CN111199836A - Preparation method of polyaniline aerogel/bamboo-based activated carbon composite material - Google Patents
Preparation method of polyaniline aerogel/bamboo-based activated carbon composite material Download PDFInfo
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 120
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 120
- 241001330002 Bambuseae Species 0.000 title claims abstract description 120
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 120
- 239000011425 bamboo Substances 0.000 title claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000004964 aerogel Substances 0.000 title claims abstract description 41
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 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 32
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 16
- 238000000034 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 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 239000003610 charcoal Substances 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 21
- 238000003763 carbonization Methods 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000467 phytic acid Substances 0.000 abstract description 14
- 229940068041 phytic acid Drugs 0.000 abstract description 14
- 235000002949 phytic acid Nutrition 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000009777 vacuum freeze-drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- -1 phytic acid anions Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004804 winding Methods 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
- H01G11/30—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
- H01G11/24—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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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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Abstract
The invention relates to a preparation method of a phytic acid and hydrochloric acid co-doped polyaniline aerogel/bamboo-based activated carbon composite material. Phytic acid and hydrochloric acid are used as a cross-linking agent and a doping agent, ammonium persulfate is used as an oxidant, water is used as a reaction solvent, and the massive polyaniline aerogel/bamboo-based activated carbon composite material with excellent performance is prepared by a vacuum freeze-drying process. The polymer aerogel/bamboo-based activated carbon composite material prepared by the method has a 3D interconnected network with multistage porosity, large surface area and pore volume, simple preparation process and low cost, and the prepared aerogel composite material has high conductivity.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer 3D nano porous composite materials, and particularly relates to a preparation method of a phytic acid and hydrochloric acid co-doped polyaniline aerogel/bamboo-based activated carbon composite material.
Background
For conductive polymers, many researchers concentrate on the research of the bulk materials, but the bulk materials often have poor mechanical properties and low specific surface area, which greatly affects the performance and further limits the application range, when the polyaniline is used as a supercapacitor material, the polyaniline is simple to synthesize, the raw materials are easy to obtain, the chemical stability is good, the capacitance characteristic is high, and a unique rapid reversible doping mechanism is the conductive polymer material which is most hopefully applied to the supercapacitor, but the polyaniline as the supercapacitor has many problems, the stability of polymer chains is poor in multiple charging and discharging processes, the form is difficult to control into a required form, and the polyaniline also affects the transportation function in various forms, the winding or chain aggregation of polymers can hinder the transportation by affecting chain segments and inter-chain tunnel effect, and when the polyaniline is in an insulating state, the resistance is increased, the large current charging and discharging performance is poor. The bamboo-based activated carbon has the advantages of easily available raw materials, cleanness, low cost, high specific surface area, porous structure and the like, and has the advantages of high charge-discharge speed, long cycle life, good stability and the like when being used as an electrode material of a supercapacitor.
The polyaniline aerogel and the bamboo-based activated carbon composite material can make up the defects and shortcomings of the two materials which are independently used as a supercapacitor, the composite material has the excellent characteristics of electric double layer capacitance and pseudocapacitance, and can be used as an excellent electrode material, phytic acid is strong acid and has strong chelating capacity, 6 phosphate groups with negative charges exist, phytic acid anions are organic bulky groups and have the capacity of interacting with a plurality of chains at one time, so that the extension or curling tendency of the formed polymer chains is lower than that of small and non-crosslinked anions such as chloride, sulfate and nitrate, the phytic acid provides a 3D interconnected nanofiber structure for polyaniline, meanwhile, ionic substances are easily approached through a well-formed and distributed pore structure, but the conductivity is relatively weak, and on the other hand, when hydrochloric acid is independently doped, the hydrochloric acid generates much high conductivity, so that a phytic acid and hydrochloric acid co-doped polyaniline aerogel three-dimensional conductive network is designed, the method is low in price and can be applied in large scale, and the synthesized polyaniline aerogel/bamboo-based activated carbon composite material has no agglomeration phenomenon.
Disclosure of Invention
The invention aims to provide a preparation method of a phytic acid and hydrochloric acid co-doped polyaniline aerogel/bamboo-based activated carbon composite material, which comprises the following steps:
the method comprises the following steps: the bamboo charcoal is prepared by cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks with deionized water, drying the bamboo blocks in an oven at 80 ℃ for 24 hours, putting the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the temperature at 800 ℃ for 2-4 hours, crushing the carbonized bamboo charcoal with a ball mill, and sieving the crushed bamboo charcoal with a 200-mesh sieve.
