CN110148530B - Preparation method of magnetic field induced nickel chloride/polyaniline supercapacitor electrode material - Google Patents
Preparation method of magnetic field induced nickel chloride/polyaniline supercapacitor electrode material Download PDFInfo
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 title claims abstract description 87
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 title claims abstract description 86
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 79
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 65
- 239000007772 electrode material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims abstract description 23
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003990 capacitor Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 210000003934 vacuole Anatomy 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 239000002114 nanocomposite Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
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- 229910021645 metal ion Inorganic materials 0.000 abstract 1
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- 230000003068 static effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
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- 229920001940 conductive polymer Polymers 0.000 description 3
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- 239000004005 microsphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000004146 energy storage Methods 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- -1 aniline radical cations Chemical class 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910000339 iron disulfide Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
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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
- H01G11/48—Conductive polymers
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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
- H01G11/84—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
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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
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Abstract
The invention discloses a preparation method of a magnetic field induced nickel chloride/polyaniline super capacitor electrode material, which comprises the following steps: dispersing camphorsulfonic acid and nickel chloride in water, adding aniline monomer, uniformly mixing, dropwise adding an ammonium persulfate aqueous solution, standing in a uniform magnetic field with the temperature of 5 ℃, the temperature of 0.5T and the magnetic field interval of 60mm, and reacting for 6-24 h; and carrying out reduced pressure suction filtration, washing and vacuum freeze drying on the obtained nano material to obtain the finished product of the nickel chloride/polyaniline electrode material. Compared with the existing supercapacitor electrode material, the finished product nickel chloride/polyaniline composite nanomaterial prepared by the method has the advantages that the nickel chloride has the pseudo-capacitance effect of metal ions, the specific surface area of the electrode material is obviously increased due to the vacuole structure formed by polyaniline, and the charge enrichment and pseudo-capacitance storage effects are enhanced; the invention has simple process and lower cost, and the prepared composite material has the advantages of light specific gravity, high energy efficiency, high energy density and the like, has higher power density and is suitable for popularization.
Description
Technical Field
The invention relates to the technical field of polymer composite electrode materials, in particular to a preparation method of a magnetic field induced nickel chloride/polyaniline supercapacitor electrode material.
Background
The twenty-first century is an information technology age, and with the comprehensive application of big data and artificial intelligence technology, a large number of electronic products provide various convenient conditions for our lives and meet various requirements in the aspects of our lives, works and the like. With the increasing dependence on portable electronic devices, the use and storage of electric energy is a first problem facing the urgent need of people. The super capacitor is a novel energy storage device between a common capacitor and a chemical energy storage battery, and has the advantages of high energy density, large specific capacitance, high power density, wide applicable environment, economy, environmental protection, maintenance free, long service life and the like.
Nickel chloride is one of ideal electrode materials which can be used as a substitute of iron disulfide, and has the advantages of high charge-discharge current density, large specific capacitance, good cycling stability and the like; the conductive polymer has wide application in the field of electrode materials of super capacitors due to the higher specific capacitance performance of the conductive polymer; polyaniline has the advantages of diversified structure, good environmental stability, low price, easy obtainment, easy processing and the like, and is widely used as an electrode material of a super capacitor.
