CN108597898A - A kind of preparation method of cobalt sulfide zinc nano material - Google Patents
A kind of preparation method of cobalt sulfide zinc nano material Download PDFInfo
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- CN108597898A CN108597898A CN201810316955.6A CN201810316955A CN108597898A CN 108597898 A CN108597898 A CN 108597898A CN 201810316955 A CN201810316955 A CN 201810316955A CN 108597898 A CN108597898 A CN 108597898A
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- Prior art keywords
- cobalt
- zinc
- presoma
- cobalt sulfide
- nano material
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- RSSFTRAQEQRZCO-UHFFFAOYSA-N [Co]=S.[Zn] Chemical compound [Co]=S.[Zn] RSSFTRAQEQRZCO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 150000001868 cobalt Chemical class 0.000 claims abstract description 22
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- 238000004073 vulcanization Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 106
- 229910052759 nickel Inorganic materials 0.000 claims description 53
- 239000006260 foam Substances 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000004959 2-nitroimidazoles Chemical class 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000007772 electrode material Substances 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000005611 electricity Effects 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 4
- 238000003491 array Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CTAQBXGVUXQQQZ-UHFFFAOYSA-N [S-2].[Zn+2].[Co+2].[S-2] Chemical compound [S-2].[Zn+2].[Co+2].[S-2] CTAQBXGVUXQQQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical class CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000004246 zinc acetate Substances 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
- H01G11/30—Electrodes characterised by their material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of preparation methods of cobalt sulfide zinc nano material.This method reacts to form metal-organic framework material as nanometer presoma with organic ligand using zinc salt, cobalt salt, and vulcanization reaction then is occurred for the presoma and sulphur-containing substance, forms hollow cobalt sulfide zinc nano material；In presoma forming process, base material is added, forerunner's precursor reactant of laminated structure is set to generate in the substrate surface, effectively reduce being stacked between presoma, to contribute to vulcanization reaction fully to occur, so that the skeleton structure of nanometer persursor material is kept good, to considerably increase the surface area of cobalt sulfide Zinc material, chemical property is improved when being applied advantageous as electrode material.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of preparation method of cobalt sulfide zinc nano material.
Background technology
Electric chemical super capacitor abbreviation ultracapacitor is a kind of a kind of storage between traditional capacitor and battery
Energy device, is a green technology for being combined the energy with environmental protection, and due to short with the charging time, power-performance is high, cycle
Stability is good, and service life is long, and pollution-free, the excellent specific properties such as economic and environment-friendly, and duration can not only be provided in application
The energy, moreover it is possible to play the role of environmental protection, therefore, received significant attention in recent years, and had a wide range of applications field, logical
The fields such as letter, electric power, electronic product, new-energy automobile are with a wide range of applications.
As a kind of important semiconductor-transition bimetallic sulfide, cobalt sulfide zinc shows excellent electrochemistry
Can, it is widely used in electro-catalysis and ultracapacitor field, is a kind of ideal electrode material.Therefore, cobalt sulfide zinc material is improved
The chemical property of material is of great significance to electro-catalysis and ultracapacitor field.
Invention content
The technical purpose of the present invention is to provide a kind of preparation method of cobalt sulfide zinc nano material, is made using this method
Cobalt sulfide zinc can improve chemical property.
In order to achieve the above technical purposes, the present inventor, which uses, forms transition metal ions and organic ligand with organic
Then vulcanization reaction shape is occurred for persursor material and sulphur-containing substance by the metal-organic framework material of skeleton as persursor material
It at the method for hollow transient metal sulfide, finds during preparing presoma, if block materials are added as base
Bottom, then nanometer forerunner precursor reactant generate in the substrate surface, can effectively avoid being stacked between nanometer persursor material,
To contribute to vulcanization reaction fully to occur, the skeleton structure of nano material is made to keep good.