Step two: the preparation method of the bamboo-based activated carbon comprises the steps of weighing bamboo charcoal and potassium hydroxide according to a certain alkali-carbon ratio, placing the bamboo charcoal and the potassium hydroxide into a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 700-900 ℃ at a certain heating speed, keeping the temperature for 2-4 hours, cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
Step three: the preparation method comprises the steps of preparing a polyaniline aerogel/bamboo-based activated carbon composite material, wherein the molar ratio of aniline to ammonium persulfate is 2: 1-4: 1, adding water and phytic acid solution into a first small bottle A according to a certain volume ratio, adding an appropriate amount of aniline solution, stirring under a magnetic force condition until white precipitates are dissolved, uniformly mixing water and hydrochloric acid into a second small bottle B, adding aniline solution, carrying out ultrasonic treatment until a clear solution is obtained, and dissolving a certain amount of ammonium persulfate into an appropriate amount of water in a third small bottle C.
Step four: weighing a certain mass of bamboo-based activated carbon powder, adding the bamboo-based activated carbon powder into a first small bottle A, stirring to be uniform, wherein the adding amount of the carbon powder is 0.1-0.5%, cooling the solution in the three small bottles to 4 ℃, mixing the solutions in the small bottles A and B after one hour, stirring for 10 seconds, immediately adding the solution in the small bottle C into the mixture, stirring for 10 seconds, rapidly gelling the solution within 3min, keeping the solution at 4 ℃ without stirring for reaction for 12 hours, and after the reaction is finished, soaking and washing with a large amount of deionized water until the pH of supernatant is neutral.
Step five: and (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
The further preferable scheme of the invention is as follows: in the activation stage of the bamboo charcoal powder, the activation temperature is between 700 and 900 ℃.
The further preferable scheme of the invention is as follows: after the phytic acid solution and the aniline are mixed, the phytic acid solution and the aniline are fully mixed under the action of magnetic stirring, and the precipitate is completely dissolved.
The further preferable scheme of the invention is as follows: the hydrochloric acid solution was mixed with aniline and sonicated to obtain a clear solution, with the aniline being completely protonated by the hydrochloric acid.
The further preferable scheme of the invention is as follows: the addition amount of the bamboo-based activated carbon powder is 0.1-0.5%.
The invention provides a preparation method of a polyaniline aerogel/bamboo-based activated carbon composite material, which is characterized in that phytic acid and hydrochloric acid are co-doped, so that the conductivity of the polyaniline aerogel is improved, the hierarchical porous 3D network structure of the aerogel is ensured, the polyaniline aerogel and the bamboo-based activated carbon are compounded with the bamboo-based activated carbon, the defects and the defects of the polyaniline aerogel and the bamboo-based activated carbon which are independently used as a super capacitor are overcome, and the composite material has the excellent characteristics of double electric layer capacitance and pseudocapacitance.
Drawings
Fig. 1 is a macroscopic photograph of the polyaniline aerogel/bamboo-based activated carbon composite material prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Micrograph (SEM) of the bamboo-based activated carbon prepared in example 1 of the present invention.
Fig. 3 is a Scanning Electron Micrograph (SEM) of the polyaniline aerogel prepared in example 1 of the present invention.
Fig. 4 is a Scanning Electron Microscope (SEM) photograph of the polyaniline aerogel/bamboo-based activated carbon composite material prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
Cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks by using deionized water, drying the bamboo blocks in an oven at the temperature of 80 ℃ for 24 hours, then placing the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the carbonization temperature at 800 ℃ for 2 hours, crushing the carbonized bamboo charcoal by using a ball mill, and sieving the crushed bamboo charcoal with a 200-mesh sieve.
Weighing a certain mass of bamboo charcoal and potassium hydroxide according to an alkali-carbon ratio of 4:1, placing the bamboo charcoal and the potassium hydroxide in a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 800 ℃ at a certain heating speed, preserving heat for 3 hours, then cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
Molar ratio of Aniline to ammonium persulfate 4:1 3 mL of water and 0.5 mL of Aniline were mixed in a first vial "A" and 1.26 mL of phytic acid (aqueous solution, 50 wt%) was added under magnetic stirring until the white precipitate dissolved, 3 mL of water and 0.5 mL of Aniline were mixed in a second vial "B" and 2.75 mL of 2 mol. L was added-1Hydrochloric acid, sonicated until a clear solution is obtained, 0.615 g of ammonium persulfate was taken up in 2 mL of water in a third vial "C".