The patent with the application number of CN201410106337.0 discloses a preparation method of a polyaniline and nickel chloride composite electrode material with high electric capacity, wherein the disclosed polyaniline and nickel chloride composite electrode material is prepared by adopting a surfactant, sulfuric acid, aniline, nickel sulfate and the like to prepare lyotropic liquid crystal and then obtaining the polyaniline and nickel chloride composite electrode material by an electrodeposition and oxidation method; the polyaniline and nickel chloride composite electrode material prepared by the scheme has complex steps, is difficult to control, has poor cycling stability in testing, is not beneficial to industrial application and cost control, and is difficult to obtain stable product performance, so that the wide application of the material is influenced.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method of a magnetic field induced nickel chloride/polyaniline supercapacitor electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material is characterized by comprising the following steps:
s1, adding camphorsulfonic acid and nickel chloride into a deionized water solution, mechanically stirring and uniformly dispersing, standing at a low temperature in a uniform magnetic field, adding an aniline monomer, mechanically stirring and uniformly mixing, then adding an ammonium persulfate aqueous solution dropwise, and uniformly stirring to obtain a mixed reaction solution;
s2, placing the mixed solution in a low-temperature uniform magnetic field for reaction for a certain time;
and S3, after the reaction is finished, carrying out vacuum filtration, washing, and carrying out vacuum freeze drying to obtain the finished product of the nickel chloride/polyaniline nanocomposite.
Preferably, in S1, the molar ratio of camphorsulfonic acid to aniline monomer is (1-5): 10.
Preferably, in S1, the molar (mol) ratio of the nickel chloride to the aniline monomer is (1-5): 10.
Preferably, in the S1, the reaction system temperature is kept at 5 ℃ low temperature.
Preferably, in S1, the uniform magnetic field strength is 0.5T, and the field spacing is 60 mm.
Preferably, in the S1, the molar ratio of the camphor sulfonic acid to the nickel chloride to the aniline monomer to the ammonium persulfate is 1 (1-5) to 1-10 (1.2-12).
Preferably, in the step S1, the uniform stirring speed is 150-200 rpm; the dropping speed of the ammonium persulfate aqueous solution is 2-4 drops/s; and maintaining the temperature of the solution system at 5 ℃ in the dropping process of the ammonium persulfate aqueous solution.
Preferably, in S2, the reaction conditions of the mixed reaction solution are: standing in a uniform magnetic field with the temperature of 5 ℃, the time of 0.5T and the magnetic field interval of 60mm, and reacting for 6-24 h.
Preferably, in S3, the washing operation is as follows: washing the product obtained by suction filtration with distilled water and absolute ethyl alcohol in sequence until the filtrate is colorless.
Preferably, in S3, the temperature of freeze drying is-30 to-40 ℃, and the time of freeze drying is 8 to 12 hours.
Preferably, the average outer diameter of the finished product nickel chloride/polyaniline nanocomposite prepared by S3 is 300-400nm, and the wall thickness is 10-15 nm.
The finished product nickel chloride/polyaniline nano composite material prepared by the invention is preferentially used as an electrode material of a super capacitor, can be coated and sprayed on a substrate material of the super capacitor by mixing an adhesive when in use, can also be subjected to field reaction induced by a magnetic field, directly grows crystals on the substrate material of the super capacitor, and is dried to obtain the electrode material which can be directly applied.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, camphorsulfonic acid is used as doping acid, aniline monomer which is purified and removed of a polymerization inhibitor and activated nickel chloride are uniformly stirred, and the aniline monomer is subjected to low-temperature standing reaction under the action of an external steady-state uniform magnetic field under the action of proper temperature and proper amount of initiator ammonium persulfate to obtain the nickel chloride/polyaniline supercapacitor electrode material with a vacuole structure.
Compared with the prior super capacitor electrodeThe material effectively increases the specific capacitance and the charge-discharge efficiency, and is characterized in that nickel chloride has good charge enrichment and storage performance, and meanwhile, the open cavity structure formed by polyaniline greatly increases the specific surface area of the electrode material, so that the contact area between the inner surface and the outer surface of a bulb and electrolyte is increased in a geometric multiple manner, the charge enrichment and storage effects are enhanced, the specific gravity is low, the energy efficiency is high, and the specific capacitance and the charge-discharge cycle stability are effectively improved. Compared with the common polyaniline super capacitor electrode material, the electrode material of the nickel chloride/polyaniline super capacitor with the vacuole structure is 1 A.g-1The specific capacitance of the capacitor reaches 801 F.g under the current density-1At 5A · g-1The specific capacitance value of the capacitor can still reach 472F g after the charge and discharge are cycled for 2000 times under the current density-1And the preparation process is simple and the cost is easy to control.