That is, the technical scheme is that：A kind of preparation method of cobalt sulfide zinc nano material, includes the following steps：
(1) zinc salt, cobalt salt and organic ligand, reaction is used to form metal-organic framework material as nanometer presoma；
(2) vulcanization reaction is occurred into for the presoma and sulphur-containing substance, forms hollow cobalt sulfide zinc nano material；
It is characterized in that：In the reaction process of the step (1), block materials are added as substrate, nano-sheet forerunner
Body is generated in the substrate surface.
The base material does not react with zinc salt, cobalt salt and organic ligand, and material is unlimited, including nickel, carbon
Deng.In order to improve the surface area of substrate, preferably there is cavernous base material, such as nickel foam, carbon cloth, carbon paper, carbon nanometer
Pipe, graphene.
As a kind of realization method, in the step (1), takes a certain amount of zinc salt to be dissolved in the first solvent with cobalt salt and formed
Organic ligand is dissolved in the second solvent and forms the second solution by the first solution；First solution is uniformly mixed to be formed with the second solution
Mixed solution is added base material, reacts to form a nanometer presoma.Preferably, in mixed solution, zinc salt and cobalt salt,
The molar ratio of organic ligand and solvent is 1:(3-8)：(0.5-6).Wherein, preferably, the molar ratio of zinc salt and cobalt salt is 1：
(0.2-5), further preferably 1：(0.5-3).
The zinc salt is unlimited, including one or more of zinc acetate, zinc nitrate, zinc chloride etc..
The cobalt salt is unlimited, including one kind or more in cobalt acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt carbonate etc.
Kind.
The organic ligand is unlimited, including in 2-methylimidazole, benzimidazole, 2- nitroimidazoles, terephthalic acid (TPA) etc.
It is one or more.
First solvent is unlimited, including water and organic solvent, and the organic solvent is unlimited, including methanol, ethyl alcohol,
It is one or more in DMF, DMA etc..
Second solvent is unlimited, including water and organic solvent, and the organic solvent is unlimited, including methanol, ethyl alcohol,
It is one or more in DMF, DMA etc..
Preferably, in the step (1), reaction time 3h-24h.
In the step (1), structure, thickness are preferably 250-300nm to presoma in the form of sheets.
Realization effect as one preferred, presoma nanometer sheet are vertically generated in substrate surface, form array arrangement, from
And being stacked between avoiding nanometer persursor material to greatest extent, contribute to vulcanization reaction fully to occur, makes a nanometer material
The skeleton structure of material keeps good.
As a kind of realization method, in the step (2), presoma is put into the organic solvent containing sulphur source, into
Row hydro-thermal reaction obtains the hollow nanometer cobalt sulfide Zinc material positioned at substrate surface.
In the step (2), sulphur source is unlimited, including one or more in thioacetamide, vulcanized sodium, thiocarbamide etc..
In the step (2), organic solvent is unlimited, including one or more in methanol, ethyl alcohol, DMF, DMA etc..
In the step (2), preferably, a concentration of 0.003-0.04g/mL of sulphur-containing solution.
Preferably, in the step (2), the temperature of hydro-thermal reaction is 100-200 DEG C.
Preferably, in the step (2), the time of hydro-thermal reaction is in 3h-10h.
Compared with prior art, the present invention forms the metal with organic backbone using transition metal ions and organic ligand
During organic framework materials are as presoma, base material is added, forerunner's precursor reactant of flaky nanometer structure is made to generate
The substrate surface, has the advantages that：
(1) presoma of laminated structure is generated in the substrate surface, is effectively reduced between two-dimensional sheet nanometer presoma
Be stacked with, contribute to vulcanization reaction fully to occur, obtain the cobalt sulfide Zinc material of hollow nano-chip arrays structure, make nanometer
The skeleton structure of persursor material keeps good, to considerably increase the surface area of cobalt sulfide Zinc material.This is conducive to vulcanize
Increase with effective contact area of electrolyte solution when cobalt Zinc material is applied as electrode material, shortens ion transmission path, carry
The rate of high electronics transfer improves specific capacitance, to improve chemical property.
(2) preferably, when selecting conductive substrates, which can be directly used as electrode basement, work as to reduce
The addition of non-conductivity adhesive when cobalt sulfide Zinc material is applied as electrode material can substantially reduce resistance, improve conductive
Property.
