CN110136975A - A kind of preparation method and applications of amorphous tetrathio cobalt molybdate/nickelous selenide nano-chip arrays composite material - Google Patents
A kind of preparation method and applications of amorphous tetrathio cobalt molybdate/nickelous selenide nano-chip arrays composite material Download PDFInfo
- Publication number
- CN110136975A CN110136975A CN201910394958.6A CN201910394958A CN110136975A CN 110136975 A CN110136975 A CN 110136975A CN 201910394958 A CN201910394958 A CN 201910394958A CN 110136975 A CN110136975 A CN 110136975A
- Authority
- CN
- China
- Prior art keywords
- nano
- chip arrays
- amorphous
- comos
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000003491 array Methods 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title description 4
- -1 nickelous selenide Chemical class 0.000 title description 3
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 239000006260 foam Substances 0.000 claims abstract description 23
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003990 capacitor Substances 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910018864 CoMoO4 Inorganic materials 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 9
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 7
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 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
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals 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
- H01G11/84—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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material, comprising the following steps: (1) under hydrothermal conditions, cabaltous nitrate hexahydrate and seven molybdic acid hydrate sodium react, and CoMoO is grown in nickel foam4Nano-chip arrays；(2) by vulcanized sodium and CoMoO4Nano-chip arrays carry out hydro-thermal reaction and form amorphous CoMoS4Nano-chip arrays；(3) under hydrothermal conditions, Nickel dichloride hexahydrate, selenium dioxide and urea react to form amorphous NiSe, and are deposited on amorphous CoMoS4The surface of nano-chip arrays finally obtains amorphous CoMoS4/ NiSe nano-chip arrays composite material.The preparation method is simple, at low cost, and amorphous CoMoS obtained4/ NiSe nano-chip arrays composite material has high specific capacitance and good cyclical stability, can be applied to electrode material for super capacitor, has a good application prospect.
Description
Technical field
The present invention relates to supercapacitor technologies fields, and in particular to be a kind of amorphous tetrathio cobalt molybdate/selenizing
The application of the preparation method of nickel nano film array composite material and the composite material as electrode material for super capacitor.
Background technique
Supercapacitor is made of electrode, electrolyte, collector and diaphragm, is a kind of novel electrochemical energy storing device.
Compared with lithium ion battery, energy density is lower for it.But it has the advantages that itself, for example power density is high, charge/discharge speed
One of fastly and have extended cycle life, thus become current research hot spot.
Supercapacitor is divided into pseudocapacitors and double layer capacitor.Pseudocapacitors rely on the faraday of electrode material surface
Redox reaction energy storage, and double layer capacitor carries out energy storage by the adsorption charge of electrode material surface.Just because of two
Person's energy storage mechnism is different, so the energy density of pseudocapacitors is much higher than double layer capacitor, but compared with lithium ion battery also
There is biggish gap.Common fake capacitance material includes transition metal oxide, transition metal hydroxide and conducting polymer,
And transient metal sulfide in recent years newly developed etc..The fake capacitance material overwhelming majority is crystalline material at present, but crystalline state material
Material is unfavorable for ion and quickly spreads, it is difficult to obtain high specific capacitance, therefore be not easy to form high-energy due to its anisotropic characteristic
The supercapacitor of density.In addition, preparing electrode of super capacitor often needing to that binder is added, bonding electrode material is played
With the effect of collector；But binder can block the hole of electrode material to a certain extent, will certainly reduce supercapacitor
Energy storage capacity.
Summary of the invention
The purpose of the present invention is to provide a kind of amorphous tetrathio cobalt molybdate/nickelous selenide (i.e. CoMoS4/ NiSe) nanometer
The preparation method of chip arrays composite material, preparation method is simple, at low cost, and amorphous CoMoS obtained4/ NiSe nanometer sheet
Array composite material has high specific capacitance and good cyclical stability, can be applied to electrode material for super capacitor, has
Good application prospect.