Drawings
FIG. 1 is a scanning electron microscope image of the microsphere type nickel chloride/polyaniline nanocomposite obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the vacuolated nickel chloride/polyaniline nanocomposite obtained in example 3 of the present invention;
FIG. 3 is a scanning electron microscope image of the tube-strip type nickel chloride/polyaniline nanocomposite obtained in example 5 of the present invention;
FIG. 4 is a scanning electron microscope image of the nickel chloride/polyaniline nanomaterial prepared under the condition of no magnetic field in the comparative example of the present invention;
FIG. 5(a) shows the ratio of the vacuole type nickel chloride/polyaniline nanocomposite obtained in example 3 of the present invention to the ratio of 1A g-1A charge-discharge curve chart measured under the current density condition;
FIG. 5(b) shows the concentration of the nickel chloride/polyaniline nanomaterial prepared under the condition of no magnetic field in the comparative example of the present invention at 1 A.g-1A charge-discharge curve chart measured under the current density condition;
FIG. 5(c) shows that the amount of the vacuole-type nickel chloride/polyaniline nanocomposite obtained in example 3 of the present invention was 5A g-1And (3) a charge-discharge curve graph measured under the current density condition.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1:
the preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material comprises the following steps:
1) dispersing 0.117g of camphorsulfonic acid and 0.649g of nickel chloride in 500ml of deionized water, mechanically stirring and uniformly dispersing, and placing in a 0.5T steady-state uniform static magnetic field; then 0.93g aniline monomer is added, and the mixed solution is kept at the temperature of 5 ℃ by using a low-temperature cooling system and is continuously stirred for 10 min; dispersing 2.74g of ammonium persulfate in 500ml of deionized water, cooling to 5 ℃ and precooling; dropwise adding an ammonium persulfate solution into a mixed solution of camphorsulfonic acid, nickel chloride and aniline, and controlling the reaction temperature to be 5 ℃;
2) after the dropwise addition is finished, stopping stirring, and standing the mixed solution system at 5 ℃ in a 0.5T steady-state uniform static magnetic field for reaction for 24 hours;
3) removing supernatant of the product obtained in the step 2), carrying out suction filtration, and washing with deionized water and absolute ethyl alcohol respectively until the filtrate is colorless; and then freezing for 10 hours at the temperature of minus 10 ℃, taking out a sample, and carrying out freeze drying for 12 hours at the temperature of minus 40 ℃ by using a freeze dryer to obtain the nickel chloride/polyaniline super capacitor electrode material with the microspheric structure, as shown in figure 1.
Example 2:
the preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material comprises the following steps:
1) dispersing 0.234g of camphorsulfonic acid and 0.516g of nickel chloride in 500ml of deionized water, mechanically stirring and uniformly dispersing, and placing in a 0.5T steady-state uniform static magnetic field; then 0.745g aniline monomer is added, and the mixed solution is kept at the temperature of 5 ℃ for continuous stirring for 10min by using a low-temperature cooling system; dispersing 2.192g of ammonium persulfate in 500ml of deionized water, cooling to 5 ℃ and precooling; dropwise adding an ammonium persulfate solution into a mixed solution of camphorsulfonic acid, nickel chloride and aniline, and controlling the reaction temperature to be 5 ℃;
2) after the dropwise addition, stopping stirring, and standing the mixed solution system at 5 ℃ in a 0.5T steady-state uniform static magnetic field for reaction for 20 hours;
3) removing supernatant of the product obtained in the step 2), carrying out suction filtration, and washing with deionized water and absolute ethyl alcohol respectively until the filtrate is colorless; and then freezing for 10 hours at the temperature of minus 10 ℃, taking out and freezing and drying for 10 hours at the temperature of minus 40 ℃ by using a freeze dryer to obtain the nickel chloride/polyaniline super capacitor electrode material with the microsphere and vacuole mixed structure.