(3) preparation method of the invention is simple, and the cobalt sulfide Zinc material of hollow nano-chip arrays structure obtained is with excellent
Different chemical property shows good redox peaks, and has efficient charge and discharge when being applied as electrode material
Process, excellent specific capacitance performance and good cyclical stability, wherein electrochemical cycle stability can be protected after recycling 1000 times
It holds 75% or more, therefore has a good application prospect in supercapacitor technologies field.
Description of the drawings
Fig. 1 is that step (2) is obtained using nickel foam as the scanning electron microscope (SEM) photograph of the presoma of substrate in the embodiment of the present invention 1；
Fig. 2 is the partial enlarged view in Fig. 1；
Fig. 3 is that step (3) is obtained using nickel foam as the scanning of the cobalt sulfide Zinc material of substrate electricity in the embodiment of the present invention 1
Mirror figure；
Fig. 4 is that the embodiment of the present invention 1 is obtained to be made by the zinc sulphide cobalt material of substrate and comparative example 1 of nickel foam
The XRD diagram of the zinc sulphide cobalt material obtained；
Fig. 5 is that the cobalt sulfide Zinc material of hollow nano-chip arrays structure made from the embodiment of the present invention 1 is electrolysed in 1M KOH
Chemical property figure in matter solution；Wherein, figure a is the cyclic voltammetry curve figure swept in difference under speed；It is that different electric currents are close to scheme b
The lower chrono amperometry figure of degree；It is specific capacitance performance map to scheme c, and figure d is cyclical stability；
Fig. 6 is the scanning electron microscope (SEM) photograph of presoma made from step (2) in comparative example 1；
Fig. 7 is the scanning electron microscope (SEM) photograph of cobalt sulfide Zinc material made from step (3) in comparative example 1.
Specific implementation mode
Present invention is further described in detail with embodiment below in conjunction with the accompanying drawings, it should be pointed out that reality as described below
It applies example to be intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows：
(1) 0.49gZn (NO are taken3)2·6H2O, 0.24g Co (NO3)2·6H2O is dissolved in 50mL water, takes 1.6g diformazans
Base imidazoles is dissolved in 50mL water；Above two solution is mixed, 5min is stirred, obtains presoma reaction solution；Zinc salt and cobalt salt,
Organic ligand, water molar ratio be 1：4：2.8, wherein zinc salt, cobalt salt molar ratio be 1:0.5.
(2) clean nickel foam is added in above-mentioned presoma reaction solution, 4h is stood at 25 DEG C；Then, bubble is taken out
Foam nickel is washed with water three times, and the presoma for obtaining that nickel foam is substrate for 24 hours is dried in 75 DEG C of vacuum drying chamber.
(3) presoma obtained in above-mentioned steps is added in the ethanol solution containing 0.003g/ml thioacetamides,
Obtain reaction solution；Reaction solution is added in ptfe autoclave liner, reacts 4h at 120 DEG C；Nickel foam is taken out,
It is washed respectively with water and ethyl alcohol and is placed in 65 DEG C of vacuum drying chamber dry 12h three times, obtain the vulcanization that nickel foam is substrate
Cobalt Zinc material.
Nickel foam made from above-mentioned steps (2) is that the scanning electron microscope (SEM) photograph of the presoma of substrate is as shown in Figure 1, 2, step (3)
The scanning electron microscope (SEM) photograph of cobalt sulfide zinc nanometer sheet material obtained is as shown in Figure 3.As can be seen that presoma made from step (2) is in
Flaky nanometer structure, size uniformity, thickness is in 250-300nm or so, and vertical-growth, in nickel foam, each nanometer sheet is presented
Array-like regular array；It is in hollow form after step (3) vulcanization, flaky nanometer structure holding is well.
Fig. 4 is step in cobalt sulfide zinc nanometer sheet material made from step in the present embodiment (3) and following comparative examples 1
(3) XRD diagram of cobalt sulfide zinc made from.In Fig. 4, cobalt sulfide Zinc material obtained is expressed as Zn-Co- in comparative example 1
S-P, wherein P indicate then powder, i.e., no powder presoma obtained in the case of base material is added obtain after over cure
The cobalt sulfide zinc powder body material arrived；Cobalt sulfide Zinc material obtained is expressed as Zn-Co-S-NF in embodiment 1, and wherein NF refers to base
Bottom nickel foam (Nickel foam) is added made from substrate NF using NF as the presoma of substrate, is then obtained after over cure
Using NF as the cobalt sulfide Zinc material of substrate.Figure 4, it is seen that Zn-Co-S-NF and Zn-Co-S-P has apparent diffraction
Peak illustrates that the material has good crystallinity.
Cobalt sulfide zinc nano material obtained above is placed in 1M KOH electrolyte solutions, to be saturated calomel as reference
Electrode, Pt, as to electrode, form three-electrode system using the cobalt sulfide zinc nano material as working electrode, test the vulcanization
The chemical property of cobalt zinc nano material, the results are shown in Figure 4.
In Fig. 5, a figures are the materials sweeps the cyclic voltammetry curves under speed in difference, shows that the cyclic voltammetry curve of closure has
Apparent redox peaks show that the material belongs to fake capacitance electrode material.
In Fig. 5, b figures are charging and discharging curve of the material under different current densities.According to specific capacitance calculation formula C=
(I* △ t)/(m* △ V), in conjunction with charging and discharging curve figure, the specific capacitance value under different current densities is calculated, as c schemes institute in Fig. 5
Show, is shown in 0.5A g-1When, specific capacitance value is up to 2354.3F g-1Left and right.
In Fig. 5, it is 10A g that d figures, which are the electrode materials in current density,-1When cyclical stability, cycle 1000 times after,
The cyclical stability of material is maintained at 83.3% or so.
Show that the nickel foam is that the hollow nano-chip arrays cobalt sulfide Zinc material of substrate can be used as electrode of super capacitor material
Material.
Comparative example 1:
The present embodiment is the comparative example of above-described embodiment 1.
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows：
(1) identical with step (1) in embodiment 1；
(2) essentially identical with the step (2) in embodiment 1, the difference is that being added without in presoma reaction solution clean
Net nickel foam states presoma reaction solution and stands 4h at 25 DEG C, obtains presoma；
(3) identical with step (3) in embodiment 1, since presoma does not have nickel foam as substrate, obtain
Cobalt sulfide Zinc material.
The scanning electron microscope (SEM) photograph of presoma made from above-mentioned steps (2) is as shown in fig. 6, hollow cobalt sulfide made from step (3)
The scanning electron microscope (SEM) photograph of zinc nanometer sheet is as shown in Figure 7.As can be seen that presoma made from step (2) has complete leaf plate shape,
But it is stacked between piece and piece；After step (3) vulcanization, leaf laminated structure is deteriorated completely.
The cobalt sulfide zinc nano material is tested, test method is identical with the method in embodiment 1, the results show that phase
With under the conditions of three-electrode system test chemical property be：Current density is in 0.5A g-1When, specific capacitance value is in 355.3F
g-1Left and right；Current density is in 10A g-1When chemical property cyclical stability be maintained at 75.8%.
It is compared with above-mentioned comparative example 1, illustrates in embodiment 1, using nickel foam as substrate, the pattern of material is maintained
Prodigious benefit.In addition, pattern can not only be kept by substrate of nickel foam, when as electrode material, electrification is also advantageously improved
Learn performance.
Embodiment 2:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows：
(1) it takes 0.49g zinc nitrates, 0.59g cobalt acetates to be dissolved in 10mL methanol, 1.58g methylimidazoles is taken to be dissolved in 5mL
In methanol；Above two solution is mixed, 30min is stirred, obtains presoma reaction solution, wherein cobalt salt, organic ligand, solvent
Molar ratio be 1：4：5, zinc salt, cobalt salt molar ratio be 1:2.
(2) clean nickel foam is added in above-mentioned presoma reaction solution, is stood for 24 hours at 25 DEG C；Then, bubble is taken out
Foam nickel is washed three times with ethyl alcohol, and the presoma for obtaining that nickel foam is substrate for 24 hours is dried in 75 DEG C of vacuum drying chamber.
(3) presoma obtained above is added in the ethanol solution containing 0.039g/mL vulcanized sodium, obtains reacting molten
Liquid；Reaction solution is added in ptfe autoclave liner, is placed in baking oven and reacts 5h at 100 DEG C；Nickel foam is taken out, point
It is not washed with water and ethyl alcohol and is placed in 80 DEG C of vacuum drying chamber dry 12h three times, obtain the cobalt sulfide that nickel foam is substrate
Zinc material.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step
(3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and
Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking；After step (3) vulcanization, nano-sheet knot
Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1
Together, the results show that the chemical property of the three-electrode system test under the same terms is：Current density is in 0.5A g-1When, than electricity
Capacitance is 1580.5F g-1, cyclical stability is maintained at 80% or so.
Embodiment 3:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows：
(1) 0.14g zinc chloride, 0.29g Co (NO are taken3)2·6H2O is dissolved in 20mL methanol, takes 1.31g dimethyl miaows
Azoles is dissolved in 20mL methanol；Above two solution is mixed, 15min is stirred, obtains presoma reaction solution, wherein zinc salt and cobalt
Salt, organic ligand, solvent molar ratio be 1：8：0.99, zinc salt, cobalt salt molar ratio be 1:1.
(2) clean nickel foam is put into above-mentioned reaction solution, is stood at room temperature for 24 hours；Then, nickel foam is taken out, is used
Methanol washs the presoma for obtaining that nickel foam is substrate three times.
(3) presoma obtained above is put into the aqueous solution dissolved with 0.04g thiocarbamides, obtains reaction solution；
Reaction solution is added in ptfe autoclave liner, reacts 8h at 150 DEG C in baking oven；Nickel foam is taken out,
It is washed respectively with water and ethyl alcohol and is placed in 65 DEG C of vacuum drying chamber dry 20h three times, obtain the vulcanization that nickel foam is substrate
Cobalt Zinc material.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step
(3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and
Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking；After step (3) vulcanization, nano-sheet knot
Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1
Together, the results show that the chemical property of the three-electrode system test under the same terms is：Current density is in 0.5A g-1When, than electricity
Capacitance is in 856.2F g-1Left and right, cyclical stability are maintained at 78.3%.
Embodiment 4:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows：
(1) 0.04gZn (COOH) is taken2·2H2O, 0.12g CoCl2·6H2O is dissolved in 40mL methanol, takes 0.08g benzene
And imidazoles is dissolved in 40mL methanol；Above two solution is mixed, 60min is stirred, obtains presoma reaction solution, wherein cobalt
Salt, organic ligand, solvent molar ratio be 1：4：1.86, zinc salt, cobalt salt molar ratio be 1:2.5.
(2) clean nickel foam is put into above-mentioned reaction solution, stands 10h at room temperature；Then, nickel foam is taken out, is used
Methanol, ethyl alcohol wash the presoma for obtaining that nickel foam is substrate three times respectively.
(3) presoma obtained above is put into dissolved with 0.028g/ml Na2In the ethanol solution of S, reaction solution is obtained；
Reaction solution is added in ptfe autoclave liner, reacts 8h at 120 DEG C in baking oven；Nickel foam is taken out, uses water respectively
It is placed on dry 20h in 65 DEG C of vacuum drying chamber three times with ethyl alcohol washing, obtains the cobalt sulfide Zinc material that nickel foam is substrate.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step
(3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and
Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking；After step (3) vulcanization, nano-sheet knot
Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1
Together, the results show that the chemical property of the three-electrode system test under the same terms is：Current density is in 0.5A g-1When, than electricity
Capacitance is in 698.3F g-1Left and right, cyclical stability are maintained at 80%.