In order to achieve the above objectives, solution of the invention is:
A kind of amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material, including CoMoO4Nanometer sheet battle array
The preparation of column, amorphous CoMoS4The preparation of nano-chip arrays and amorphous CoMoS4/ NiSe nano-chip arrays composite material
Prepare three steps；
The CoMoO4The preparation method of nano-chip arrays be first at room temperature, the nickel foam cleaned is immersed in six water
In the mixed aqueous solution for closing cobalt nitrate and seven molybdic acid hydrate sodium, 80~180 DEG C of progresss hydro-thermal reactions are heated to seal to, keep the temperature 4~
10h is cooled to room temperature, and obtains reaction product A；Then it by reaction product A cleaning, drying, obtains being grown in the nickel foam
CoMoO4Nano-chip arrays；
The amorphous CoMoS4The preparation method of nano-chip arrays be first at room temperature, growth is had into the CoMoO4It receives
The nickel foam of rice chip arrays is placed in sodium sulfide solution, is heated to seal to 60~120 DEG C of progress hydro-thermal reactions, keeps the temperature 4~10h,
It then cools to room temperature, obtains reaction product B, then by reaction product B cleaning, drying, obtain being grown in the nickel foam
Amorphous CoMoS4Nano-chip arrays；
The amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material be first at room temperature, will grow
There is the amorphous CoMoS4The mixing that the nickel foam of nano-chip arrays is placed in Nickel dichloride hexahydrate, selenium dioxide and urea is water-soluble
In liquid, 100~200 DEG C of progress hydro-thermal reactions are heated to seal to, 5~20h is kept the temperature, then cools to room temperature, obtain reaction product C；
Finally by reaction product C cleaning, drying, the amorphous CoMoS is obtained4/ NiSe nano-chip arrays composite material.
In the mixed aqueous solution of the cabaltous nitrate hexahydrate and seven molybdic acid hydrate sodium, the cabaltous nitrate hexahydrate and seven hydrations
The molar ratio of sodium molybdate is 1:0.5~2, and the amount ratio of the cabaltous nitrate hexahydrate and deionized water is 1mmol:10~15mL.
In the sodium sulfide solution, the amount ratio of the vulcanized sodium and deionized water is 1mmol: 25~35mL.
In the mixed aqueous solution of the Nickel dichloride hexahydrate, selenium dioxide and urea, the Nickel dichloride hexahydrate, titanium dioxide
The molar ratio of selenium and urea is 1: 1~4: 5~20, the amount ratio of the Nickel dichloride hexahydrate and deionized water is 1mmol: 50~
70mL。
The cleaning step is successively multiple using deionized water and ethyl alcohol cleaning.
The drying is vacuum drying.
The amorphous CoMoS4Application of/NiSe nano-chip arrays the composite material as electrode material for super capacitor.
After adopting the above technical scheme, a kind of amorphous CoMoS of the present invention4The system of/NiSe nano-chip arrays composite material
Preparation Method has the advantage that
(1) preparation method is simple, at low cost, reproducible；
(2) amorphous CoMoS4/ NiSe nano-chip arrays composite material is grown directly upon in foam nickel base, is effectively kept away
The use of binder is opened；
(3) the amorphous CoMoS being prepared4/ NiSe nano-chip arrays composite material can form open pore structure, promote
Into electrolyte and interelectrode contact；
(4) the amorphous CoMoS4In/NiSe nano-chip arrays composite material, CoMoS4It is amorphous structure with NiSe,
It can be spread for ion and channel abundant is provided, to have high specific capacitance and high cyclical stability.
