
The volume ratio of cobalt acid nickel carbon nanotube foam before nickel/sulphur cobalt nickel carbon nanotube foam and vulcanization is 1:10, this is just the electricity
Pole material is suitable for miniaturization energy storage device and provides possibility.
Fig. 2 is nickel sulfide manufactured in the present embodiment/sulphur cobalt nickel carbon nanotube foamed composite XRD diagram, the portion a in figure
It is divided into NiS2Standard PDF card, b part be NiCo2S4Standard PDF card, c part be nickel sulfide manufactured in the present embodiment/
The XRD curve of sulphur cobalt nickel carbon nanotube foamed composite, as can be seen from Figure 2 the basic composite sulfuration nickel of the composite material,
The characteristic peak of sulphur cobalt nickel.
Fig. 3 is nickel sulfide manufactured in the present embodiment/sulphur cobalt nickel carbon nanotube foamed composite vulcanization front and back SEM figure,
In Fig. 3, (a-b) is the cobalt acid nickel carbon nanotube foam (i.e. the product of step 3 acquisition) before the vulcanization of different amplification
SEM figure, (c-f) is nickel sulfide/sulphur cobalt nickel carbon nanotube foam SEM figure after the vulcanization of different amplification, from Fig. 3
As can be seen that the skeleton of carbon nanotube foam is collapsed after vulcanization, the structure of active material nanometer sheet is also by certain journey
The destruction of degree, lamella is thinning, and hole occurs, and which increases the contacts between active material and foam, increases material
Whole electric conductivity, while also increasing the contact between material and electrolyte, quick for electronic and ionic transmit that provide can
Energy.
The nickel sulfide of volume contraction manufactured in the present embodiment/sulphur cobalt nickel carbon nanotube foam can be used as super capacitor electrode
Pole material, Fig. 4, Fig. 5 are the cyclic voltammogram and charging and discharging curve figure of the electrode.
Fig. 4 sweeps following under speed in difference for nickel sulfide manufactured in the present embodiment/sulphur cobalt nickel carbon nanotube foamed composite
Ring voltammogram, visible more symmetrical redox peaks in figure, with fast increase is swept, there is no biggish changes for cyclic voltammetry curve
Change, illustrates that its high rate performance is preferable.
Fig. 5 is nickel sulfide manufactured in the present embodiment/sulphur cobalt nickel carbon nanotube foamed composite under different current densities
Charging and discharging curve, an as can be seen from Figure 5 obvious charge and discharge platform, this is by the counterfeit electricity of nickel sulfide/sulphur cobalt nickel
Hold generation；In 1A g-1The quality specific capacitance of the material is 2905F g under current density-1, be higher than and the routine reported at present
Quality specific capacitance is about 2000F g-1。
Fig. 6 is nickel sulfide manufactured in the present embodiment/sulphur cobalt nickel carbon nanotube foamed composite cycle life figure,
10A g-1Current density under circulation 10000 circle after, capacity retention is still 83%, shows good cyclical stability.
In specific implementation, within the scope of 95.0-98.0%, the mass fraction of concentrated nitric acid exists the mass fraction of the concentrated sulfuric acid
Within the scope of 65.0-68.0%, the purpose of invention can be achieved.
Embodiment 2
In the present embodiment, step (1), (2), (3) with embodiment 1, step (4) is specific as follows: taking concentration is 0.006mol
L-1The solution of vulcanized sodium is transferred in 50mL ptfe autoclave, is supported on carbon nanotube foam for what step (3) obtained
On cobalt acid nickel immerse solution in, 100 DEG C of hydro-thermal reaction 8h, after being cooled to room temperature, take out sample be washed with distilled water 2~3
Secondary, dry 12h, obtains nickel sulfide/sulphur cobalt nickel carbon nanotube foam under the conditions of 60 DEG C.