Weighing a certain mass of bamboo-based activated carbon powder (the content of the carbon powder is 0.1%), adding the bamboo-based activated carbon powder into a first bottle A, stirring to be uniform, cooling the solution in the three bottles to 4 ℃, mixing the solutions in the bottles A and B after one hour, stirring for 10 seconds, immediately adding the solution in the bottle C into the mixture, stirring for 10 seconds again, quickly gelling the solution within 3min, keeping the solution at 4 ℃ without stirring for 12 hours, and after the reaction is finished, soaking and washing with a large amount of deionized water until the pH of the supernatant is neutral.
And (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
As shown in the macroscopic photograph of the attached FIG. 1, the composite aerogel prepared by the method is dark green and blocky.
Figure 2 is an SEM photograph of the bamboo-based activated carbon obtained from the preparation of example 1, and it can be seen from the picture that the product still has some intact channels in the micron order.
Fig. 3 is an SEM photograph of the polyaniline aerogel prepared in example 1, from which it can be seen that the product has a 3D network porous structure.
Fig. 4 is an SEM picture of the polyaniline aerogel/bamboo-based activated carbon composite prepared in example 1, from which it can be seen that the bamboo-based activated carbon is coated with the polyaniline aerogel.
Example 2
Cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks by using deionized water, drying the bamboo blocks in an oven at the temperature of 80 ℃ for 24 hours, then placing the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the carbonization temperature at 800 ℃ for 2 hours, crushing the carbonized bamboo charcoal by using a ball mill, and sieving the crushed bamboo charcoal with a 200-mesh sieve.
Weighing a certain mass of bamboo charcoal and potassium hydroxide according to an alkali-carbon ratio of 4:1, placing the bamboo charcoal and the potassium hydroxide in a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 700 ℃ at a certain heating speed, preserving heat for 2 hours, then cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
Molar ratio of Aniline to ammonium persulfate 4:1 3 mL of water and 0.5 mL of Aniline were mixed in a first vial "A" and 1.26 mL of phytic acid (aqueous solution, 50 wt%) was added under magnetic stirring until the white precipitate dissolved, 3 mL of water and 0.5 mL of Aniline were mixed in a second vial "B" and 2.75 mL of 2 mol. L was added-1Hydrochloric acid, sonicated until a clear solution is obtained, in a third vial "C", 0.615 g of ammonium persulfate are taken in solutionDissolved in 2 mL of water.
Weighing a certain mass of bamboo-based activated carbon powder (the content of the carbon powder is 0.2%), adding the bamboo-based activated carbon powder into a first small bottle A, stirring to be uniform, cooling the solution in the three small bottles to 4 ℃, mixing the solutions in the small bottles A and B after one hour, stirring for 10 seconds, immediately adding the solution in the small bottle C into the mixture, stirring for 10 seconds again, quickly gelling the solution within 3min, keeping the temperature at 4 ℃ for 12 hours without stirring, and after the reaction is finished, soaking and washing with a large amount of deionized water until the pH of the supernatant is neutral.
And (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
Example 3
Cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks by using deionized water, drying the bamboo blocks in an oven at the temperature of 80 ℃ for 24 hours, then placing the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the carbonization temperature at 800 ℃ for 2 hours, crushing the carbonized bamboo charcoal by using a ball mill, and sieving the crushed bamboo charcoal with a 200-mesh sieve.
Weighing a certain mass of bamboo charcoal and potassium hydroxide according to an alkali-carbon ratio of 4:1, placing the bamboo charcoal and the potassium hydroxide in a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 900 ℃ at a certain heating speed, preserving heat for 2 hours, then cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
Aniline to ammonium persulfate molar ratio of 4:1, 3 mL of water and 0.5 mL of aniline in a first vial "A" were mixed and 1.26 mL of phytic acid (aqueous solution, 50 wt%) was added under magnetic stirring until the white precipitate dissolved, 3 mL of water and 0.5 mL of aniline in a second vial "B" were mixed and 2.75 mL of aniline at a concentration of 2 mol. L was added-1Hydrochloric acid, sonicated until a clear solution is obtained, 0.615 g of ammonium persulfate was taken up in 2 mL of water in a third vial "C".
Weighing a certain mass of bamboo-based activated carbon powder (the content of the carbon powder is 0.3%), adding the bamboo-based activated carbon powder into the first small bottle A, and stirring to be uniform. The solutions in the three vials were cooled to 4 ℃ and one hour later, the solutions in vials a and B were mixed and stirred for 10 seconds, then immediately the solution in vial C was added to the above mixture and stirred for another 10 seconds, the solution rapidly gelled within 3min and then left unstirred at 4 ℃ for 12 hours, after the reaction was complete, rinsed with copious amounts of deionized water until the supernatant pH was neutral.