Detailed description of the invention
Fig. 1 is the resulting CoMoO of the embodiment of the present invention 14Nano-chip arrays, amorphous CoMoS4Nano-chip arrays and
CoMoS4The X-ray diffractogram of/NiSe nano-chip arrays composite material；
Fig. 2 is the resulting amorphous CoMoS of the embodiment of the present invention 14Nano-chip arrays and amorphous CoMoS4/ NiSe nanometers
The selective electron diffraction figure of chip arrays composite material；
Fig. 3 is the resulting amorphous CoMoS of the embodiment of the present invention 14The energy spectrum diagram of/NiSe nano-chip arrays composite material；
Fig. 4 is the resulting amorphous CoMoS of the embodiment of the present invention 14The photoelectron energy of/NiSe nano-chip arrays composite material
Spectrogram；
Fig. 5 is the resulting CoMoO of the embodiment of the present invention 14Nano-chip arrays, amorphous CoMoS4Nano-chip arrays and without fixed
Shape CoMoS4The scanning electron microscope (SEM) photograph of/NiSe nano-chip arrays composite material；
Fig. 6 is the resulting amorphous CoMoS of the embodiment of the present invention 14Nano-chip arrays and amorphous CoMoS4/ NiSe nanometers
Specific capacitance relational graph of the chip arrays composite material under different current densities；
Fig. 7 is CoMoS in the embodiment of the present invention 14Energy density-power of/NiSe//AC Asymmetric Supercapacitor is close
Spend graph of relation；
Fig. 8 is CoMoS in the embodiment of the present invention 14The stable circulation linearity curve of/NiSe//AC Asymmetric Supercapacitor
Figure.
Specific embodiment
In order to further explain the technical solution of the present invention, being explained in detail below by specific embodiment the present invention
It states.
Embodiment 1
One, the preparation of composite material
A kind of amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material, comprising the following steps:
Step 1, at room temperature, by 5mmol cabaltous nitrate hexahydrate, seven molybdic acid hydrate sodium of 2.5mmol and 50mL deionized water
It is added in 100mL autoclave, stirring and dissolving, obtains mixed aqueous solution A；
The nickel foam cleaned is immersed in mixed aqueous solution A by step 2, and by autoclave be heated to seal to 80 DEG C into
Row hydro-thermal reaction keeps the temperature 10h, is cooled to room temperature, obtains reaction product A；
Reaction product A is successively cleaned for several times with deionized water and ethyl alcohol, and is dried in vacuo 12h at 60 DEG C by step 3,
Obtain being grown in the CoMoO in nickel foam4Nano-chip arrays；
Step 4, at room temperature, 2mmol vulcanized sodium and 50mL deionized water are added in 100mL autoclave, are stirred molten
Solution, obtains sodium sulfide solution；
Step 5, the growth for obtaining step 3 have CoMoO4The nickel foam of nano-chip arrays is placed in sodium sulfide solution, and
Autoclave is heated to seal to 60 DEG C of progress hydro-thermal reactions, 10h is kept the temperature, is cooled to room temperature, obtains reaction product B；
Reaction product B is successively cleaned for several times with deionized water and ethyl alcohol, and is dried in vacuo 12h at 60 DEG C by step 6,
Obtain being grown in the amorphous CoMoS in nickel foam4Nano-chip arrays；
Step 7, at room temperature, by 1mmol Nickel dichloride hexahydrate, 1mmol selenium dioxide, 5mmol urea and 50mL go from
Sub- water is added in 100mL autoclave, stirring and dissolving, obtains the mixed aqueous solution of Nickel dichloride hexahydrate, selenium dioxide and urea
B；
Step 8, the growth for obtaining step 6 have amorphous CoMoS4The nickel foam of nano-chip arrays is placed in mixed aqueous solution
In B, and autoclave is heated to seal to 100 DEG C of progress hydro-thermal reactions, keeps the temperature 20h, at this time under hydrothermal conditions, six chloride hydrates
Nickel, selenium dioxide and urea reaction form amorphous NiSe, and are deposited on amorphous CoMoS4The surface of nano-chip arrays, then
It is cooled to room temperature, obtains reaction product C；
Reaction product C is successively cleaned for several times with deionized water and ethyl alcohol, and is dried in vacuo 12h at 60 DEG C by step 9,
Obtain amorphous CoMoS4/ NiSe nano-chip arrays composite material.
Two, structural characterization
XRD is tested as shown in Figure 1, CoMoO4Nano-chip arrays are crystalline state, and CoMoS4Nano-chip arrays and CoMoS4/
The X-ray diffractogram of NiSe nano-chip arrays composite material does not have diffraction maximum, illustrates CoMoS4Nano-chip arrays and CoMoS4/
NiSe nano-chip arrays composite material is amorphous structure.
