CN106683906A - Graphene zinc sulfide nanoparticle composites and preparation method - Google Patents
Graphene zinc sulfide nanoparticle composites and preparation method Download PDFInfo
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- CN106683906A CN106683906A CN201611165377.8A CN201611165377A CN106683906A CN 106683906 A CN106683906 A CN 106683906A CN 201611165377 A CN201611165377 A CN 201611165377A CN 106683906 A CN106683906 A CN 106683906A
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- graphene
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- sulfide nano
- nano particles
- zinc sulfide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 20
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 20
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 19
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000012798 spherical particle Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical class [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 3
- JYTNGEWJAZCVAN-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O JYTNGEWJAZCVAN-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910016323 MxSy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 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
- H01G11/84—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
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- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a graphene zinc sulfide nanoparticle composite material and preparation method which relates to the electrode material technical field, the graphene zinc sulfide nanoparticle material is a spherical particle of uniform shape and size and structure of the shell with graphene covering zinc sulfide. The particle diameter is 50-100nm. The graphene zinc sulfide nanoparticle composite material and preparation method has the advantages of simple structure and strong repeatability, the zinc sulfide nanoparticle is disperse evenly in the grapheme, the electrical conductivity is improved and the high the specific capacitance and good circulation stability is provided.
Description
Technical field
The present invention relates to electrode material technical field, and in particular to a kind of Graphene zine sulfide nano particles composite and
Its preparation method.
Background technology
The metal ion of transient metal sulfide MxSy (M=Cu, Mn, Co, Ni, Fe, Mo, Bi) has 3d valence shells,
There may be special photoelectricity magnetic performance, so as to be widely used in photocatalysis, solar control material, fuel cell, lithium
The multiple fields such as battery, superconductor, are one of important directions of current investigation of materials.Transient metal sulfide is possible to replace expensive
Metal is applied to fuel cell field as the catalyst of redox reaction；In field of lithium, the mistake with layer structure
It is very outstanding electrode material to cross metal sulfide；Additionally, application of the transient metal sulfide on solar absorptive material
Also widely studied.
In recent years, scientists found that transient metal sulfide can also be used as electrode material for super capacitor, and it has
The specific capacitance higher than metal-oxide and power density.For example, Wei et al. one-step synthesis NiS2Hollow nanospheres, the material
Material not only has good adsorptivity to organic dyestuff, also can be as the electrode material of ultracapacitor, while with high ratio electricity
Hold and cyclical stability.Lin et al. is by Co9S8With the complex of three-dimensional grapheme as positive pole, Graphene gel as negative pole,
High performance Asymmetric Supercapacitor is obtained, its output voltage is up to 1.8V, be 910W Kg in power density-1When, energy
Density has reached 31.6W h Kg-1.Huang et al. is by the MoS of stratiform2It is compound with Graphene, obtain the crosslinking net of conduction
Structure, which not only improves the efficiency of transmission of electronics, promotes electrolyte diffusion, also prevent electrode material in charge and discharge process
Change in volume, so as to get electrode material have very stable cycle performance.But for zinc sulfide electrode material but rarely has
Report.
The content of the invention
The invention provides a kind of Graphene and zinc blende nano-wire composite, it have it is larger be put into specific surface area,
It is applied on ultracapacitor as electrode material, not only with the good cyclical stability also specific surface with superelevation
Product and specific capacitance, and prepare simply, it is easy to use.
To realize object above, the present invention is achieved by the following technical programs：
A kind of preparation method of Graphene zine sulfide nano particles composite, comprises the following steps：
(1) 250ml there-necked flasks are placed in ice-water bath, sequentially add 80ml concentrated sulphuric acids, 2g graphite, 1g sodium nitrates, stirring 1
Hour；It is less than under conditions of 10 DEG C in keeping temperature, 3g potassium permanganate is slowly added in flask, stir 1 hour, cancels water
Bath；2) it is less than under conditions of 20 DEG C in keeping temperature, is slowly added to 6g potassium permanganate into flask, addition finishes post-heating to 35
DEG C, insulated and stirred 60 minutes；90ml distilled water is slowly added to in flask, 80 DEG C is warming up to, insulated and stirred 30 minutes；To solution
The hydrogen peroxide of middle addition 7ml 30%, 55ml distilled water stands 12 hours；3) using 3% dilute hydrochloric acid, distilled water enters to product
Row is rinsed, and is centrifuged 3 times, obtains graphene oxide suspension；
(2) 25mL dimethyl sulfoxides are added in 25mL graphene oxide suspensions, after ultrasonic disperse is uniform, addition zinc source,
Ammonium chloride and surfactant, 30~60min of magnetic agitation, it is 5.6~6.3 to adjust pH, is transferred to molten at 180~250 DEG C
Agent thermal response 12~20 hours, naturally cools to room temperature, collects sample；
(3) it is dried to obtain high uniformity dispersed sulfur zinc/Graphene composite wood with acetone and alcohol washes sample respectively
Material.