Example 3:
the preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material comprises the following steps:
1) dispersing 0.351g of camphorsulfonic acid and 0.387g of nickel chloride in 500ml of deionized water, mechanically stirring and uniformly dispersing, and placing in a 0.5T steady-state uniform static magnetic field; then 0.559g of aniline monomer is added, and the mixed solution is kept at the temperature of 5 ℃ for continuous stirring for 10min by using a low-temperature cooling system; 1.643g of ammonium persulfate is dispersed in 500ml of deionized water, and the temperature is reduced to 5 ℃ for precooling; dropwise adding an ammonium persulfate solution into a mixed solution of camphorsulfonic acid, nickel chloride and aniline, and controlling the reaction temperature to be 5 ℃;
2) after the dropwise addition, stopping stirring, and standing the mixed solution system at 5 ℃ in a 0.5T steady-state uniform static magnetic field for reaction for 16 h;
3) removing supernatant of the product obtained in the step 2), carrying out suction filtration, and washing with deionized water and absolute ethyl alcohol respectively until the filtrate is colorless; then freezing for 10 hours at-10 ℃, taking out and freezing and drying for 8 hours at-30 ℃ by using a freeze dryer to obtain the nickel chloride/polyaniline supercapacitor electrode material with the vacuole structure, wherein a Scanning Electron Microscope (SEM) picture of the nickel chloride/polyaniline supercapacitor electrode material is shown in figure 2.
Example 4:
the preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material comprises the following steps:
1) dispersing 0.469g of camphorsulfonic acid and 0.258g of nickel chloride in 500ml of deionized water, mechanically stirring and uniformly dispersing, and placing in a 0.5T steady-state uniform static magnetic field; then 0.377g aniline monomer is added, and the mixed solution is kept at the temperature of 5 ℃ by using a low-temperature cooling system and is continuously stirred for 10 min; dispersing 1.095g of ammonium persulfate in 500ml of deionized water, cooling to 5 ℃ and precooling; dropwise adding an ammonium persulfate solution into a mixed solution of camphorsulfonic acid, nickel chloride and aniline, and controlling the reaction temperature to be 5 ℃;
2) after the dropwise addition, stopping stirring, and standing the mixed solution system at 5 ℃ in a 0.5T steady-state uniform static magnetic field for reaction for 12 hours;
3) removing supernatant of the product obtained in the step 2), carrying out suction filtration, and washing with deionized water and absolute ethyl alcohol respectively until the filtrate is colorless; and then freezing for 10 hours at the temperature of minus 10 ℃, taking out and freezing and drying for 8 hours at the temperature of minus 30 ℃ by using a freeze dryer to obtain the nickel chloride/polyaniline super capacitor electrode material with the tubular and vacuole mixed structure.
Example 5:
the preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material comprises the following steps:
1) dispersing 0.586g of camphorsulfonic acid and 0.129g of nickel chloride in 500ml of deionized water, mechanically stirring and uniformly dispersing, and placing in a 0.5T steady-state uniform static magnetic field; then 0.186g aniline monomer is added, and the mixed solution is kept at 5 ℃ for continuous stirring for 10min by using a low-temperature cooling system; 0.547g of ammonium persulfate is dispersed in 500ml of deionized water, and the temperature is reduced to 5 ℃ for precooling; dropwise adding an ammonium persulfate solution into a mixed solution of camphorsulfonic acid, nickel chloride and aniline, and controlling the reaction temperature to be 5 ℃;
2) after the dropwise addition is finished, stopping stirring, and standing the mixed solution system at 5 ℃ in a 0.5T steady-state uniform static magnetic field for reaction for 8 hours;
3) removing supernatant of the product obtained in the step 2), carrying out suction filtration, and washing with deionized water and absolute ethyl alcohol respectively until the filtrate is colorless; and then freezing for 10 hours at the temperature of minus 10 ℃, taking out and freezing and drying for 8 hours at the temperature of minus 30 ℃ by using a freeze dryer to obtain the nickel chloride/polyaniline super capacitor electrode material with the tubular strip structure, wherein the nickel chloride/polyaniline super capacitor electrode material is shown in figure 3.
