CN106449178A - Method for preparing sulfonated graphene oxide/tin oxide/polyaniline composite material - Google Patents
Method for preparing sulfonated graphene oxide/tin oxide/polyaniline composite material Download PDFInfo
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- CN106449178A CN106449178A CN201611039198.XA CN201611039198A CN106449178A CN 106449178 A CN106449178 A CN 106449178A CN 201611039198 A CN201611039198 A CN 201611039198A CN 106449178 A CN106449178 A CN 106449178A
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- graphene oxide
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- sno
- aniline
- polyaniline
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910001887 tin oxide Inorganic materials 0.000 title abstract 7
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 75
- 239000000084 colloidal system Substances 0.000 claims abstract description 30
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 108
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 16
- 238000006277 sulfonation reaction Methods 0.000 claims description 13
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 8
- 229910006735 SnO2SnO Inorganic materials 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 229950000244 sulfanilic acid Drugs 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing a sulfonated graphene oxide/tin oxide/polyaniline composite material. The method comprises the following steps: depositing tin oxide particles among graphene oxide sheet layers by using a hydrothermal method, preparing three-dimensional graphene oxide/tin oxide complex colloid, and sulfonating the prepared colloid by using aminobenzene sulfonic acid; coating /polyaniline on the sulfonated three-dimensional graphene oxide/tin oxide complex by adopting an interfacial polymerization method, so as to obtain the sulfonated graphene oxide/tin oxide/polyaniline three-dimensional meshed composite material. The method disclosed by the invention is simple in preparation process, green, environmental-friendly and reliable, and the prepared sulfonated graphene oxide/tin oxide/polyaniline composite material takes the three-dimensional porous meshed shape, has the advantages of regular space structure, high energy density and power density and excellent cycle performance and is an ideal super-capacitor electrode material.
Description
Technical field
The invention belongs to novel energy field of material technology, super with hydro-thermal method and oxidative polymerization method preparation particularly to one kind
The preparation method of level capacitor sulfoxidation Graphene/composite material of stannic oxide/polyaniline.
Background technology
Ultracapacitor due to there is high-energy-density and power density and outstanding cycle performance etc. and as quick
Primary selection with high-power energy stocking system field.Electrode material in ultracapacitor rises to the performance of ultracapacitor
To vital effect, therefore, realizing the wide variety of most important thing of ultracapacitor is to prepare and develop high performance electricity
Pole material.
Conducting polymer, transition metal oxide and material with carbon element are three kinds of materials that electrode material for super capacitor is commonly used.
Overcome the shortcomings of that using the advantageous characteristic of these three materials homogenous material has that to prepare combination electrode material be super electricity at present
One of focus of container electrode investigation of materials.Ding etc. synthesizes SnO by dip coating2@PANI and then and redox graphene
It is compounded to form the SnO of 3-D nano, structure2@PANI/rGO trielement composite material, this materials show very high reversible than electric capacity simultaneously
There is outstanding high rate performance and cycle performance（H. Ding, et al. Ternary SnO2@PANI/rGO
nanohybrids as excellent anode materials for lithium-ion batteries[J].
Electrochimica Acta, 2015, 157: 205-210.）.Nguyen etc. adopts two-step method synthesizing graphite alkene/nanometer
SnO2/ PANI material, this composite has high rate capability（V.H. Nguyen, et al. Ultrasmall SnO2
nanoparticle-intercalated graphene@polyaniline composites as an active
electrode material for supercapacitors in different electrolytes[J].
Synthetic Metals, 2015, 207: 110-115.）.Liu etc. synthesized by tin dioxide nano-particle, Graphene and
The composite of polyaniline composition simultaneously studies the performance of its positive electrode as high performance lithium ion battery.This composite
Nanostructured can effectively adjust the volumetric expansion during tin ash lithiumation, the nanoparticle in suppression cyclic process simultaneously
Reunite and there is outstanding cyclical stability.（H. Liu, et al. A reduced graphene oxide/SnO2/
polyaniline nanocomposite for the anode material of Li-ion batteries[J].
Solid State Ionics, 2016, 294: 6-14. ）.