Preferably, graphene oxide concentration in a solvent is 0.5~10mg/mL.
Preferably, it is characterised in that ZnCl2、Zn(NO3)2、ZnSO4、Zn(CH3COO)2In one kind.
Preferably, the Zn2+Concentration be 1.25~2.5g/L.
Preferably, the surfactant is dodecylbenzene sodium sulfonate, cetyl benzenesulfonic acid sodium, dodecyl front three
One kind in base ammonium bromide, mercaptobenzothiazoler, mercaptoethanol, lauryl mercaptan.
Preferably, the concentration of the surfactant is 0.125~0.425mg/mL.
A kind of Graphene zinc sulfide nano-material is shape, spherical particle of uniform size, with graphene coated sulfuration
The nucleocapsid structure of zinc, nucleocapsid structure microgranule is less than 50~100nm.
Beneficial effects of the present invention：Had using the method for preparing zinc sulfide/graphene composite material of the present invention
Following advantage：A () synthetic method is simple, repeatable strong, acts on through the dispersion and carrying of Graphene, lives in combination with surface
Property agent peptizaiton, Zinc sulfide nano-particle can be made to be dispersed on Graphene, zine sulfide nano particles particle diameter be 50
~100nm；(b) in the presence of Zinc sulfide nano-particle and surfactant, the problem easily reunited between graphene sheet layer
It is overcome, forms excellent conductive network of knowing clearly, improves the electric conductivity of zinc sulfide；C () dimethyl sulfoxide serves not only as reaction molten
Agent, and be the raw material for preparing zinc sulfide as sulphur source；D () Jing electro-chemical tests show to be prepared into by the method for the present invention
To zinc sulfide/porous carbon composite there is high specific capacitance and good cyclical stability.
Specific embodiment
To make purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described, it is clear that described embodiment is a part of embodiment of the invention, rather than
Whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative work premise
Lower obtained every other embodiment, belongs to the scope of protection of the invention.
Embodiment 1：
A kind of Graphene zinc sulfide nano-material is shape, spherical particle of uniform size, with graphene coated sulfuration
The nucleocapsid structure of zinc, nucleocapsid structure mean particle dia is 50nm.
A kind of preparation method of Graphene zine sulfide nano particles composite, comprises the following steps：
(1) 250ml there-necked flasks are placed in ice-water bath, sequentially add 80ml concentrated sulphuric acids, 2g graphite, 1g sodium nitrates, stirring 1
Hour；It is less than under conditions of 10 DEG C in keeping temperature, 3g potassium permanganate is slowly added in flask, stir 1 hour, cancels water
Bath；2) it is less than under conditions of 20 DEG C in keeping temperature, is slowly added to 6g potassium permanganate into flask, addition finishes post-heating to 35
DEG C, insulated and stirred 60 minutes；90ml distilled water is slowly added to in flask, 80 DEG C is warming up to, insulated and stirred 30 minutes；To solution
The hydrogen peroxide of middle addition 7ml 30%, 55ml distilled water stands 12 hours；3) using 3% dilute hydrochloric acid, distilled water enters to product
Row is rinsed, and is centrifuged 3 times, obtains concentration for 3mg/mL graphene oxide suspensions；
(2) add 25mL dimethyl sulfoxides, after ultrasonic disperse is uniform, add 62.5mg in 25mL graphene oxide suspensions
ZnCl2, 6.68mg ammonium chloride and 31.25mg mercaptobenzothiazolers, 30~60min of magnetic agitation, it is 5.6~6.3 to adjust pH, is turned
Solvent thermal reaction 12~20 hours at 180~250 DEG C are moved to, room temperature is naturally cooled to, sample is collected；
(3) it is dried to obtain high uniformity dispersed sulfur zinc/Graphene composite wood with acetone and alcohol washes sample respectively
Material.
