CN110223853A - A kind of preparation and application of polyaniline nano linear array/graphene hollow sphere - Google Patents
A kind of preparation and application of polyaniline nano linear array/graphene hollow sphere Download PDFInfo
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- CN110223853A CN110223853A CN201910540426.9A CN201910540426A CN110223853A CN 110223853 A CN110223853 A CN 110223853A CN 201910540426 A CN201910540426 A CN 201910540426A CN 110223853 A CN110223853 A CN 110223853A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical class OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000004151 quinonyl group Chemical group 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to field of nano material preparation, disclose the preparation and application of a kind of polyaniline nano linear array/graphene hollow sphere.Graphene hollow sphere is prepared by template of nano nickel particles first, polyaniline nano linear array is then grown in the hollow ball surface of graphene by the method for in-situ polymerization, obtains a kind of high performance polyaniline nano linear array/graphene hollow sphere.Present invention process process is simple, at low cost, when polyaniline nano linear array/graphene hollow sphere of preparation is used as electrode material for super capacitor, the high specific capacitance with 643 F/g in the case where current density is 1 A/g.After being assembled into symmetrical supercapacitor, in the case where current density is 1 A/g after charge and discharge cycles 5000 times still with 89% capacity retention.
Description
Technical field
The invention belongs to field of nano material preparation, are related to a kind of system of polyaniline nano linear array/graphene hollow sphere
Standby and application.
Background technique
Supercapacitor is also known as electrochemical capacitor, has have extended cycle life, charge/discharge speed is fast and power density is high etc.
Feature.Supercapacitor can be divided into two kinds of fundamental types: double layer capacitor and pseudocapacitors according to its charge-storage mechanism.It is living
Property electrode material is broadly divided into three types: carbon material, conductive polymer material and metal oxide.
Graphene as excellent carbon material there is excellent electric conductivity, the chemical stability of superelevation and long circulating to stablize
Property, it is widely used in the electrode material of supercapacitor.But since graphene nanometer sheet is inevitably assembled and double
The mechanism of electric layer capacitor, although stability is fine, specific capacitance is relatively low.In contrast, fake capacitance material (conductive polymer
Sub- material and metal oxide), since quick faraday's redox reaction of electrode material surface or near surface can be significant
Improve specific capacitance.Polyaniline has high theoretical specific capacitance (2.0 × 10 as a kind of excellent conducting polymer3F/g), soft
It good toughness and is readily synthesized, therefore is widely used as electrode material for super capacitor.But its stability is poor, to a certain extent
Limit its further application.
The synergistic effect that the optimization structure of reasonable graphene and polyaniline both will be played effectively is designed, is promoted compound
The chemical property of material.In order to effectively avoid the agglomeration traits of graphene, we are prepared for graphene hollow sphere, spherical
Structure not only solves agglomeration traits and also provides stable skeleton for the building of composite material.Then use the side of in-situ polymerization
Method grows polyaniline nano linear array on the surface of graphene hollow sphere.Polyaniline not only increases the fake capacitance of composite material,
Its unique array structure is even more to greatly increase the contact area of composite material and electrolyte, it will is further improved multiple
The chemical property of condensation material.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of polyaniline nano linear array/super electricity of graphene hollow sphere
The preparation method of container electrode material.
A kind of preparation method of polyaniline nano linear array/graphene hollow sphere electrode material for super capacitor of the present invention is
It carries out according to the following steps:
Step 1: 0.05~0.2mol/L nickel chloride is dissolved in water, 80% hydrazine hydrate is then added, is stirring evenly and then adding into 50%
Sodium hydroxide, reaction is nano nickel particles until obtaining gray precipitate in 50~80 DEG C of water-baths, washs and freezes later and is dry
It is dry；
Step 2: 1~3g nano nickel particles are put into flask, and 30~50mL triethylene glycol is added, stirs evenly and be added 3
~6 drip 50% sodium hydroxide solutions, are heated to reflux 6~12h at 220~250 DEG C, after precipitating clean dry, protect in Ar atmosphere
Lower 500 DEG C of heat treatment 1h is protected, is then placed in dilute hydrochloric acid and etches away nano nickel particles, obtain graphene hollow sphere, wash later
And freeze-drying；
Step 3: the graphene hollow sphere of above-mentioned preparation is heat-treated 1h at 500~900 DEG C under Ar atmosphere protection；
It is added step 4: being immersed in graphene hollow sphere after 3~5h is impregnated in stirring in the 1mol/L sulfuric acid solution containing aniline
The 1mol/L sulfuric acid solution containing ammonium persulfate of equal volume, after mixing evenly at 0~-5 DEG C reaction 12~for 24 hours, will produce
Object washing and freeze-drying, obtain polyaniline nano linear array/graphene hollow sphere, wherein the molar ratio of aniline and ammonium persulfate
For 4:1.