Therefore high-performance super capacitor electrode material is prepared for it in electrochemical energy storage using simple synthetic technology
The application in field is significant.The present invention is with three-dimensional graphene oxide, SnCl4It is raw material with NaOH, using hydro-thermal method
Three-dimensional graphene oxide/tin ash the composite colloids of preparation, then with aminobenzenesulfonic acid to the three-dimensional graphene oxide of preparation/
Tin ash composite colloids carry out sulfonation and can get sulfonation three-dimensional graphene oxide/tin ash complex.Finally adopt
Interfacial polymerization cladding polyaniline particles on sulfonation three-dimensional graphene oxide/tin ash complex prepare sulfoxidation stone
Black alkene/three-dimensional porous the netty compound material of tin ash/polyaniline.Gained composite has regular space structure, high energy
Metric density and power density, outstanding cycle performance, are a kind of preferable electrode material for super capacitor, are especially suitable for industry
Metaplasia is produced.
Content of the invention
It is an object of the invention to provide a kind of preparation side of sulfoxidation Graphene/composite material of stannic oxide/polyaniline
Method.
Thinking of the present invention：Three-dimensional graphene oxide/tin ash composite colloids are prepared with hydro-thermal method, and uses amino phenyl sulfonyl
Acid carries out sulfonation to the colloid of preparation, then adopts interfacial polymerization to be combined in the three-dimensional graphene oxide/tin ash of sulfonation
Above thing, cladding polyaniline prepares sulfoxidation Graphene/three-dimensional porous netty compound material of tin ash/polyaniline.
Concretely comprise the following steps：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution and
NaOH solution, is transferred in autoclave after supersound process 5 min, 185 DEG C of reaction 8 h, after naturally cooling to room temperature, uses
Deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/SnO2Colloid；Described SnCl4With the amount of the material of NaOH it
Than for 1:4, obtained graphene oxide/SnO2SnO in colloid2Mass ratio with graphene oxide is 0.1 ~ 2:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05 ~ 2g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution is
Oil phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h, oil-water interfaces at 0 ~ 5 DEG C
Substantial amounts of blackish green product occurs, after filtering, washing, 12 hs is dried at 60 DEG C sulfoxidation Graphene/titanium dioxide is obtained
Stannum/polyaniline composite material.
The inventive method preparation process is simple, environmental protection, reliability, and obtained composite is three-dimensional porous net
Shape, has regular space structure, high-energy-density and power density, outstanding cycle performance, is one kind preferably super electricity
Container electrode material.
Brief description
Fig. 1 is sweeping of prepared sulfoxidation Graphene/composite material of stannic oxide/polyaniline in the embodiment of the present invention 19
Retouch electron microscope.
Specific embodiment
Embodiment 1：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution（Contain
0.0864 g SnCl4）And NaOH solution（Containing 0.0531 g NaOH）, it is transferred in autoclave after supersound process 5 min,
185 DEG C of reaction 8 h, after naturally cooling to room temperature, deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/
SnO2Colloid；Described SnCl4Ratio with the amount of the material of NaOH is 1:4, obtained graphene oxide/SnO2SnO in colloid2
Mass ratio with graphene oxide is 0.1:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 3 DEG C, oil-water interfaces occur
Substantial amounts of blackish green product, through filter, washing after, at 60 DEG C be dried 12 h i.e. be obtained sulfoxidation Graphene/tin ash/
Polyaniline composite material.
Embodiment 2：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution（Contain
0.1728 g SnCl4）And NaOH solution（Containing 0.1062 g NaOH）, it is transferred in autoclave after supersound process 5 min,
185 DEG C of reaction 8 h, after naturally cooling to room temperature, deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/
SnO2Colloid；Described SnCl4Ratio with the amount of the material of NaOH is 1:4, obtained graphene oxide/SnO2SnO in colloid2
Mass ratio with graphene oxide is 0.2:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 3 DEG C, oil-water interfaces occur
Substantial amounts of blackish green product, through filter, washing after, at 60 DEG C be dried 12 h i.e. be obtained sulfoxidation Graphene/tin ash/
Polyaniline composite material.
Embodiment 3：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution（Contain
0.2161 g SnCl4）And NaOH solution（Containing 0.1327 g NaOH）, it is transferred in autoclave after supersound process 5 min,
185 DEG C of reaction 8 h, after naturally cooling to room temperature, deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/
SnO2Colloid；Described SnCl4Ratio with the amount of the material of NaOH is 1:4, obtained graphene oxide/SnO2SnO in colloid2
Mass ratio with graphene oxide is 0.25:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 3 DEG C, oil-water interfaces occur
Substantial amounts of blackish green product, through filter, washing after, at 60 DEG C be dried 12 h i.e. be obtained sulfoxidation Graphene/tin ash/
Polyaniline composite material.