Through detecting, nickel sulfide/sulphur cobalt nickel carbon nanotube foam that the present embodiment benefit obtains is 1A g in current density-1Under
Quality specific capacitance, test resulting capacitor be 2307F g-1。
Embodiment 3
In the present embodiment preparation step, step (1), (2), (3) with embodiment 1, step (4) is as follows: taking the concentration to be
0.006mol L-1Sodium sulfide solution is transferred in 50mL ptfe autoclave, is supported on carbon nanometer for what step (3) obtained
Cobalt acid nickel on envelope foam immerses in solution, 110 DEG C of hydro-thermal reaction 8h, after being cooled to room temperature, takes out sample distillation washing
It washs 2~3 times, dry 12h, obtains nickel sulfide/sulphur cobalt nickel carbon nanotube foam under the conditions of 60 DEG C.
Through detecting, nickel sulfide/sulphur cobalt nickel carbon nanotube foam that the present embodiment benefit obtains is 1A g in current density-1Under
Quality specific capacitance, test resulting capacitor be 2750F g-1。
Embodiment 4
In the present embodiment preparation step, step (1), (2), (3) with embodiment 1, step (4) is as follows: taking the concentration to be
0.006mol L-1Sodium sulfide solution be transferred in 50mL ptfe autoclave, by step (3) obtain the carbon that is supported on receive
Cobalt acid nickel on mitron foam immerses in solution, 130 DEG C of hydro-thermal reaction 8h, after being cooled to room temperature, takes out sample distilled water
Washing 2~3 times dries 12h under the conditions of 60 DEG C to get nickel sulfide/sulphur cobalt nickel carbon nanotube foam is arrived.
Through detecting, nickel sulfide/sulphur cobalt nickel carbon nanotube foam that the present embodiment benefit obtains is 1A g in current density-1Under
Quality specific capacitance, test resulting capacitor be 2800F g-1。
Embodiment 5
In the present embodiment preparation step, step (1), (2), (3) are the same as embodiment 1.Rapid (4) are as follows step by step: taking the concentration to be
0.006mol L-1The solution of vulcanized sodium is simultaneously transferred in 50mL ptfe autoclave, is supported on carbon for what step (3) obtained
Cobalt acid nickel on nanotube foam immerses in solution, 140 DEG C of hydro-thermal reaction 8h, after being cooled to room temperature, takes out sample distillation
Water washing 2~3 times, 12h is dried under the conditions of 60 DEG C to get nickel sulfide/sulphur cobalt nickel carbon nanotube foam is arrived.
Through detecting, nickel sulfide/sulphur cobalt nickel carbon nanotube foam that the present embodiment benefit obtains is 1A g in current density-1Under
Quality specific capacitance, test resulting capacitor be 2645F g-1。
Embodiment 6
In the present embodiment preparation step, step (1), (2), (3) are the same as embodiment 1.Step (4) is specific as follows: taking the concentration to be
0.003mol L-1The solution of vulcanized sodium is simultaneously transferred in 50mL ptfe autoclave, is supported on carbon for what step (3) obtained
Cobalt acid nickel on nanotube foam immerses in solution, 120 DEG C of hydro-thermal reaction 8h, after being cooled to room temperature, takes out sample distillation
Water washing 2~3 times, 12h is dried under the conditions of 60 DEG C to get nickel sulfide/sulphur cobalt nickel carbon nanotube foam is arrived.
Through detecting, nickel sulfide/sulphur cobalt nickel carbon nanotube foam that the present embodiment benefit obtains is 1A g in current density-1Under
Quality specific capacitance, test resulting capacitor be 2745F g-1。
Embodiment 7
In the present embodiment preparation step, step (1), (2), (3) with embodiment 1, step (4) is specific as follows: taking the concentration to be
0.012mol L-1Sodium sulfide solution and be transferred in 50mL ptfe autoclave, step (3) obtain the carbon that is supported on receive
Cobalt acid nickel on mitron foam immerses in solution, 120 DEG C of hydro-thermal reaction 8h, after being cooled to room temperature, takes out sample distilled water
Washing 2~3 times dries 12h under the conditions of 60 DEG C to get nickel sulfide/sulphur cobalt nickel carbon nanotube foam is arrived.