And (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
Example 3
Cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks with deionized water, drying the bamboo blocks in an oven at 80 ℃ for 24 hours, putting the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the carbonization temperature at 800 ℃ and preserving the heat for 2 hours. And crushing the carbonized bamboo charcoal by using a ball mill and sieving by using a 200-mesh sieve.
Weighing a certain mass of bamboo charcoal and potassium hydroxide according to an alkali-carbon ratio of 4:1, placing the bamboo charcoal and the potassium hydroxide in a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 800 ℃ at a certain heating speed, preserving heat for 2 hours, then cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
Molar ratio of Aniline to ammonium persulfate 4:1 3 mL of water and 0.5 mL of Aniline were mixed in a first vial "A" and 1.26 mL of phytic acid (aqueous solution, 50 wt%) was added under magnetic stirring until the white precipitate dissolved, 3 mL of water and 0.5 mL of Aniline were mixed in a second vial "B" and 2.75 mL of 2 mol. L was added-1Hydrochloric acid, sonicated until a clear solution is obtained, 0.615 g of ammonium persulfate was taken up in 2 mL of water in a third vial "C".
Weighing a certain mass of bamboo-based activated carbon powder (the content of the carbon powder is 0.4%), adding the bamboo-based activated carbon powder into a first small bottle A, stirring to be uniform, cooling the solution in the three small bottles to 4 ℃, mixing the solutions in the small bottles A and B after one hour, stirring for 10 seconds, immediately adding the solution in the small bottle C into the mixture, stirring for 10 seconds again, quickly gelling the solution within 3min, keeping the temperature at 4 ℃ for 12 hours without stirring, and after the reaction is finished, soaking and washing with a large amount of deionized water until the pH of the supernatant is neutral.
And (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
Example 5
Cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks by using deionized water, drying the bamboo blocks in an oven at the temperature of 80 ℃ for 24 hours, then placing the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the carbonization temperature at 800 ℃ for 2 hours, crushing the carbonized bamboo charcoal by using a ball mill, and sieving the crushed bamboo charcoal with a 200-mesh sieve.
Weighing a certain mass of bamboo charcoal and potassium hydroxide according to an alkali-carbon ratio of 4:1, placing the bamboo charcoal and the potassium hydroxide in a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 800 ℃ at a certain heating speed, preserving heat for 2 hours, then cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
Molar ratio of Aniline to ammonium persulfate 4:1 3 mL of water and 0.5 mL of Aniline were mixed in a first vial "A" and 1.26 mL of phytic acid (aqueous solution, 50 wt%) was added under magnetic stirring until the white precipitate dissolved, 3 mL of water and 0.5 mL of Aniline were mixed in a second vial "B" and 2.75 mL of 2 mol. L was added-1Hydrochloric acid, sonicated until a clear solution is obtained, 0.615 g of ammonium persulfate was taken up in 2 mL of water in a third vial "C".
Weighing a certain mass of bamboo-based activated carbon powder (the content of the carbon powder is 0.2%), adding the bamboo-based activated carbon powder into a first small bottle A, stirring to be uniform, cooling the solution in the three small bottles to 4 ℃, mixing the solutions in the small bottles A and B after one hour, stirring for 10 seconds, immediately adding the solution in the small bottle C into the mixture, stirring for 10 seconds again, quickly gelling the solution within 3min, keeping the temperature at 4 ℃ for 12 hours without stirring, and after the reaction is finished, soaking and washing with a large amount of deionized water until the pH of the supernatant is neutral.
And (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. The preparation method of the polyaniline aerogel/bamboo-based activated carbon composite material comprises the following steps:
the method comprises the following steps: the bamboo charcoal is prepared by cutting bamboo joints with a certain length into bamboo blocks with equal length along the axial direction, cleaning the bamboo blocks with deionized water, drying the bamboo blocks in an oven at 80 ℃ for 24 hours, putting the bamboo blocks with a certain mass in a porcelain boat, moving the porcelain boat into a medium carbonization furnace for carbonization treatment, keeping the temperature at 800 ℃ for 2-4 hours, crushing the carbonized bamboo charcoal with a ball mill, and sieving the crushed bamboo charcoal with a 200-mesh sieve.