Comparative example:
s1, dispersing 0.351g of camphorsulfonic acid and 0.387g of nickel chloride in 500ml of deionized water, and mechanically stirring and uniformly dispersing; then 0.559g of aniline monomer is added, and the mixed solution is kept at the temperature of 5 ℃ for continuous stirring for 10min by using a low-temperature cooling system; 1.643g of ammonium persulfate is dispersed in 500ml of deionized water, and the temperature is reduced to 5 ℃ for precooling; dropwise adding an ammonium persulfate solution into a mixed solution of camphorsulfonic acid, nickel chloride and aniline, and controlling the reaction temperature to be 5 ℃;
s2, stopping stirring after the dropwise addition is finished, and continuously standing the mixed solution system at the temperature of 5 ℃ for reaction for 16 hours;
s3, removing supernatant of the product obtained in the step 2), filtering, and washing with deionized water and absolute ethyl alcohol respectively until the filtrate is colorless; then freezing for 10 hours at-10 ℃, taking out and freeze-drying for 8 hours at-30 ℃ by using a freeze dryer, thus obtaining the nickel chloride/polyaniline composite material, as shown in figure 4. TABLE 1 preparation process conditions and specific capacitance of finished nickel chloride/polyaniline nanocomposite
As shown in table 1, the scanning electron microscope characterization of examples 1 to 5 and comparative example are performed, and only example 1, example 3, example 5 and comparative example are listed, as shown in fig. 1 to 4; constant-current charge and discharge tests are carried out on the electrode material of the nickel chloride/polyaniline supercapacitor with the vacuole structure obtained in the example 3 and the sea cucumber-like nickel chloride/polyaniline nanocomposite obtained in the comparative example, and the obtained comparison result is shown in fig. 5.
As shown in fig. 1-4 and table 1, as the content of camphorsulfonic acid increases (the molar ratio of aniline to nickel chloride is substantially unchanged), the morphology of the final nickel chloride/polyaniline composite material changes from microsphere-void-tube strip to significantly change the specific surface area. The nickel chloride/polyaniline super capacitor electrode material with the vacuole structure is obtained in the embodiment 3, and polyaniline is in an open vacuole structure.
On the other hand, the content of the template agent (camphorsulfonic acid) is increased, and the crystal growth of polyaniline is promoted. The mechanism analysis is as follows: polyaniline belongs to anisotropic organic polymer materials, so that the polyaniline has anisotropic magnetic susceptibility, and the magnitude and the direction of the magnetization energy received by different configurations in a magnetic field are different. When the macromolecule is under the condition of an external magnetic field, the molecular crystal is promoted to rotate when the difference value caused by the magnitude of the magnetization energy and the angular momentum of the molecular crystal in different directions reaches a certain degree, and the molecular crystal stops rotating to an equilibrium position, namely the position with the minimum magnetization energy, so that the orientation effect is formed on the appearance and the structure of the molecular crystal. The benzene ring on the main chain of the polyaniline belongs to diamagnetic groups, so the polyaniline has anisotropic diamagnetism, and when the polyaniline grows under the induction of a magnetic field, molecular crystals grow along the direction vertical to the magnetic field, and the growth is inhibited in the direction parallel to the magnetic field. And, with the gradual growth of molecular chains, steric hindrance between molecules further hinders the induced orientation effect of the magnetic field.