Embodiment 4：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution（Contain
0.4321 g SnCl4）And NaOH solution（Containing 0.2654 g NaOH）, it is transferred in autoclave after supersound process 5 min,
185 DEG C of reaction 8 h, after naturally cooling to room temperature, deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/
SnO2Colloid；Described SnCl4Ratio with the amount of the material of NaOH is 1:4, obtained graphene oxide/SnO2SnO in colloid2
Mass ratio with graphene oxide is 0.5:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 3 DEG C, oil-water interfaces occur
Substantial amounts of blackish green product, through filter, washing after, at 60 DEG C be dried 12 h i.e. be obtained sulfoxidation Graphene/tin ash/
Polyaniline composite material.
Embodiment 5：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution（Contain
0.8642 g SnCl4）And NaOH solution（Containing 0.5308 g NaOH）, it is transferred in autoclave after supersound process 5 min,
185 DEG C of reaction 8 h, after naturally cooling to room temperature, deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/
SnO2Colloid；Described SnCl4Ratio with the amount of the material of NaOH is 1:4, obtained graphene oxide/SnO2SnO in colloid2
Mass ratio with graphene oxide is 1:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 3 DEG C, oil-water interfaces occur
Substantial amounts of blackish green product, through filter, washing after, at 60 DEG C be dried 12 h i.e. be obtained sulfoxidation Graphene/tin ash/
Polyaniline composite material.
Embodiment 6：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution（Contain
1.7285 g SnCl4）And NaOH solution（Containing 1.0616 g NaOH）, it is transferred in autoclave after supersound process 5 min,
185 DEG C of reaction 8 h, after naturally cooling to room temperature, deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/
SnO2Colloid；Described SnCl4Ratio with the amount of the material of NaOH is 1:4, obtained graphene oxide/SnO2SnO in colloid2
Mass ratio with graphene oxide is 2:1.
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；So
Add 0.94 g sodium nitrite in its solution backward, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, anti-in ice bath
10 min are answered to obtain aromatic diazo salt.
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained,
React 2 h under condition of ice bath, that is, obtain the graphene oxide/tin ash complex solution of sulfonation.
(4) aniline weighing 0.05g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 3 DEG C, oil-water interfaces occur
Substantial amounts of blackish green product, through filter, washing after, at 60 DEG C be dried 12 h i.e. be obtained sulfoxidation Graphene/tin ash/
Polyaniline composite material.
Embodiment 7：
The step repeating embodiment 1, the consumption only changing aniline in step (4) is 0.1223 mL.
Embodiment 8：
The step repeating embodiment 1, the consumption only changing aniline in step (4) is 0.2447 mL.
Embodiment 9：
The step repeating embodiment 1, the consumption only changing aniline in step (4) is 0.4894 mL.
Embodiment 10：
The step repeating embodiment 1, the consumption only changing aniline in step (4) is 0.9788 mL.
Embodiment 11：
The step repeating embodiment 1, the consumption only changing aniline in step (4) is 1.9575 mL.
Embodiment 12：
The step repeating embodiment 2, the consumption only changing aniline in step (4) is 0.1223 mL.
Embodiment 13：
The step repeating embodiment 2, the consumption only changing aniline in step (4) is 0.2447 mL.
Embodiment 14：
The step repeating embodiment 2, the consumption only changing aniline in step (4) is 0.4894 mL.
Embodiment 15：
The step repeating embodiment 2, the consumption only changing aniline in step (4) is 0.9788 mL.
Embodiment 16：
The step repeating embodiment 2, the consumption only changing aniline in step (4) is 1.9575 mL.
Embodiment 17：
The step repeating embodiment 3, the consumption only changing aniline in step (4) is 0.1223 mL.
Embodiment 18：
The step repeating embodiment 3, the consumption only changing aniline in step (4) is 0.2447 mL.
Embodiment 19：
The step repeating embodiment 3, the consumption only changing aniline in step (4) is 0.4894 mL.
Embodiment 20：
The step repeating embodiment 3, the consumption only changing aniline in step (4) is 0.9788 mL.
Embodiment 21：
The step repeating embodiment 3, the consumption only changing aniline in step (4) is 1.9575 mL.
Embodiment 22：
The step repeating embodiment 4, the consumption only changing aniline in step (4) is 0.1223 mL.
Embodiment 23：
The step repeating embodiment 4, the consumption only changing aniline in step (4) is 0.2447 mL.