A kind of application of polyaniline nano linear array/graphene hollow sphere electrode material for super capacitor, it is characterised in that
Polyaniline nano linear array/graphene hollow sphere is used as electrode material for super capacitor.
Compared to existing technology, the invention has the following beneficial effects:
1. the present invention uses graphene hollow sphere as substrate, the reunion of graphene nanometer sheet is not only avoided, it is spherical hollow
Structure further improves chemical property while increasing stability；
2. the present invention grows polyaniline nano linear array on graphene hollow sphere greatly improves composite material and electrolyte
Contact area, when as electrode material for super capacitor current density be 1A/g under with 643F/g high specific capacitance.Group
After dressing up symmetrical supercapacitor, in the case where current density is 1A/g, the still capacitor with 89% is kept after charge and discharge cycles 5000 times
Rate；
3. operation of the present invention is simple, can be prepared on a large scale.
Detailed description of the invention:
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene hollow sphere；
Fig. 2 is polyaniline nano linear array/graphene hollow sphere scanning electron microscope (SEM) photograph；
Fig. 3 is polyaniline nano linear array/graphene hollow sphere transmission electron microscope picture；
Fig. 4 is polyaniline nano linear array/graphene hollow sphere X ray diffracting spectrum；
Fig. 5 is polyaniline nano linear array/graphene hollow sphere Raman map；
Fig. 6 is polyaniline nano linear array/graphene hollow sphere Cyclic voltamogram curve；
Fig. 7 is polyaniline nano linear array/graphene hollow sphere constant current charge-discharge curve；
Fig. 8 is specific capacity curve of the polyaniline nano linear array/graphene hollow sphere under different current densities；
Fig. 9 is polyaniline nano linear array/graphene hollow sphere stable circulation linearity curve；
Specific embodiment
Invention is further described in detail combined with specific embodiments below, it should be pointed out that example as described below
It is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
Polyaniline nano linear array/graphene hollow sphere preparation method, comprising the following steps:
Step 1: 0.05~0.2mol/L nickel chloride is dissolved in water, 80% hydrazine hydrate is then added, is stirring evenly and then adding into 50%
Sodium hydroxide, reaction is nano nickel particles until obtaining gray precipitate in 50~80 DEG C of water-baths, washs and freezes later and is dry
It is dry；
Step 2: 1~3g nano nickel particles are put into flask, and 30~50mL triethylene glycol is added, stirs evenly and be added 3
~6 drip 50% sodium hydroxide solutions, are heated to reflux 6~12h at 220~250 DEG C, after precipitating clean dry, protect in Ar atmosphere
Lower 500 DEG C of heat treatment 1h is protected, is then placed in dilute hydrochloric acid and etches away nano nickel particles, obtain graphene hollow sphere, wash later
And freeze-drying；
Step 3: the graphene hollow sphere of above-mentioned preparation is heat-treated 1h at 500~900 DEG C under Ar atmosphere protection；
It is added step 4: being immersed in graphene hollow sphere after 3~5h is impregnated in stirring in the 1mol/L sulfuric acid solution containing aniline
The 1mol/L sulfuric acid solution containing ammonium persulfate of equal volume, after mixing evenly at 0~-5 DEG C reaction 12~for 24 hours, will produce
Object washing and freeze-drying, obtain polyaniline nano linear array/graphene hollow sphere, wherein the molar ratio of aniline and ammonium persulfate
For 4:1.
Embodiment 2:
Polyaniline nano linear array/graphene hollow sphere preparation method, comprising the following steps:
Step 1: 0.05~0.2mol/L nickel chloride is dissolved in water, 80% hydrazine hydrate is then added, is stirring evenly and then adding into 50%
Sodium hydroxide, reaction is nano nickel particles until obtaining gray precipitate in 60~80 DEG C of water-baths, washs and freezes later and is dry
It is dry；
Step 2: 2~3g nano nickel particles are put into flask, and 30~50mL triethylene glycol is added, stirs evenly and be added 4
~6 drip 50% sodium hydroxide solutions, are heated to reflux 8~12h at 230~250 DEG C, after precipitating clean dry, protect in Ar atmosphere
Lower 500 DEG C of heat treatment 1h is protected, is then placed in dilute hydrochloric acid and etches away nano nickel particles, obtain graphene hollow sphere, wash later
And freeze-drying；
Step 3: the graphene hollow sphere of above-mentioned preparation is heat-treated 1h at 600~900 DEG C under Ar atmosphere protection；
It is added step 4: being immersed in graphene hollow sphere after 4~5h is impregnated in stirring in the 1mol/L sulfuric acid solution containing aniline
The 1mol/L sulfuric acid solution containing ammonium persulfate of equal volume, after mixing evenly at 0~-5 DEG C reaction 16~for 24 hours, will produce
Object washing and freeze-drying, obtain polyaniline nano linear array/graphene hollow sphere, wherein the molar ratio of aniline and ammonium persulfate
For 4:1.