As shown in FIG. 5, the constant current charge and discharge test was performed on the electrode material of the vacuole-structured nickel chloride/polyaniline supercapacitor obtained in example 3 and the sea cucumber-like nickel chloride/polyaniline obtained in equal proportion, and the charge and discharge curve of the electrode material of the vacuole-structured nickel chloride/polyaniline supercapacitor obtained in example 3 was shown to be at 1 A.g-1The maximum specific capacitance can reach 801 F.g at the current density of (2)-1，At 5A · g-1The specific capacitance of the charge-discharge curve under the current density of (1) can still reach 472F g after 2000 times of charge-discharge cycles-1The charging and discharging curve chart of the sea cucumber-shaped nickel chloride/polyaniline obtained by the comparative example is 1 A.g-1Has a maximum specific capacitance of only 343F g at a current density of (1)-1And the potential drop is very severe.
The open porous structure of the nickel chloride/polyaniline nano composite material with the vacuole structure effectively increases the specific surface area of the material, and the sea cucumber-like nickel chloride/polyaniline obtained by comparison with the proportion has higher specific capacitance and better charge-discharge cycle stability, which shows that the magnetic field induction can be used for controlling the nano morphological structure of the polyaniline, and the mechanism is as follows: according to the prior art, magnetic fields have been shown to influence free-radical polymerization reactions. Aniline polymerization is a typical free radical polymerization, and the research in the early stage of the subject group finds that the conductive polymer has smaller interplanar spacing, larger lattice size and better crystallinity with the introduction of an external magnetic field. The magnetic field is a special electromagnetic field form under an extreme condition, and can transfer high-intensity energy to the atomic scale of a substance in a non-contact manner, change the arrangement, matching and migration of atoms and molecules, and influence chemical equilibrium, Zeeman effect and the like. Therefore, theoretically, the shape, structure and even electrical and magnetic properties of the polyaniline product can be regulated and controlled by using a strong magnetic field. Theoretically, the method explains that the polyaniline prepared under the induction of a magnetic field has better crystallinity, more compact chain structure and higher degree of order. In addition, magnetic fields parallel to the surface of the applied electrode are more effective than perpendicular fields; the aniline radical cations are oriented along the lorentz force and the magnetic field can also stabilize the intermediate radicals, and the polyaniline chains are stretched by the magnetic field. The induced direction of the magnetic field not only increases the crystallinity but also reduces the energy barrier to charge transport and can also increase the degree of delocalization of the polarons along the chain. Therefore, the polyaniline and nickel chloride composite material prepared by magnetic field induction has better crystallinity and conductivity, and effectively promotes the charge transmission of the active layer.
Therefore, the invention fully controls the morphological structure and the specific surface area of the nickel chloride/polyaniline composite material under the coordination of magnetic field induction and a template agent (camphorsulfonic acid), finally uses the nickel chloride/polyaniline composite material with a cavity structure as an electrode material with the optimal specific capacitance value, and generates cavity balls with holes due to the induction effect of the magnetic field, thereby not only greatly increasing the external surface area of the material, but also facilitating the electrolyte to enter the inside of the bulb to contact with the internal surface of the cavity. Compared with the sea cucumber-shaped nickel chloride/polyaniline composite material prepared under the condition of no magnetic field, the vacuole structure is favorable for rapidly carrying out charge transmission between the electrolyte and the electrode material, the internal resistance of the electrode material is reduced, and the conclusion is verified through the cyclic charge-discharge data. The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. The preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material is characterized by comprising the following steps:
s1, adding camphorsulfonic acid and nickel chloride into a deionized water solution, mechanically stirring and uniformly dispersing, standing at a low temperature in a uniform magnetic field, adding an aniline monomer, mechanically stirring and uniformly mixing, then adding an ammonium persulfate aqueous solution dropwise, and uniformly stirring to obtain a mixed reaction solution;
s2, placing the mixed solution in a low-temperature uniform magnetic field for reaction for a certain time;
s3, after the reaction is finished, carrying out vacuum filtration, washing, and carrying out vacuum freeze drying to obtain a finished product of the nickel chloride/polyaniline nanocomposite material, wherein the finished product of the nickel chloride/polyaniline nanocomposite material is specifically a nickel chloride/polyaniline supercapacitor electrode material with a vacuole structure, and polyaniline is in an open vacuole structure;
in the S1, the molar (mol) ratio of the camphorsulfonic acid to the aniline monomer is (1-5) to 10;
in the S1, the molar (mol) ratio of the nickel chloride to the aniline monomer is (1-5) to 10;
in the step S1, the uniform stirring speed is 150-200 rpm; the dropping speed of the ammonium persulfate aqueous solution is 2-4 drops/s; maintaining the temperature of a solution system at 5 ℃ in the dropping process of the ammonium persulfate aqueous solution;
in the step S2, the reaction conditions of the mixed reaction solution are: standing in a uniform magnetic field with the temperature of 5 ℃, the time of 0.5T and the magnetic field interval of 60mm, and reacting for 6-24 h.