Fig. 2 is amorphous CoMoS4Nano-chip arrays and amorphous CoMoS4The constituency of/NiSe nano-chip arrays composite material
Wide and fuzzy annulus is presented in electron diffraction diagram, further illustrates that the two is amorphous structure.
By testing amorphous CoMoS4The energy spectrum diagram (such as Fig. 3) and photoelectron energy of/NiSe nano-chip arrays composite material
Spectrogram (such as Fig. 4) confirms that the composite material is by CoMoS4It is formed with NiSe.
Scanning electron microscope result is as shown in figure 5, the CoMoO that explanation is grown in nickel foam4、 CoMoS4And CoMoS4/NiSe
What composite material was presented is nano-chip arrays, has open pore structure.
Three, performance test
1, directly with amorphous CoMoS4Nano-chip arrays and amorphous CoMoS4/ NiSe nano-chip arrays composite material is
Working electrode, Hg/HgO electrode are reference electrode, and 3mol/L KOH aqueous solution is electrolyte, carry out three electrode tests.Test knot
Fruit as shown in fig. 6, when current density be 1A/g when, amorphous CoMoS4The specific capacitance of/NiSe nano-chip arrays composite material is high
It is more than amorphous CoMoS up to 5757F/g4The specific capacitance (2776F/g) of nano-chip arrays；When current density rises to 10A/g,
Amorphous CoMoS4The specific capacitance of/NiSe nano-chip arrays composite material can still maintain high specific capacitance (3120F/g), explanation
This material is forthright with good times.
2, with amorphous CoMoS4/ NiSe nano-chip arrays composite material is anode, and active carbon (AC) is cathode, 3mol/
L KOH aqueous solution is electrolyte, is assembled into CoMoS4/ NiSe//AC Asymmetric Supercapacitor, and it is measured in different electric currents
Charging and discharging curve under density, to obtain energy density-saturation effect curve graph.As shown in fig. 7, being in power density
When 875W/kg, the energy density of the capacitor is up to 69Wh/kg.
Under conditions of current density is 5A/g, the survey of charge and discharge cycles stability is carried out to the Asymmetric Supercapacitor
Examination, test results are shown in figure 8: after 10000 circulations, capacitor can still keep about 86% specific capacitance, illustrate this capacitor
With good cyclical stability, the amorphous CoMoS of preparation4/ NiSe nano-chip arrays composite material can be used as super capacitor
Equipment material is applied.
Embodiment 2
A kind of amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material, comprising the following steps:
Step 1, at room temperature, 5mmol cabaltous nitrate hexahydrate, seven molybdic acid hydrate sodium of 10mmol and 75mL deionized water are added
Enter into 100mL autoclave, stirring and dissolving, obtains mixed aqueous solution A；
The nickel foam cleaned is immersed in mixed aqueous solution A by step 2, and by autoclave be heated to seal to 180 DEG C into
Row hydro-thermal reaction keeps the temperature 4h, is cooled to room temperature, obtains reaction product A；
Reaction product A is successively cleaned for several times with deionized water and ethyl alcohol, and is dried in vacuo 12h at 60 DEG C by step 3,
Obtain being grown in the CoMoO in nickel foam4Nano-chip arrays；
Step 4, at room temperature, 2mmol vulcanized sodium and 70mL deionized water are added in 100mL autoclave, are stirred molten
Solution, obtains sodium sulfide solution；
Step 5, the growth for obtaining step 3 have CoMoO4The nickel foam of nano-chip arrays is placed in sodium sulfide solution, and
Autoclave is heated to seal to 120 DEG C of progress hydro-thermal reactions, 4h is kept the temperature, is cooled to room temperature, obtains reaction product B；
Reaction product B is successively cleaned for several times with deionized water and ethyl alcohol, and is dried in vacuo 12h at 60 DEG C by step 6,
Obtain being grown in the amorphous CoMoS in nickel foam4Nano-chip arrays；
Step 7, at room temperature, 1mmol Nickel dichloride hexahydrate, 4mmol selenium dioxide, 20mmol urea and 70mL are gone
Ionized water is added in 100mL autoclave, stirring and dissolving, and the mixing for obtaining Nickel dichloride hexahydrate, selenium dioxide and urea is water-soluble
Liquid B；
Step 8, the growth for obtaining step 6 have amorphous CoMoS4The nickel foam of nano-chip arrays is placed in mixed aqueous solution
In B, and autoclave is heated to seal to 200 DEG C of progress hydro-thermal reactions, keeps the temperature 5h, at this time under hydrothermal conditions, six chloride hydrates
Nickel, selenium dioxide and urea reaction form amorphous NiSe, and are deposited on amorphous CoMoS4The surface of nano-chip arrays, then
It is cooled to room temperature, obtains reaction product C；
Reaction product C is successively cleaned for several times with deionized water and ethyl alcohol, and is dried in vacuo 12h at 60 DEG C by step 9,
Obtain amorphous CoMoS4/ NiSe nano-chip arrays composite material.