Embodiment 2：
A kind of Graphene zinc sulfide nano-material is shape, spherical particle of uniform size, with graphene coated sulfuration
The nucleocapsid structure of zinc, nucleocapsid structure mean particle dia is 100nm.
A kind of preparation method of Graphene zine sulfide nano particles composite, comprises the following steps：
(1) 250ml there-necked flasks are placed in ice-water bath, sequentially add 80ml concentrated sulphuric acids, 2g graphite, 1g sodium nitrates, stirring 1
Hour；It is less than under conditions of 10 DEG C in keeping temperature, 3g potassium permanganate is slowly added in flask, stir 1 hour, cancels water
Bath；2) it is less than under conditions of 20 DEG C in keeping temperature, is slowly added to 6g potassium permanganate into flask, addition finishes post-heating to 35
DEG C, insulated and stirred 60 minutes；90ml distilled water is slowly added to in flask, 80 DEG C is warming up to, insulated and stirred 30 minutes；To solution
The hydrogen peroxide of middle addition 7ml 30%, 55ml distilled water stands 12 hours；3) using 3% dilute hydrochloric acid, distilled water enters to product
Row is rinsed, and is centrifuged 3 times, obtains concentration for 0.5mg/mL graphene oxide suspensions；
(2) add 25mL dimethyl sulfoxides, after ultrasonic disperse is uniform, add 125mg in 25mL graphene oxide suspensions
Zn(NO3)2, 3.34mg ammonium chloride and 62.5mg dodecylbenzene sodium sulfonate, 30~60min of magnetic agitation, adjust pH be 5.6~
6.3, solvent thermal reaction 12~20 hours at 180~250 DEG C are transferred to, room temperature is naturally cooled to, collect sample；
(3) it is dried to obtain high uniformity dispersed sulfur zinc/Graphene composite wood with acetone and alcohol washes sample respectively
Material.
Embodiment 3：
A kind of Graphene zinc sulfide nano-material is shape, spherical particle of uniform size, with graphene coated sulfuration
The nucleocapsid structure of zinc, nucleocapsid structure mean particle dia is 50nm.
A kind of preparation method of Graphene zine sulfide nano particles composite, comprises the following steps：
(1) 250ml there-necked flasks are placed in ice-water bath, sequentially add 80ml concentrated sulphuric acids, 2g graphite, 1g sodium nitrates, stirring 1
Hour；It is less than under conditions of 10 DEG C in keeping temperature, 3g potassium permanganate is slowly added in flask, stir 1 hour, cancels water
Bath；2) it is less than under conditions of 20 DEG C in keeping temperature, is slowly added to 6g potassium permanganate into flask, addition finishes post-heating to 35
DEG C, insulated and stirred 60 minutes；90ml distilled water is slowly added to in flask, 80 DEG C is warming up to, insulated and stirred 30 minutes；To solution
The hydrogen peroxide of middle addition 7ml 30%, 55ml distilled water stands 12 hours；3) using 3% dilute hydrochloric acid, distilled water enters to product
Row is rinsed, and is centrifuged 3 times, obtains concentration for 10mg/mL graphene oxide suspensions；
(2) add 25mL dimethyl sulfoxides, after ultrasonic disperse is uniform, add 93.7mg in 25mL graphene oxide suspensions
Zn(CH3COO)2, 3.34mg ammonium chloride and 46.87mg Dodecyl trimethyl ammonium chloride, 30~60min of magnetic agitation adjusts pH
For 5.6~6.3, solvent thermal reaction 12~20 hours at 180~250 DEG C are transferred to, naturally cool to room temperature, collect sample；
(3) it is dried to obtain high uniformity dispersed sulfur zinc/Graphene composite wood with acetone and alcohol washes sample respectively
Material.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposit between operating
In any this actual relation or order.And, term " including ", "comprising" or its any other variant are intended to
Nonexcludability is included, so that a series of process, method, article or equipment including key elements not only will including those
Element, but also including other key elements being not expressly set out, or also include for this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element for being limited by sentence "including a ...", it is not excluded that
Also there is other identical element in process, method, article or equipment including the key element.