Embodiment 3:
Polyaniline nano linear array/graphene hollow sphere preparation method, comprising the following steps:
Step 1: 0.05~0.2mol/L nickel chloride is dissolved in water, 80% hydrazine hydrate is then added, is stirring evenly and then adding into 50%
Sodium hydroxide, reaction is nano nickel particles until obtaining gray precipitate in 70~80 DEG C of water-baths, washs and freezes later and is dry
It is dry；
Step 2: 2.5~3g nano nickel particles are put into flask, and 40~50mL triethylene glycol is added, stirs evenly and adds
Enter 5~6 50% sodium hydroxide solutions of drop, 10~12h is heated to reflux at 240~250 DEG C, after precipitating clean dry, in Ar gas
Atmosphere protects lower 500 DEG C of heat treatment 1h, is then placed in dilute hydrochloric acid and etches away nano nickel particles, obtains graphene hollow sphere, later
Washing and freeze-drying；
Step 3: the graphene hollow sphere of above-mentioned preparation is heat-treated 1h at 700~900 DEG C under Ar atmosphere protection；
Add step 4: being immersed in graphene hollow sphere after 4.5~5h is impregnated in stirring in the 1mol/L sulfuric acid solution containing aniline
Enter the 1mol/L sulfuric acid solution containing ammonium persulfate of equal volume, after mixing evenly at 0~-5 DEG C reaction 20~for 24 hours, will
Product washing and freeze-drying, obtain polyaniline nano linear array/graphene hollow sphere, wherein mole of aniline and ammonium persulfate
Than for 4:1.
Using following verification experimental verifications effect of the present invention:
Test one: polyaniline nano linear array/graphene hollow sphere preparation method of this test is realized by the following method:
Step 1: 23.77g nickel chloride is dissolved in water, 80% hydrazine hydrate of 25ml is then added, is cooled to room temperature addition to temperature
50% sodium hydroxide of 16ml, reaction until obtaining gray precipitate is nano nickel particles in 80 DEG C of water-baths, washing later and
Freeze-drying；
Step 2: 2.5g nano nickel particles are put into flask, and 40mL triethylene glycol is added, stirs evenly and 5 drops are added
50% sodium hydroxide solution is heated to reflux 12h at 220 DEG C, after precipitating clean dry, 500 DEG C of heat under Ar atmosphere protection
1h is handled, is then placed in dilute hydrochloric acid and etches away nano nickel particles, obtain graphene hollow sphere, washs and is freeze-dried later；
Step 3: the graphene hollow sphere of above-mentioned preparation is heat-treated 1h at 900 DEG C under Ar atmosphere protection；
It is added on an equal basis step 4: being immersed in graphene hollow sphere after 5h is impregnated in stirring in the 1mol/L sulfuric acid solution containing aniline
The 1mol/L sulfuric acid solution containing ammonium persulfate of volume, reacts at -5 DEG C for 24 hours after mixing evenly, and product is washed and freezed
It is dry, polyaniline nano linear array/graphene hollow sphere is obtained, wherein the molar ratio of aniline and ammonium persulfate is 4:1.
Test two: carry out electro-chemical test of the polyaniline nano linear array/graphene hollow sphere as working electrode, specifically
It operates as follows:
Example 8:1:1 in mass ratio is by polyaniline nano linear array/graphene hollow sphere, conductive black and Kynoar (PVDF)
Mixing, is added suitable N-Methyl pyrrolidone (NMP) and grinds, it is uniformly then applied to 1 × 1cm2Stainless (steel) wire
On, electrode slice is made after carrying out tabletting under 10MPa pressure after 120 DEG C of dry 12h in vacuum tank.
The present invention uses the chemical property of three electrode test system research materials.Using paillon as to electricity in three electrodes
Pole, Ag/AgCl electrode are tested as reference electrode, the sulfuric acid solution of 1mol/L as electrolyte.
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene hollow sphere, and as can be seen from the figure the diameter of graphene hollow sphere is about
500nm。
Fig. 2 is polyaniline nano linear array/graphene hollow sphere scanning electron microscope (SEM) photograph, and as can be seen from the figure polyaniline is received
Nanowire arrays are uniformly grown in the hollow ball surface of graphene.
Fig. 3 is polyaniline nano linear array/graphene hollow sphere transmission electron microscope picture, and as can be seen from the figure polyaniline is received
The length of nanowire arrays is about 220nm.
