CN108010736A - NiCo is constructed based on nickel foam template2S4@Ni(OH)2@PPy materials are used for the method for ultracapacitor - Google Patents
NiCo is constructed based on nickel foam template2S4@Ni(OH)2@PPy materials are used for the method for ultracapacitor Download PDFInfo
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- CN108010736A CN108010736A CN201810032192.2A CN201810032192A CN108010736A CN 108010736 A CN108010736 A CN 108010736A CN 201810032192 A CN201810032192 A CN 201810032192A CN 108010736 A CN108010736 A CN 108010736A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 title claims abstract description 38
- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 31
- 239000006260 foam Substances 0.000 title claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000002071 nanotube Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 85
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 235000019441 ethanol Nutrition 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 17
- 239000012498 ultrapure water Substances 0.000 claims description 17
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000012901 Milli-Q water Substances 0.000 claims description 6
- 229910017709 Ni Co Inorganic materials 0.000 claims description 6
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 6
- 239000004809 Teflon Substances 0.000 claims description 6
- 229920006362 Teflon® Polymers 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 229920000128 polypyrrole Polymers 0.000 description 35
- 244000061458 Solanum melongena Species 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Method of the 2@PPy materials of NiCo2S4@Ni (OH) for ultracapacitor, method and step 1 are constructed based on nickel foam template the invention discloses a kind of) prepare NiCo2S4Nano-tube array：2) NiCo is prepared2S4@Ni(OH)2；3) NiCo is prepared2S4@Ni(OH)2@PPy.Preparation method of the present invention is simple, and cost is relatively low.The super capacitor anode material of preparation has higher area specific capacity and power density, shows good chemical property.And NiCo is synthesized first2S4@Ni(OH)2@PPy core shell structures, have novelty；Good chemical property, has practicality.
Description
Technical field
The invention belongs to super capacitor anode material synthesis technical field, is related to one kind and is constructed based on nickel foam template
NiCo2S4@Ni(OH)2The preparation method of@PPy core shell structures.
Background technology
As the transition of fossil energy is exploited and is drastically consumed, energy problem and environmental degradation have enjoyed people to pay close attention to.
Exploitation at present cleans cheap environmental-friendly energy-storage travelling wave tube to alleviate the energy crisis of current social, for developing national economy,
Realize that sustainable development is of great significance.At present, ultracapacitor is considered as effective approach as emerging energy-storage travelling wave tube
One of.Research shows：1. compared to lithium ion battery, super capacitor material has the power density of higher, can realize quick
Discharge and recharge；2. aqueous super capacitor material has the characteristics that green, nonpollution environment are friendly, have in power energy field
Application value.
The preparation method of super capacitor anode material has been used for it on carrying transition metal sulfide in situ in nickel foam
It has been reported that but be prepared in situ multi-layer core-shell structure be used for super capacitor system report it is very few.Hydro-thermal method is in nickel foam
NiCo is constructed in template2S4Nano-tube array, and in NiCo2S4The ultra-thin Ni of growth in situ (OH) on nano-tube array2Nanometer sheet, greatly
Big lifting NiCo2S4The specific surface area of nanotube matrix, improves specific capacitance；Secondary load polypyrrole (PPy) lifts the conduction of matrix
Property, increase electric transmission effect.In addition, in NiCo2S4Ni (OH) is loaded on nano-tube array at the same time2With PPy as super
The nearly no report of capacitor anode material.
The content of the invention
Present invention aims at provide one kind to construct 2@PPy materials of NiCo2S4@Ni (OH) for surpassing based on nickel foam template
The method of level capacitor.The positive electrode is green, environmental-friendly, and has high specific surface area and high conductance
Rate, has high power density and area specific capacity compared to other positive electrodes of growth in situ.Show it in high power, height
There is larger application potential in security and power field.