Above example only to illustrate technical scheme, rather than a limitation；Although with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that：It still can be to aforementioned each enforcement
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic；And these modification or
Replace, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Claims (7)
1. a kind of preparation method of Graphene zine sulfide nano particles composite, it is characterised in that comprise the following steps：
(1) 250ml there-necked flasks are placed in ice-water bath, sequentially add 80ml concentrated sulphuric acids, 2g graphite, 1g sodium nitrates, stirring 1 is little
When；It is less than under conditions of 10 DEG C in keeping temperature, 3g potassium permanganate is slowly added in flask, stir 1 hour, cancels water-bath；
2) it is less than under conditions of 20 DEG C in keeping temperature, is slowly added to 6g potassium permanganate into flask, addition finishes post-heating to 35 DEG C,
Insulated and stirred 60 minutes；90ml distilled water is slowly added to in flask, 80 DEG C is warming up to, insulated and stirred 30 minutes；To in solution
The hydrogen peroxide of 7ml 30%, 55ml distilled water is added to stand 12 hours；3) using 3% dilute hydrochloric acid, distilled water carries out to product
Rinse, be centrifuged 3 times, obtain graphene oxide suspension；
(2) add 25mL dimethyl sulfoxides, after ultrasonic disperse is uniform, add zinc source, chlorination in 25mL graphene oxide suspensions
Ammonium and surfactant, 30~60min of magnetic agitation, it is 5.6~6.3 to adjust pH, is transferred to the solvent thermal at 180~250 DEG C
Reaction 12~20 hours, naturally cools to room temperature, collects sample；
(3) it is dried to obtain high uniformity dispersed sulfur zinc/graphene composite material with acetone and alcohol washes sample respectively.
2. the preparation method of Graphene zine sulfide nano particles composite as claimed in claim 1, it is characterised in that described
Graphene oxide concentration in a solvent is 0.5~10mg/mL.
3. the preparation method of Graphene zine sulfide nano particles composite as claimed in claim 2, it is characterised in that ZnCl2、
Zn(NO3)2、ZnSO4、Zn(CH3COO)2In one kind.
4. the preparation method of Graphene zine sulfide nano particles composite as claimed in claim 3, it is characterised in that described
Zn2+Concentration be 1.25~2.5g/L.
5. the preparation method of Graphene zine sulfide nano particles composite as claimed in claim 4, it is characterised in that described
Surfactant is dodecylbenzene sodium sulfonate, cetyl benzenesulfonic acid sodium, Dodecyl trimethyl ammonium chloride, sulfydryl benzo thiophene
One kind in azoles, mercaptoethanol, lauryl mercaptan.
6. the preparation method of Graphene zine sulfide nano particles composite as claimed in claim 5, it is characterised in that described
The concentration of surfactant is 0.625~1.25mg/mL.
7. it is that shape, size are equal that the present invention also provides a kind of arbitrary described Graphene zinc sulfide nano-material of claim 1~6
Even spherical particle, the nucleocapsid structure with graphene coated zinc sulfide, nucleocapsid structure mean particle dia is 50~100nm.
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| CN107591253A (en) * | 2017-09-08 | 2018-01-16 | 南陵县生产力促进中心 | A kind of ultracapacitor graphene/zinc sulfide nano-material and preparation method thereof |
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| CN108766783A (en) * | 2018-06-13 | 2018-11-06 | 常熟理工学院 | A kind of preparation method of fiber/graphene/zinc sulphide flexible electrode material |
| CN110752320A (en) * | 2018-07-24 | 2020-02-04 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN109712756A (en) * | 2018-12-28 | 2019-05-03 | 黑龙江科技大学 | A kind of electric conductivity is decided by the preparation method of the conducing composite material of applied electric field |
| CN115626670A (en) * | 2022-10-25 | 2023-01-20 | 天能新能源(湖州)有限公司 | Potassium ion battery negative electrode material and preparation method thereof |
| CN115626670B (en) * | 2022-10-25 | 2023-12-05 | 天能新能源(湖州)有限公司 | Potassium ion battery anode material and preparation method thereof |
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