Fig. 4 is polyaniline nano linear array/graphene hollow sphere X ray diffracting spectrum, the feature of graphene hollow sphere
Peak is present in 25.9 ° of positions, (002) crystal face of corresponding graphene, and the characteristic peak of polyaniline appears in 9.1 °, and 14.8 °,
At 20.8 ° and 25.9 ° of positions, (001) of corresponding polyaniline, (011), (020) and (200) crystal face, polyaniline nano linear array/
The characteristic peak of graphene hollow sphere is similar with the characteristic peak of graphene hollow sphere and polyaniline, is combining polyaniline nano linear array
Polyaniline nano-line successful growth known to column/graphene hollow sphere scanning electron microscope and transmission electron microscope map analysis is hollow in graphene
Ball surface.
Fig. 5 is polyaniline nano linear array/graphene hollow sphere Raman map, and the characteristic peak of graphene hollow sphere occurs
In 1351cm-1And 1592cm-1At position, SP is respectively corresponded3The coplanar vibration of orbital hybridization carbon atom and SP2The carbon atom of hydridization
Coplanar vibration, the characteristic peak of polyaniline appears in 1174cm-1, 1241cm-1, 1338cm-1, 1409cm-1,1505cm-1With
1604cm-1At position, the C-H bending of quinone ring, the C-H bending of phenyl ring are respectively represented, the C-N of phenyl ring is stretched, and the C-C of quinone ring is curved
The C=N of song, quinone ring is stretched and the C=C of phenyl ring is stretched.
Fig. 6 is polyaniline nano linear array/graphene hollow sphere cyclic voltammetry curve, it can be seen from the figure that with
The increase of sweep speed, polyaniline nano linear array/graphene hollow ball electrode redox current density obviously increase, this
Show that polyaniline nano linear array/hollow ball electrode of graphene has good high rate performance.
Fig. 7 and Fig. 8 is polyaniline nano linear array/graphene hollow sphere constant current charge-discharge curve and polyaniline respectively
Specific capacity curve of the nano-wire array/graphene hollow sphere under different current densities, even if as can be seen from the figure in high electricity
Under current density composite material still maintained higher specific capacity (1A/g:643F/g, 2A/g:625F/g, 4A/g:594F/g,
6A/g:575F/g, 8A/g:504F/g, 10A/g:492F/g), it was demonstrated that composite material has good rate capability.
Fig. 9 is that polyaniline nano linear array/graphene hollow sphere is assembled into electric current after symmetrical supercapacitor in 1A/g
Cyclical stability test under density, as can be seen from the figure can reach in the capacity retention rate of the material after 5000 circulations
89%, show preferable cyclical stability.
Claims (7)
1. a kind of preparation and application of polyaniline nano linear array/graphene hollow sphere, which comprises the following steps:
Step 1: 0.05~0.2 mol/L nickel chloride is dissolved in water, 80% hydrazine hydrate is then added, is stirring evenly and then adding into
50% sodium hydroxide, reaction is nano nickel particles until obtaining gray precipitate in 50~80 DEG C of water-baths, is washed later and cold
It is lyophilized dry；
Step 2: 1~3 g nano nickel particles are put into flask, and 30~50 mL triethylene glycols are added, stir evenly
And 3~6 50% sodium hydroxide solutions of drop are added, and 6~12 h are heated to reflux at 220~250 DEG C, after precipitating clean dry,
500 DEG C of 1 h of heat treatment, are then placed in dilute hydrochloric acid and etch away nano nickel particles, obtain graphene under Ar atmosphere protection
Hollow sphere is washed later and is freeze-dried；
Step 3: the graphene hollow sphere of above-mentioned preparation is heat-treated 1 h under Ar atmosphere protection at 500~900 DEG C；
Step 4: graphene hollow sphere, which is immersed in stirring in the 1 mol/L sulfuric acid solution containing aniline, impregnates 3~5 h
The 1 mol/L sulfuric acid solution containing ammonium persulfate of equal volume is added afterwards, reacts 12 at 0~-5 DEG C after mixing evenly
Product is washed and is freeze-dried, obtains polyaniline nano linear array/graphene hollow sphere by~24 h.
2. the preparation method described according to claim 1, which is characterized in that nickel chloride, hydrazine hydrate, hydroxide in the first step
The molar ratio of sodium is 1:4:4.
3. the preparation method described according to claim 1, which is characterized in that the concentration of dilute hydrochloric acid is 3~5 in second step
mol/L。
4. the preparation method described according to claim 1, which is characterized in that the heating being heat-treated in second step and third step
Rate is 5~10 DEG C/min.
5. the preparation method described according to claim 1, which is characterized in that mole of aniline and ammonium persulfate in the 4th step
Than for 4:1.
6. the preparation method described according to claim 1, which is characterized in that the volume of sulfuric acid is 40~50 in the 4th step
mL。
7. the preparation method described according to claim 1, which is characterized in that produced obtained by the first step, second step and the 4th step
Object uses deionized water and ethanol washing three times respectively.
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