2. Step two: the preparation method of the bamboo-based activated carbon comprises the steps of weighing bamboo charcoal and potassium hydroxide according to a certain alkali-carbon ratio, placing the bamboo charcoal and the potassium hydroxide into a nickel crucible, transferring the nickel crucible into an activation furnace, heating to an activation temperature of 700-900 ℃ at a certain heating speed, keeping the temperature for 2-4 hours, cooling to room temperature, repeatedly washing an activated product to be neutral by using dilute hydrochloric acid and distilled water, carrying out suction filtration, and placing the suction filtration product in a vacuum oven at 80 ℃ for drying for 12 hours to obtain a final product.
3. Step three: the preparation method comprises the steps of preparing a polyaniline aerogel/bamboo-based activated carbon composite material, wherein the molar ratio of aniline to ammonium persulfate is 2: 1-4: 1, adding water and phytic acid solution into a first small bottle A according to a certain volume ratio, adding a proper amount of aniline solution, stirring under a magnetic force state until white precipitates are dissolved, uniformly mixing a certain amount of water and hydrochloric acid into a second small bottle B, adding aniline solution, carrying out ultrasonic treatment until a clear solution is obtained, and dissolving a certain amount of ammonium persulfate into water in a third small bottle C.
4. Step four: weighing a certain mass of bamboo-based activated carbon powder, adding the bamboo-based activated carbon powder into a first small bottle A, stirring to be uniform, wherein the adding amount of the carbon powder is 0.1-0.5%, cooling the solution in the three small bottles to 4 ℃, mixing the solutions in the small bottles A and B after one hour, stirring for 10 seconds, immediately adding the solution in the small bottle C into the mixture, stirring for 10 seconds, rapidly gelling the solution within 3min, keeping the solution at 4 ℃ without stirring for reaction for 12 hours, and after the reaction is finished, soaking and washing with a large amount of deionized water until the pH of supernatant is neutral.
5. Step five: and (3) freezing the soaked and washed composite material in a refrigerator at the temperature of-20 ℃ for 12h, then drying the composite material in a vacuum freeze dryer for 72h, and removing water in the aerogel to obtain the polyaniline aerogel/bamboo-based activated carbon composite material.
6. The method as claimed in claim 1, wherein the first stage of the bamboo-based activated carbon preparation process is bamboo charcoal preparation.
7. The method as claimed in claim 1, wherein the second stage of the bamboo-based activated carbon preparation is activation of bamboo charcoal.
8. The preparation method of claim 1, wherein the activation temperature of the bamboo charcoal is 700-900 ℃.
9. The preparation method according to claim 1, wherein the heat preservation time is 2-4 h when the bamboo charcoal is activated.
10. The preparation method of claim 1, wherein the preparation of the polyaniline aerogel/bamboo-based activated carbon composite material is carried out in an environment of 4 ℃ and the reaction time is 12 hours.
11. The preparation method according to claim 1, wherein the molar ratio of aniline to ammonium persulfate is 2: 1-4: 1.
12. The method according to claim 1, wherein the amount of the bamboo-based activated carbon added is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134318A (en) * | 2011-01-14 | 2011-07-27 | 陈晓红 | Method for preparing bamboo charcoal/polyaniline composite material by adopting bamboo charcoal |
| CN106145283A (en) * | 2015-04-02 | 2016-11-23 | 北京化工大学 | The bamboo matrix activated carbon being applied in capacitance method desalting technology and material modified preparation thereof and test |
| CN106298284A (en) * | 2016-09-11 | 2017-01-04 | 桂林理工大学 | A kind of preparation method of electrically conductive polyaniline/graphene oxide composite electrode material |
-
2018
- 2018-11-16 CN CN201811365545.7A patent/CN111199836A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134318A (en) * | 2011-01-14 | 2011-07-27 | 陈晓红 | Method for preparing bamboo charcoal/polyaniline composite material by adopting bamboo charcoal |
| CN106145283A (en) * | 2015-04-02 | 2016-11-23 | 北京化工大学 | The bamboo matrix activated carbon being applied in capacitance method desalting technology and material modified preparation thereof and test |
| CN106298284A (en) * | 2016-09-11 | 2017-01-04 | 桂林理工大学 | A kind of preparation method of electrically conductive polyaniline/graphene oxide composite electrode material |
Non-Patent Citations (1)
| Title |
|---|
| A. KHOSROZADEH等: ""A high-capacitance solid-state supercapacitor based on free-standing film of polyaniline and carbon particles"", 《APPLIED ENERGY》 * |
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