The purpose of the present invention is by the following technical programs to solve：
NiCo is constructed based on nickel foam template2S4@Ni(OH)2@PPy materials are used for the method for ultracapacitor, including following
Step：
1) NiCo is prepared2S4Nano-tube array：
Before synthesis, 1 × 3cm of nickel foam is immersed into acetone successively, HCl solution, is then dried in atmosphere, is denoted as sample
Product A；By 0.1~0.4 mM of NiCl2·6H2O, 0.1~0.8 mM of CoCl2·6H2O and 1.0~5.0 mM of urea
Progress room temperature magnetic agitation in 5~30 milliliters of ultra-pure waters is dissolved in, until forming royal purple clear solution, is denoted as solution B；Will
Sample A and solution B are transferred in the autoclave of 10~50 milliliters of teflon lineds at the same time, and 6 are kept at 110~130 DEG C
~10 it is small when, then cooled to room temperature, the Ni-Co precursors in obtained nickel foam are washed with ultra-pure water and EtOH Sonicate
It is several times and dry, it is denoted as sample C；Then sample C is placed in together with the aqueous solution of 5~30 milliliters of vulcanized sodium in autoclave and
When holding 8~10 is small at 80~100 DEG C, product uses ethanol and milli-Q water repeatedly, and collects the nickel foam sample so prepared
Product, and be dried in vacuum overnight at 50~70 DEG C, it is denoted as sample D；
2) NiCo is prepared2S4@Ni(OH)2
By 0.1~1.5 mM of NiCl2·6H2O and 0.1~5 mM of urea is dissolved in 5~30 milliliters of ultra-pure waters, into
Row room temperature magnetic agitation, until forming greenish transparent solution, is denoted as solution E, is then transferred to sample D and solution E at the same time
In 10~50 milliliters of autoclaves and when holding 1~2 is small at 90~110 DEG C, after cooled to room temperature, gained sample with ethanol
With ultrapure water for several times, when vacuum drying 10~14 is small at 50~70 DEG C, it is denoted as sample F；
3) NiCo is prepared2S4@Ni(OH)2@PPy
0.01~2 mM of p-methyl benzenesulfonic acid p-TSA is first dissolved in 1~10 milliliter of absolute ethyl alcohol, then above-mentioned
1~10 microlitre of pyrrole monomer is added in solution, sonic oscillation orders solution obtained above until formation clear pale yellow color solution
Entitled solution G, equally, 0.01~0.05mmol ammonium persulfates is completely dissolved in 0.5~5 milliliter of ultra-pure water, obtain Solution H,
In order to synthesize NiCo2S4@Ni(OH)2@PPy samples, sample F is first placed in watch crystal, and volume is micro- for 50~300
The solution G risen is shifted and dripped on sample surfaces, then Solution H is added in sample in a manner of sample to ensure that sample fills
Point infiltration, afterwards by the sample of processing place in the dark 20~24 it is small when, with methanol wash collection NiCo2S4@Ni(OH)2@
PPy samples, then when 50~70 DEG C of vacuum drying 10~14 are small, obtain NiCo2S4@Ni(OH)2@PPy materials.
In step 1), the molar ratio of the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea is 1:2:12.
In step 2), the molar ratio of the nickel chloride and urea is 1:3.
In step 3), the molar ratio of the pyrrole monomer and ammonium persulfate is 2.7:1.
The invention has the advantages that：
The present invention is that one kind constructs NiCo based on nickel foam template2S4@Ni(OH)2The preparation method of@PPy core shell structures.This
Invention preparation method is simple, and cost is relatively low.The super capacitor anode material of preparation has higher area specific capacity and power
Density, shows good chemical property.And NiCo is synthesized first2S4@Ni(OH)2@PPy core shell structures, have novelty；
Good chemical property, has practicality.
Brief description of the drawings
Fig. 1 understands Ni (OH)2Successfully it is supported on NiCo2S4Surface.
Fig. 2 understands that PPy is successfully supported on NiCo2S4Surface, forms NiCo2S4@Ni(OH)2@PPy composite materials.
Fig. 3 understands NiCo2S4@Ni(OH)2@PPy composite materials keep array pattern, and diameter is about 300~400nm.
Fig. 4 is NiCo2S4@Ni(OH)2Constant current charge-discharge curve of the@PPy composite materials in 2M KOH electrode solutions.
Embodiment
With reference to shown in Fig. 1, wherein (220), (311), (400), (511), (440) correspond to the NiCo in PDF cards2S4
Phase, (006), (015), (016), (110) correspond to the Ni (OH) in PDF cards2Phase.Solid line and dotted line represent respectively in figure
The corresponding NiCo of PDF#20-0782 and PDF#38-07152S4Phase and Ni (OH)2Phase.It can thus be appreciated that Ni (OH)2Successfully it is supported on
NiCo2S4Surface.
With reference to shown in Fig. 2,1020cm-1And 1370cm-1NiCo is corresponded to respectively2S4@Ni(OH)2In@PPy composite materials
Ni-S and=C-H flexural vibrations absorption bands.Prove that PPy is successfully supported on NiCo2S4Surface.
With reference to shown in Fig. 4, I, II, III, IV, V, VI, VII represents current density as 5,10,20,30,40,50,60mA
cm-2Under the conditions of corresponding constant current charge-discharge collection of illustrative plates.
Embodiment 1：
1) NiCo is prepared2S4Nano-tube array：
Before synthesis, nickel foam (1 × 3cm) is immersed into acetone successively, HCl solution, to remove in ethanol and ultra-pure water
Oxide layer and impurity on surface, are then dried in atmosphere, are denoted as sample A；By 0.21 mM of NiCl2·6H2O, 0.42 milli
Mole CoCl2·6H2O and 2.56 mM of urea is dissolved in progress room temperature magnetic agitation in 15 milliliters of ultra-pure waters, deep until being formed
Aubergine clear solution, is denoted as solution B；Sample A and solution B are transferred to the autoclave of 25 milliliters of teflon lineds at the same time
In, kept at 110~130 DEG C 6~10 it is small when, then cooled to room temperature, by the Ni-Co precursors in obtained nickel foam
Washed several times and dried with ultra-pure water and EtOH Sonicate, be denoted as sample C；Then by the aqueous solution of sample C and 15 milliliters of vulcanized sodium
Be placed in together in autoclave and at 80~100 DEG C keep 8~10 it is small when, product uses ethanol and milli-Q water repeatedly, and receives
Collect the nickel foam sample so prepared, and be dried in vacuum overnight at 50~70 DEG C, be denoted as sample D.
2) NiCo is prepared2S4@Ni(OH)2
By 0.86 mM of NiCl2·6H2O and 2.6 mM of urea is dissolved in 15 milliliters of ultra-pure waters, carries out room temperature magnetic force
Stirring, until forming greenish transparent solution, is denoted as solution E.Then sample D and solution E are transferred to 25 milliliters of high pressures at the same time
In kettle and when holding 2 is small at 90~110 DEG C.After cooled to room temperature, gained sample with ethanol and ultrapure water for several times,
When vacuum drying 10~14 is small at 50~70 DEG C, sample F is denoted as.
3) NiCo is prepared2S4@Ni(OH)2@PPy
0.06 mM of p-methyl benzenesulfonic acid (p-TSA) is first dissolved in 3 milliliters of absolute ethyl alcohols, then in above-mentioned solution
3 microlitres of pyrrole monomers are added, sonic oscillation is until form clear pale yellow color solution.Solution obtained above is named as solution G.
Equally, 0.016 mM of ammonium persulfate is completely dissolved in 2 milliliters of ultra-pure waters, obtains Solution H.In order to synthesize NiCo2S4@Ni
(OH)2@PPy samples, sample F is first placed in watch crystal, and the solution G that volume is 180 microlitres is shifted and drips to sample
On product surface, then Solution H is added in sample in a manner of sample to ensure sample fully penetrated, afterwards by the sample of processing
Product place in the dark 24 it is small when.Washed with methanol and collect NiCo2S4@Ni(OH)2@PPy samples, then in 50~70 DEG C of vacuum
Dry 10~14h.Obtain NiCo2S4@Ni(OH)2@PPy materials.
Embodiment 2：
1) NiCo is prepared2S4Nano-tube array：
Before synthesis, nickel foam (1 × 3cm) is immersed into acetone successively, HCl solution, to remove in ethanol and ultra-pure water
Oxide layer and impurity on surface, are then dried in atmosphere, are denoted as sample A；By 0.21 mM of NiCl2·6H2O, 0.42 milli
Mole CoCl2·6H2O and 2.56 mM of urea is dissolved in progress room temperature magnetic agitation in 15 milliliters of ultra-pure waters, deep until being formed
Aubergine clear solution, is denoted as solution B；Sample A and solution B are transferred to the autoclave of 25 milliliters of teflon lineds at the same time
In, kept at 110~130 DEG C 6~10 it is small when, then cooled to room temperature, by the Ni-Co precursors in obtained nickel foam
Washed several times and dried with ultra-pure water and EtOH Sonicate, be denoted as sample C；Then by the aqueous solution of sample C and 15 milliliters of vulcanized sodium
Be placed in together in autoclave and at 80~100 DEG C keep 8~10 it is small when, product uses ethanol and milli-Q water repeatedly, and receives
Collect the nickel foam sample so prepared, and be dried in vacuum overnight at 50~70 DEG C, be denoted as sample D.
2) NiCo is prepared2S4@Ni(OH)2
By 0.86 mM of NiCl2·6H2O and 2.6 mM of urea is dissolved in 15 milliliters of ultra-pure waters, carries out room temperature magnetic force
Stirring, until forming greenish transparent solution, is denoted as solution E.Then sample D and solution E are transferred to 25 milliliters of high pressures at the same time
In kettle and when holding 2 is small at 90~110 DEG C.After cooled to room temperature, gained sample with ethanol and ultrapure water for several times,
When vacuum drying 10~14 is small at 50~70 DEG C, sample F is denoted as.
3) NiCo is prepared2S4@Ni(OH)2@PPy
0.06 mM of p-methyl benzenesulfonic acid (p-TSA) is first dissolved in 3 milliliters of absolute ethyl alcohols, then in above-mentioned solution
4 microlitres of pyrrole monomers are added, sonic oscillation is until form clear pale yellow color solution.Solution obtained above is named as solution G.
Equally, 0.021 mM of ammonium persulfate is completely dissolved in 2 milliliters of ultra-pure waters, obtains Solution H.In order to synthesize NiCo2S4@Ni
(OH)2@PPy samples, sample F is first placed in watch crystal, and the solution G that volume is 180 microlitres is shifted and drips to sample
On product surface, then Solution H is added in sample in a manner of sample to ensure sample fully penetrated, afterwards by the sample of processing
Product place in the dark 24 it is small when.Washed with methanol and collect NiCo2S4@Ni(OH)2@PPy samples, then in 50~70 DEG C of vacuum
Dry 10~14h.Obtain NiCo2S4@Ni(OH)2@PPy materials.
Embodiment 3：
1) NiCo is prepared2S4Nano-tube array：
Before synthesis, nickel foam (1 × 3cm) is immersed into acetone successively, HCl solution, to remove in ethanol and ultra-pure water
Oxide layer and impurity on surface, are then dried in atmosphere, are denoted as sample A；By 0.21 mM of NiCl2·6H2O, 0.42 milli
Mole CoCl2·6H2O and 2.56 mM of urea is dissolved in progress room temperature magnetic agitation in 15 milliliters of ultra-pure waters, deep until being formed
Aubergine clear solution, is denoted as solution B；Sample A and solution B are transferred to the autoclave of 25 milliliters of teflon lineds at the same time
In, kept at 110~130 DEG C 6~10 it is small when, then cooled to room temperature, by the Ni-Co precursors in obtained nickel foam
Washed several times and dried with ultra-pure water and EtOH Sonicate, be denoted as sample C；Then by the aqueous solution of sample C and 15 milliliters of vulcanized sodium
Be placed in together in autoclave and at 80~100 DEG C keep 8~10 it is small when, product uses ethanol and milli-Q water repeatedly, and receives
Collect the nickel foam sample so prepared, and be dried in vacuum overnight at 50~70 DEG C, be denoted as sample D.
2) NiCo is prepared2S4@Ni(OH)2
By 0.86 mM of NiCl2·6H2O and 2.6 mM of urea is dissolved in 15 milliliters of ultra-pure waters, carries out room temperature magnetic force
Stirring, until forming greenish transparent solution, is denoted as solution E.Then sample D and solution E are transferred to 25 milliliters of high pressures at the same time
In kettle and when holding 2 is small at 90~110 DEG C.After cooled to room temperature, gained sample with ethanol and ultrapure water for several times,
When vacuum drying 10~14 is small at 50~70 DEG C, sample F is denoted as.
3) NiCo is prepared2S4@Ni(OH)2@PPy
0.06 mM of p-methyl benzenesulfonic acid (p-TSA) is first dissolved in 3 milliliters of absolute ethyl alcohols, then in above-mentioned solution
5 microlitres of pyrrole monomers are added, sonic oscillation is until form clear pale yellow color solution.Solution obtained above is named as solution G.
Equally, 0.0267 mM of ammonium persulfate is completely dissolved in 2 milliliters of ultra-pure waters, obtains Solution H.In order to synthesize NiCo2S4@Ni
(OH)2@PPy samples, sample F is first placed in watch crystal, and the solution G that volume is 180 microlitres is shifted and drips to sample
On product surface, then Solution H is added in sample in a manner of sample to ensure sample fully penetrated, afterwards by the sample of processing
Product place in the dark 24 it is small when.Washed with methanol and collect NiCo2S4@Ni(OH)2@PPy samples, then in 50~70 DEG C of vacuum
When drying 10~14 is small.Obtain NiCo2S4@Ni(OH)2@PPy materials.
Embodiment 4：
1) NiCo is prepared2S4Nano-tube array：
Before synthesis, nickel foam (1 × 3cm) is immersed into acetone successively, HCl solution, to remove in ethanol and ultra-pure water
Oxide layer and impurity on surface, are then dried in atmosphere, are denoted as sample A；By 0.21 mM of NiCl2·6H2O, 0.42 milli
Mole CoCl2·6H2O and 2.56 mM of urea is dissolved in progress room temperature magnetic agitation in 15 milliliters of ultra-pure waters, deep until being formed
Aubergine clear solution, is denoted as solution B；Sample A and solution B are transferred to the autoclave of 25 milliliters of teflon lineds at the same time
In, kept at 110~130 DEG C 6~10 it is small when, then cooled to room temperature, by the Ni-Co precursors in obtained nickel foam
Washed several times and dried with ultra-pure water and EtOH Sonicate, be denoted as sample C；Then by the aqueous solution of sample C and 15 milliliters of vulcanized sodium
Be placed in together in autoclave and at 80~100 DEG C keep 8~10 it is small when, product uses ethanol and milli-Q water repeatedly, and receives
Collect the nickel foam sample so prepared, and be dried in vacuum overnight at 50~70 DEG C, be denoted as sample D.
2) NiCo is prepared2S4@Ni(OH)2
By 0.86 mM of NiCl2·6H2O and 2.6 mM of urea is dissolved in 15 milliliters of ultra-pure waters, carries out room temperature magnetic force
Stirring, until forming greenish transparent solution, is denoted as solution E.Then sample D and solution E are transferred to 25 milliliters of high pressures at the same time
In kettle and when holding 2 is small at 90~110 DEG C.After cooled to room temperature, gained sample with ethanol and ultrapure water for several times,
When vacuum drying 10~14 is small at 50~70 DEG C, sample F is denoted as.
3) NiCo is prepared2S4@Ni(OH)2@PPy
0.06 mM of p-methyl benzenesulfonic acid (p-TSA) is first dissolved in 3 milliliters of absolute ethyl alcohols, then in above-mentioned solution
6 microlitres of pyrrole monomers are added, sonic oscillation is until form clear pale yellow color solution.Solution obtained above is named as solution G.