Above-described embodiment and schema and non-limiting product form and style of the invention, any technical field it is common
The appropriate changes or modifications that technical staff does it all should be regarded as not departing from patent category of the invention.
Claims (7)
1. a kind of amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material, it is characterised in that: including CoMoO4
The preparation of nano-chip arrays, amorphous CoMoS4The preparation of nano-chip arrays and amorphous CoMoS4/ NiSe nano-chip arrays are multiple
Three steps of preparation of condensation material；
The CoMoO4The preparation method of nano-chip arrays be first at room temperature, the nickel foam cleaned is immersed in six hydration nitre
In the mixed aqueous solution of sour cobalt and seven molybdic acid hydrate sodium, 80~180 DEG C of progress hydro-thermal reactions are heated to seal to, keep the temperature 4~10h,
It is cooled to room temperature, obtains reaction product A；Then it by reaction product A cleaning, drying, obtains being grown in the nickel foam
CoMoO4Nano-chip arrays；
The amorphous CoMoS4The preparation method of nano-chip arrays be first at room temperature, growth is had into the CoMoO4Nanometer sheet
The nickel foam of array is placed in sodium sulfide solution, is heated to seal to 60~120 DEG C of progress hydro-thermal reactions, keeps the temperature 4~10h, then
It is cooled to room temperature, obtains reaction product B, then by reaction product B cleaning, drying, the nothing for obtaining being grown in the nickel foam is fixed
Shape CoMoS4Nano-chip arrays；
The amorphous CoMoS4The preparation method of/NiSe nano-chip arrays composite material is that first at room temperature, growth is had described
Amorphous CoMoS4The nickel foam of nano-chip arrays is placed in the mixed aqueous solution of Nickel dichloride hexahydrate, selenium dioxide and urea,
100~200 DEG C of progress hydro-thermal reactions are heated to seal to, 5~20h is kept the temperature, then cools to room temperature, obtain reaction product C；
Finally by reaction product C cleaning, drying, the amorphous CoMoS is obtained4/ NiSe nano-chip arrays composite material.
2. a kind of amorphous CoMoS according to claim 14The preparation method of/NiSe nano-chip arrays composite material,
It is characterized in that: in the mixed aqueous solution of the cabaltous nitrate hexahydrate and seven molybdic acid hydrate sodium, the cabaltous nitrate hexahydrate and seven water
The molar ratio for closing sodium molybdate is 1:0.5~2, the amount ratio of the cabaltous nitrate hexahydrate and deionized water be 1mmol:10~
15mL。
3. a kind of amorphous CoMoS according to claim 14The preparation method of/NiSe nano-chip arrays composite material,
Be characterized in that: in the sodium sulfide solution, the amount ratio of the vulcanized sodium and deionized water is 1mmol: 25~35mL.