Through detecting, nickel sulfide/sulphur cobalt nickel carbon nanotube foam that the present embodiment benefit obtains is 1A g in current density-1Under
Quality specific capacitance, test resulting capacitor be 2630Fg-1。
Above example only to illustrate technical solution of the present invention rather than limits, although carrying out referring to preferred embodiments to the present invention
It is described in detail, it will be apparent to an ordinarily skilled person in the art that can modify to technical solution of the present invention, but it is
It is intended to be within the scope of the claims of the invention.
Claims (8)
1. a kind of nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method, the specific steps of which are as follows:
(a) single-walled carbon nanotube is dissolved in mixed solution, 70 DEG C of reflux 2h, filtering and cleaning to filter residue is neutrality, then plus
Enter distilled water and obtains acidification single-walled carbon nanotube dispersion liquid；The mixed solution after the concentrated sulfuric acid and concentrated nitric acid mixing by obtaining；
Polyurethane foam is immersed in the acidification single-walled carbon nanotube dispersion liquid of step (a) acquisition by (), then takes out drying, weight
Multiple above-mentioned submergence-drying steps twice, obtain the polyurethane foam for being coated with carbon pipe；The polyurethane foam of carbon coated pipe is placed in
Calcination 15-20 s on alcolhol burner obtains carbon nanotube foam；
(c) nickel chloride, cobalt chloride, urea are dissolved in methanol aqueous solution, obtain pink colour solution, the carbon that step (b) is obtained
Nanotube foam is in the pink colour solution, and 120 DEG C of 6 h of hydro-thermal reaction, then 300 DEG C of calcining at constant temperature 2h, obtain being supported on carbon
Cobalt acid nickel on nanotube foam；
(d) the cobalt acid nickel on the carbon nanotube foam of step (c) acquisition is immersed in sodium sulfide solution, 120 DEG C of hydro-thermal reactions 8
H obtains the nickel sulfide/sulphur cobalt nickel carbon nanotube foam then to distill drying after water washing.
2. nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method according to claim 1, which is characterized in that
The concentration of step (a) the acidification single-walled carbon nanotube dispersion liquid is 1 mg mL-1。
3. nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method according to claim 1, which is characterized in that
The concentration of step (d) sodium sulfide solution is 0.003-0.012 mol L-1。
4. nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method according to claim 1, which is characterized in that step
(c) in the pink colour solution, nickel chloride, cobalt chloride, urea concentration be followed successively by 0.005 mol L-1、0.01 mol L-1、0.4
mol L-1。
5. according to nickel sulfide described in claim 1/sulphur cobalt nickel carbon nanotube foam preparation method, which is characterized in that step (a)
In the mixed solution, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
6. nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method according to claim 1, which is characterized in that step
(b) polyurethane foam obtains by the following method: polyurethane foam is successively used to washing powder, distilled water, anhydrous second
After alcohol is cleaned, in 60 DEG C of dry 12 h.
7. nickel sulfide/sulphur cobalt nickel carbon nanotube foam preparation method according to claim 4, which is characterized in that step
(a) in the mixed solution, the mass fraction of the concentrated sulfuric acid is 95.0-98.0%, and the mass fraction of the concentrated nitric acid is
65.0-68.0%.
8. the nickel sulfide as prepared by claim 1-6 either method/sulphur cobalt nickel carbon nanotube foam is as supercapacitor
Application in electrode.
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| CN110197769A (en) * | 2019-05-16 | 2019-09-03 | 华南师范大学 | A kind of composite carbon nanometer tube material and its preparation method and application |
| CN110336047A (en) * | 2019-07-16 | 2019-10-15 | 运城学院 | Nickel cobalt sulfide/graphene composite material zinc and air cell bifunctional catalyst preparation method |
| CN113551814A (en) * | 2021-06-23 | 2021-10-26 | 浙江工业大学 | Preparation method and application of electrode material with carbon/MOF three-dimensional continuum structure |
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| CN113551814A (en) * | 2021-06-23 | 2021-10-26 | 浙江工业大学 | Preparation method and application of electrode material with carbon/MOF three-dimensional continuum structure |
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