2. The preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material according to claim 1, wherein in the step S1, the temperature of the reaction system is kept at a low temperature of 5 ℃.
3. The method for preparing the magnetic field-induced nickel chloride/polyaniline supercapacitor electrode material according to claim 1, wherein in S1, the reaction uniform magnetic field strength is 0.5T, and the field spacing is 60 mm.
4. The preparation method of the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material according to claim 1, wherein in S1, the molar ratio of camphorsulfonic acid, nickel chloride, aniline monomer and ammonium persulfate is 1 (1-5): 1-10): 1.2-12.
5. The method for preparing the electrode material of the magnetic field induced nickel chloride/polyaniline supercapacitor as claimed in claim 1, wherein the average outer diameter of the finished product nickel chloride/polyaniline nanocomposite prepared by the step S3 is 300-400nm, and the wall thickness is 10-15 nm.
6. A method for preparing the magnetic field induced nickel chloride/polyaniline supercapacitor electrode material according to any one of claims 1 to 5, wherein the prepared finished nickel chloride/polyaniline nanocomposite is used as the supercapacitor electrode material and is 1A ∙ g-1Has a specific capacitance of 801F ∙ g-1At 5A ∙ g-1The specific capacitance value of the capacitor can still reach 472F ∙ g after being circularly charged and discharged for 2000 times under the current density-1。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733821A (en) * | 2005-08-26 | 2006-02-15 | 重庆大学 | Preparation method of high conductivity polyaniline in magnetic field |
| CN108010735A (en) * | 2018-01-10 | 2018-05-08 | 合肥师范学院 | The preparation of polyaniline/graphene oxide and the application in electrode of super capacitor |
| WO2018184341A1 (en) * | 2017-04-07 | 2018-10-11 | 苏州海凌达电子科技有限公司 | Preparation method for high-performance material for use in supercapacitor |
| CN108774320A (en) * | 2018-07-02 | 2018-11-09 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of nickel oxide loaded polyaniline |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733821A (en) * | 2005-08-26 | 2006-02-15 | 重庆大学 | Preparation method of high conductivity polyaniline in magnetic field |
| WO2018184341A1 (en) * | 2017-04-07 | 2018-10-11 | 苏州海凌达电子科技有限公司 | Preparation method for high-performance material for use in supercapacitor |
| CN108010735A (en) * | 2018-01-10 | 2018-05-08 | 合肥师范学院 | The preparation of polyaniline/graphene oxide and the application in electrode of super capacitor |
| CN108774320A (en) * | 2018-07-02 | 2018-11-09 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of nickel oxide loaded polyaniline |
Non-Patent Citations (1)
| Title |
|---|
| Magnetic-field assisted synthesis of carbon dots-doped polyaniline nanotubes with a high-performance supercapacitance;Jian Liu;《Synthetic Metals》;20181004;第246卷;文章第23-25页，原理图1 * |
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