Embodiment 24：
The step repeating embodiment 4, the consumption only changing aniline in step (4) is 0.4894 mL.
Embodiment 25：
The step repeating embodiment 4, the consumption only changing aniline in step (4) is 0.9788 mL.
Embodiment 26：
The step repeating embodiment 4, the consumption only changing aniline in step (4) is 1.9575 mL.
Embodiment 27：
The step repeating embodiment 5, the consumption only changing aniline in step (4) is 0.1223 mL.
Embodiment 28：
The step repeating embodiment 5, the consumption only changing aniline in step (4) is 0.2447 mL.
Embodiment 29：
The step repeating embodiment 5, the consumption only changing aniline in step (4) is 0.4894 mL.
Embodiment 30：
The step repeating embodiment 5, the consumption only changing aniline in step (4) is 0.9788 mL.
Embodiment 31：
The step repeating embodiment 5, the consumption only changing aniline in step (4) is 1.9575 mL.
Embodiment 32：
The step repeating embodiment 6, the consumption only changing aniline in step (4) is 0.1223 mL.
Embodiment 33：
The step repeating embodiment 6, the consumption only changing aniline in step (4) is 0.2447 mL.
Embodiment 34：
The step repeating embodiment 6, the consumption only changing aniline in step (4) is 0.4894 mL.
Embodiment 35：
The step repeating embodiment 6, the consumption only changing aniline in step (4) is 0.9788 mL.
Embodiment 36：
The step repeating embodiment 6, the consumption only changing aniline in step (4) is 1.9575 mL.
Claims (1)
1. a kind of preparation method of sulfoxidation Graphene/composite material of stannic oxide/polyaniline is it is characterised in that concrete steps
For：
(1) 0.5 g graphene oxide is dissolved in 100 mL deionized waters, ultrasonic 30 min, adds SnCl4Solution and
NaOH solution, is transferred in autoclave after supersound process 5 min, 185 DEG C of reaction 8 h, after naturally cooling to room temperature, uses
Deionized water cleaning gleanings to neutral, that is, obtain graphene oxide/SnO2Colloid；Described SnCl4With the amount of the material of NaOH it
Than for 1:4, obtained graphene oxide/SnO2SnO in colloid2Mass ratio with graphene oxide is 0.1 ~ 2:1；
(2) 2.30 g p-aminobenzene sulfonic acid are added in 100 mL deionized waters, and are slowly heated to being completely dissolved；Then to
Add 0.94 g sodium nitrite in its solution, be sufficiently stirred for the concentrated hydrochloric acid adding 2 mL concentration to be 12mol/L, in ice bath, react 10
Min obtains aromatic diazo salt；
(3) graphene oxide/SnO that step (1) is obtained2Colloid adds in the aromatic diazo salt that step (2) is obtained, in ice bath
Under the conditions of react 2 h, that is, obtain the graphene oxide/tin ash complex solution of sulfonation；
(4) aniline weighing 0.05 ~ 2g is substantially dissolved in 50 mL chloroforms, prepared aniline solution, then with aniline solution as oil
Phase, is obtained complex solution as aqueous phase with step (3), using interfacial polymerization, reacts 24 h at 0 ~ 5 DEG C, oil-water interfaces go out
Existing substantial amounts of blackish green product, after filtering, washing, is dried 12 h and sulfoxidation Graphene/titanium dioxide is obtained at 60 DEG C
Stannum/polyaniline composite material.
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| CN107867715A (en) * | 2017-11-07 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin dioxide nanometer material for low concentration Nitrogen dioxide testing and products thereof and application |
| CN108010730A (en) * | 2017-11-20 | 2018-05-08 | 桂林理工大学 | The preparation method of polyaniline nano linear array/graphene film/tin dioxide composite material |
| CN112531152A (en) * | 2020-11-11 | 2021-03-19 | 张叶芳 | Electrode material for lithium battery and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107867715A (en) * | 2017-11-07 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin dioxide nanometer material for low concentration Nitrogen dioxide testing and products thereof and application |
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| CN108010730A (en) * | 2017-11-20 | 2018-05-08 | 桂林理工大学 | The preparation method of polyaniline nano linear array/graphene film/tin dioxide composite material |
| CN112531152A (en) * | 2020-11-11 | 2021-03-19 | 张叶芳 | Electrode material for lithium battery and preparation method thereof |
| CN112531152B (en) * | 2020-11-11 | 2022-12-27 | 山东兴丰新能源科技有限公司 | Electrode material for lithium battery and preparation method thereof |
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