4. a kind of amorphous CoMoS according to claim 14The preparation method of/NiSe nano-chip arrays composite material,
It is characterized in that: in the mixed aqueous solution of the Nickel dichloride hexahydrate, selenium dioxide and urea, the Nickel dichloride hexahydrate, dioxy
The molar ratio for changing selenium and urea is 1: 1~4: 5~20, and the amount ratio of the Nickel dichloride hexahydrate and deionized water is 1mmol: 50
~70mL.
5. a kind of amorphous CoMoS according to claim 14The preparation method of/NiSe nano-chip arrays composite material,
Be characterized in that: the cleaning step is successively multiple using deionized water and ethyl alcohol cleaning.
6. a kind of amorphous CoMoS according to claim 14The preparation method of/NiSe nano-chip arrays composite material,
Be characterized in that: the drying is vacuum drying.
7. a kind of amorphous CoMoS according to claim 14The preparation method of/NiSe nano-chip arrays composite material is made
The standby obtained amorphous CoMoS4Application of/NiSe nano-chip arrays the composite material as electrode material for super capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910394958.6A CN110136975B (en) | 2019-05-13 | 2019-05-13 | Preparation method and application of amorphous cobalt tetrathiomolybdate/nickel selenide nanosheet array composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910394958.6A CN110136975B (en) | 2019-05-13 | 2019-05-13 | Preparation method and application of amorphous cobalt tetrathiomolybdate/nickel selenide nanosheet array composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110136975A true CN110136975A (en) | 2019-08-16 |
| CN110136975B CN110136975B (en) | 2021-01-05 |
Family
ID=67573721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910394958.6A Active CN110136975B (en) | 2019-05-13 | 2019-05-13 | Preparation method and application of amorphous cobalt tetrathiomolybdate/nickel selenide nanosheet array composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110136975B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155145A (en) * | 2020-01-15 | 2020-05-15 | 浙江农林大学 | Bifunctional electrolytic water electrode with super-wettability and preparation method thereof |
| CN111437840A (en) * | 2020-05-22 | 2020-07-24 | 辽宁大学 | 3D hierarchical flower-like MoS2@CoMoS4Z-type heterostructure photoelectric catalyst and preparation method and application thereof |
| CN111463418A (en) * | 2020-04-24 | 2020-07-28 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| US11183343B1 (en) | 2020-08-15 | 2021-11-23 | United Arab Emirates University | Composite material for supercapacitor electrodes |
| CN114724866A (en) * | 2022-03-11 | 2022-07-08 | 上海健康医学院 | Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355463A (en) * | 2015-11-09 | 2016-02-24 | 电子科技大学 | Flexible supercapacitor electrode and device preparation method |
| CN106057480A (en) * | 2016-08-11 | 2016-10-26 | 浙江大学 | Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN107342174A (en) * | 2017-09-12 | 2017-11-10 | 信阳师范学院 | A kind of two-dimensional layer CoMoS4Nanometer sheet is the preparation method of electrode material for super capacitor |
| CN107930671A (en) * | 2017-12-06 | 2018-04-20 | 福州大学 | A kind of ternary metal sulfide/graphite phase carbon nitride composite photocatalyst material and its preparation method and application |
-
2019
- 2019-05-13 CN CN201910394958.6A patent/CN110136975B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355463A (en) * | 2015-11-09 | 2016-02-24 | 电子科技大学 | Flexible supercapacitor electrode and device preparation method |
| CN106057480A (en) * | 2016-08-11 | 2016-10-26 | 浙江大学 | Three-dimensional porous selenide nanocomposite used for super capacitor and preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN107342174A (en) * | 2017-09-12 | 2017-11-10 | 信阳师范学院 | A kind of two-dimensional layer CoMoS4Nanometer sheet is the preparation method of electrode material for super capacitor |
| CN107930671A (en) * | 2017-12-06 | 2018-04-20 | 福州大学 | A kind of ternary metal sulfide/graphite phase carbon nitride composite photocatalyst material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| YUN-KAI WANG等: "Coprecipitation Reaction System Synthesis and Lithium-Ion Capacitor Energy Storage Application of the Porous Structural Bimetallic Sulfide CoMoS4 Nanoparticles", 《ACS OMEGA》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155145A (en) * | 2020-01-15 | 2020-05-15 | 浙江农林大学 | Bifunctional electrolytic water electrode with super-wettability and preparation method thereof |