Embodiment 5:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows：
(1) 0.23g anhydrous zinc chlorides, 1.5g Co (NO are taken3)2·6H2O is dissolved in 60mL ethyl alcohol, takes 2.4g dimethyl
Imidazoles is dissolved in 20mL ethyl alcohol；Above two solution is mixed, 15min is stirred, obtains presoma reaction solution, wherein cobalt salt,
Organic ligand, solvent molar ratio be：1：4.3：1.87, zinc salt, cobalt salt molar ratio be 1:3.
(2) clean nickel foam is put into above-mentioned presoma reaction solution, stands 5h at room temperature；Then, foam is taken out
Nickel washs the presoma for obtaining that nickel foam is substrate three times with methanol.
(3) presoma obtained above is put into the aqueous solution dissolved with 0.014g/ml thioacetamides, obtains reacting molten
Liquid；Reaction solution is added in ptfe autoclave liner, reacts 8h at 150 DEG C in baking oven；Nickel foam is taken out, is used respectively
Water and ethyl alcohol washing are placed on dry 20h in 65 DEG C of vacuum drying chamber three times, obtain the cobalt sulfide zinc material that nickel foam is substrate
Material.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step
(3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and
Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking；After step (3) vulcanization, nano-sheet knot
Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1
Together, the results show that the chemical property of the three-electrode system test under the same terms is：Current density is in 0.5A g-1When, than electricity
Capacitance is in 583.4F g-1Left and right, cyclical stability are maintained at 76.2%.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cobalt sulfide zinc nano material, includes the following steps：
(1) zinc salt, cobalt salt and organic ligand, reaction is used to form metal-organic framework material as nanometer presoma；
(2) vulcanization reaction is occurred into for the presoma and sulphur-containing substance, forms hollow cobalt sulfide zinc nano material；
It is characterized in that：In the reaction process of the step (1), block materials are added as substrate, the life of nano-sheet presoma
At in the substrate surface.
2. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that：The base material includes
Nickel and/or carbon.
3. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that：The base material is in more
Pore structure.
4. the preparation method of cobalt sulfide zinc nano material as claimed in claim 3, it is characterized in that：The base material is bubble
One or several kinds in foam nickel, carbon cloth, carbon paper, carbon nanotube, graphene.
5. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that：The zinc salt includes acetic acid
One or more of zinc, zinc nitrate, zinc chloride；
Preferably, the cobalt salt includes one or more in cobalt acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt carbonate；
Preferably, the organic ligand includes in 2-methylimidazole, benzimidazole, 2- nitroimidazoles, terephthalic acid (TPA)
It is one or more.
6. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that：It is preceding in the step (1)
Drive body structure in the form of sheets, thickness 250-300nm.
7. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that：It is preceding in the step (1)
It drives body nanometer sheet vertically to generate in substrate surface, forms array arrangement.
8. the preparation method of the cobalt sulfide zinc nano material as described in any claim in claim 1 to 7, it is characterized in that：
It in the step (1), takes a certain amount of zinc salt and cobalt salt to be dissolved in the first solvent and forms the first solution, organic ligand is dissolved in the
Two solvents form the second solution；First solution is uniformly mixed to form mixed solution with the second solution, base material is added, is occurred
Reaction forms nanometer presoma；
Preferably, in mixed solution, the molar ratio of zinc salt and cobalt salt, organic ligand and solvent is 1:(3-8)：(0.5-6)；
Preferably, the molar ratio of zinc salt and cobalt salt is 1：(0.2-5), further preferably 1:(0.5-3).
9. the preparation method of the cobalt sulfide zinc nano material as described in any claim in claim 1 to 7, it is characterized in that：
In the step (2), presoma is put into the organic solvent containing sulphur source and is reacted；
Preferably, sulphur source includes one or more in thioacetamide, vulcanized sodium, thiocarbamide；
Preferably, organic solvent includes one or more in methanol, ethyl alcohol, DMF, DMA；
Preferably, a concentration of 0.003-0.04g/mL of sulfur-bearing solvent.
10. the preparation method of cobalt sulfide zinc nano material as claimed in claim 9, it is characterized in that：In the step (2),
Reaction temperature is 100-200 DEG C；
Preferably, in the step (2), the reaction time is in 3h-10h.
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