Equally, 0.032 mM of ammonium persulfate is completely dissolved in 2 milliliters of ultra-pure waters, obtains Solution H.In order to synthesize NiCo2S4@Ni
(OH) 2@PPy samples, sample F is first placed in watch crystal, and the solution G that volume is 180 microlitres is shifted and drips to sample
On product surface, then Solution H is added in sample in a manner of sample to ensure sample fully penetrated, afterwards by the sample of processing
Product place in the dark 24 it is small when.Washed with methanol and collect NiCo2S4@Ni (OH) 2@PPy samples, then in 50~70 DEG C of vacuum
When drying 10~14 is small.Obtain 2@PPy materials of NiCo2S4@Ni (OH).
Claims (4)
1. NiCo is constructed based on nickel foam template2S4@Ni(OH)2@PPy materials are used for the method for ultracapacitor, its feature exists
In comprising the following steps：
1) NiCo is prepared2S4Nano-tube array：
Before synthesis, 1 × 3cm of nickel foam is immersed into acetone successively, HCl solution, is then dried in atmosphere, is denoted as sample A；
By 0.1~0.4 mM of NiCl2·6H2O, 0.1~0.8 mM of CoCl2·6H2O and 1.0~5.0 mM of urea dissolving
Room temperature magnetic agitation is carried out in 5~30 milliliters of ultra-pure waters, until forming royal purple clear solution, is denoted as solution B；By sample
A and solution B are transferred in the autoclave of 10~50 milliliters of teflon lineds at the same time, and 6~10 are kept at 110~130 DEG C
Hour, then cooled to room temperature, the Ni-Co precursors in obtained nickel foam are washed several times with ultra-pure water and EtOH Sonicate
And it is dry, it is denoted as sample C；Then sample C is placed in together with the aqueous solution of 5~30 milliliters of vulcanized sodium in autoclave and 80~
When holding 8~10 is small at 100 DEG C, product uses ethanol and milli-Q water repeatedly, and collects the nickel foam sample so prepared, and
It is dried in vacuum overnight at 50~70 DEG C, is denoted as sample D；
2) NiCo is prepared2S4@Ni(OH)2
By 0.1~1.5 mM of NiCl2·6H2O and 0.1~5 mM of urea is dissolved in 5~30 milliliters of ultra-pure waters, is carried out normal
Warm magnetic agitation, until forming greenish transparent solution, is denoted as solution E, sample D and solution E are then transferred to 10 at the same time~
Keep in 50 milliliters of autoclaves and at 90~110 DEG C 1~2 it is small when, after cooled to room temperature, gained sample with ethanol and super
Pure water rinsing for several times, when vacuum drying 10~14 is small at 50~70 DEG C, is denoted as sample F；
3) NiCo is prepared2S4@Ni(OH)2@PPy
0.01~2 mM of p-methyl benzenesulfonic acid p-TSA is first dissolved in 1~10 milliliter of absolute ethyl alcohol, then in above-mentioned solution
Solution obtained above is named as by 1~10 microlitre of pyrrole monomer of middle addition, sonic oscillation until formation clear pale yellow color solution
Solution G, equally, 0.01~0.05mmol ammonium persulfates is completely dissolved in 0.5~5 milliliter of ultra-pure water, obtain Solution H, in order to
Synthesize NiCo2S4@Ni(OH)2@PPy samples, sample F is first placed in watch crystal, is 50~300 microlitres by volume
Solution G is shifted and dripped on sample surfaces, then Solution H is added in sample in a manner of sample to ensure that sample fully oozes
Thoroughly, afterwards by the sample of processing place in the dark 20~24 it is small when, with methanol wash collect NiCo2S4@Ni(OH)2@PPy samples
Product, then when 50~70 DEG C of vacuum drying 10~14 are small, obtain NiCo2S4@Ni(OH)2@PPy materials.
2. preparation method according to claim 1, is characterized in that：In step 1), the Nickel dichloride hexahydrate, six hydration chlorine
The molar ratio for changing cobalt and urea is 1:2:12.
3. preparation method according to claim 1, is characterized in that：In step 2), the molar ratio of the nickel chloride and urea
For 1:3.
4. preparation method according to claim 1, is characterized in that：In step 3), the pyrrole monomer and ammonium persulfate
Molar ratio is 2.7:1.
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