| CN111463418A (en) * | 2020-04-24 | 2020-07-28 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| CN111463418B (en) * | 2020-04-24 | 2022-12-27 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| CN111437840A (en) * | 2020-05-22 | 2020-07-24 | 辽宁大学 | 3D hierarchical flower-like MoS2@CoMoS4Z-type heterostructure photoelectric catalyst and preparation method and application thereof |
| CN111437840B (en) * | 2020-05-22 | 2021-10-22 | 辽宁大学 | 3D hierarchical flower-like MoS2@CoMoS4Z-type heterostructure photoelectric catalyst and preparation method and application thereof |
| US11183343B1 (en) | 2020-08-15 | 2021-11-23 | United Arab Emirates University | Composite material for supercapacitor electrodes |
| CN114724866A (en) * | 2022-03-11 | 2022-07-08 | 上海健康医学院 | Binder-free vanadium-doped nickel selenide nano array material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110136975B (en) | 2021-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110136975A (en) | A kind of preparation method and applications of amorphous tetrathio cobalt molybdate/nickelous selenide nano-chip arrays composite material | |
| CN106972155B (en) | A kind of bimetallic oxide and preparation method and application based on MOFs | |
| CN104129818B (en) | A kind of nickel cobalt oxide material and preparation method thereof | |
| CN108054019B (en) | NiCo of laminated structure2S4@NixCo(1-x)(OH)2Preparation method and application of composite material | |
| CN108773859B (en) | Vulcanized nano material and preparation method and application thereof | |
| CN103956483B (en) | The preparation method and application of cobalt acid zinc/nickel oxide core-shell nano linear array | |
| CN105957728B (en) | A kind of nickel cobalt double-hydroxide/NiCo2S4Composite nano materials, its preparation method and the application as electrode material for super capacitor | |
| CN109546143A (en) | Ternary cathode material with porous structure and preparation method thereof | |
| CN106910639B (en) | A kind of NiTe for electrode material for super capacitor2Preparation method | |
| CN107275105A (en) | Electrode material for super capacitor and preparation method thereof | |
| CN105702475B (en) | A kind of super capacitor anode material nickel ferrite based magnetic loaded and preparation method thereof | |
| CN106783202B (en) | A kind of bimetallic selenides electrode material for super capacitor CuxMoySezPreparation method | |
| CN109133199A (en) | A kind of preparation method of the spherical nanometer molybdic acid nickel electrode material of high circulation performance | |
| CN110304612A (en) | A kind of two ferrous selenide nanometer sheets for lithium ion battery negative material | |
| CN110310835A (en) | A kind of nano flower-like NiS@NiCo2S4Micro-, nano-electrode material and its preparation method and application | |
| CN109686592A (en) | Two nickelous selenide nano-array electrode material of white beech mushroom shape and preparation method thereof | |
| CN110010359A (en) | A kind of preparation method of nickel cobalt/hydroxide combination electrode material | |
| CN108831755A (en) | A kind of preparation method of electrode for capacitors multi-element composite material | |
| CN110415986B (en) | Ni-doped CoO/C composite material and preparation method thereof | |
| CN102897849A (en) | Method of preparing super-capacitor electrode material | |
| CN107316749B (en) | Co3O4@CoWO4The preparation method and applications of nano-wire array Core-shell structure material | |
| CN108597899B (en) | NiSe for supercapacitor2-Ni2O3Nanocomposite and preparation method thereof | |
| CN110223850A (en) | A kind of quick in situ preparation method of high-performance nickel hydroxide electrode material | |
| CN108666144A (en) | A kind of three-dimensional flower-shaped cobalt hydroxide-graphene composite material and preparation method thereof | |
| CN109216042A (en) | A kind of cobalt aluminium double-hydroxide/redox graphene composite material and preparation method of morphology controllable |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |