CN117153573B - Graphene reinforced aluminum-based supercapacitor current collector and preparation method thereof - Google Patents
Graphene reinforced aluminum-based supercapacitor current collector and preparation method thereof Download PDFInfo
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
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- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 8
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- 238000003825 pressing Methods 0.000 claims description 8
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Abstract
The invention relates to the technical field of capacitors and discloses a graphene reinforced aluminum-based supercapacitor current collector and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a graphene reinforced aluminum-based supercapacitor current collector and a preparation method thereof.
Background
The super capacitor has the advantages of high power density, long cycle life and the like, and is an electrochemical energy storage device with wide application. The metal aluminum has rich reserves, low cost and good safety and reliability, is a current collector material widely used by the existing super capacitor, has low specific capacitance and poor multiplying power performance, and prevents the development and application of the super capacitor.
The graphene has the advantages of high specific surface area, high strength and good conductivity, and can provide a buffer space for volume change for the electrode material, so that the graphene has wide application prospects in the aspects of super capacitor current collectors and electrode materials. However, graphene is easy to agglomerate, the specific surface area can be reduced, and the transmission of electrons in the charge and discharge processes of the capacitor is affected, so that the specific capacitance is reduced.
The porous carbon material has rich pore canal structure, excellent conductivity and high electron and ion transmission efficiency; however, the actual specific capacitance of the porous carbon material is low, and the current method for improving the specific capacitance of the porous carbon material mainly comprises methods of heteroatom doping, metal oxide compounding and the like; the invention aims to in-situ compound graphene and sulfur/phosphorus doped porous carbon to obtain the aluminum-based supercapacitor current collector material with large specific capacitance and good rate capability.
Disclosure of Invention
The invention solves the following technical problems: the graphene and sulfur/phosphorus doped porous carbon are compounded in situ, so that the problems of lower specific capacitance and poor multiplying power performance of the traditional aluminum-based supercapacitor current collector are solved.
The technical scheme of the invention is as follows:
a preparation method of a graphene reinforced aluminum-based supercapacitor current collector comprises the following steps:
step one: washing the aluminum foil with a sodium hydroxide solution with the mass fraction of 4% and water, adding the washed aluminum foil into a chemical etching solution, carrying out chemical etching, taking out the aluminum foil, washing with water, drying, and cutting into wafers to obtain an aluminum foil current collector;
step two: graphene oxide, benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate) are treated) Adding into dimethyl sulfoxide, stirring for 6-12 hr, and adding pentaerythritol spiro phosphoryl dichloride (herba Lespedezae Cuneatae)>) Reacting for 36-72h in the nitrogen atmosphere at 30-50 ℃, filtering, washing with water and ethanol, and drying to obtain the porous polymer coated graphene;
step three: carbonizing porous polymer coated graphene in a resistance furnace at 750-900 ℃ for 2-3h in nitrogen atmosphere to obtain porous carbon coated graphene;
step four: adding the porous carbon coated graphene, the conductive agent and the binder into ethanol according to the ratio of 8:1:1, stirring to be sticky, coating the sticky on the surface of an aluminum foil current collector, and pressing the sticky on a tablet press to obtain the graphene reinforced aluminum-based supercapacitor current collector.
Further, the mass fraction of HCl in the chemical etching solution in the first step is 5-8%, H 2 SO 4 Is 1-3% of Al by mass 2 (SO 4 ) 3 The mass fraction of (3-6%).
Further, the chemical etching temperature in the first step is 15-35 ℃ and the chemical etching time is 30-90 s.
Further, in the step two, the mass of benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate), pentaerythritol spiro phosphoryl dichloride and pyridine are (180-400)%, (220-550)% and (60-150)% of the mass of graphene oxide in sequence.
Further, the preparation method of the benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate) comprises the following steps: adding 5-nitrothiophene-2-formic acid, phloroglucinol and p-toluenesulfonic acid into toluene, carrying out reflux reaction for 18-36h at 110-125 ℃, carrying out reduced pressure distillation, washing with acetone, placing the crude product into a reaction kettle, adding methanol and Pd/C catalyst, introducing hydrogen into the reaction kettle, reacting for 1-3h at room temperature, filtering, carrying out reduced pressure distillation on the filtrate, washing with water and acetone, and drying to obtain benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate). The preparation reaction route is as follows:
further, the dosages of the 5-nitrothiophene-2-formic acid and the p-toluenesulfonic acid are respectively 420-560% and 14-20% of the weight of the phloroglucinol.
Further, the solvent is toluene or xylene.
Further, the flow rate of the hydrogen is 5-10 mL/min, and the pressure of the introduced hydrogen into the reaction kettle is controlled to be 0.1-0.2 MPa.
Further, the loading amount of the porous carbon coated graphene on the surface of the aluminum foil current collector in the fourth step is 5-15mg/cm 2 。
The beneficial technical effects of the invention are as follows: (1) Utilizing hydroxyl and carboxyl on the surface of graphene oxide to generate hydrogen bond interaction with amino and ester oxygen atoms of benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate) so as to realize in-situ modification of the graphene oxide; further, the triamino contained in benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate) and pentaerythritol spirophosphoryl dichloride are subjected to polymerization reaction on the surface of graphene oxide to obtain porous polymer coated graphene, so that the graphene is uniformly loaded into the porous polymer, and finally, sulfur/phosphorus doped porous carbon coated graphene is obtained through high-temperature carbonization, so that the graphene is uniformly dispersed in the porous carbon, the dispersibility of graphene nanoparticles is improved, and the agglomeration of the graphene nanoparticles is reduced.
(2) According to the invention, the porous carbon coated graphene, the conductive agent and the adhesive are coated on the surface of the aluminum foil current collector to prepare the graphene reinforced aluminum-based supercapacitor current collector, the porous carbon coated graphene has a high specific surface area, the contact area between an electrode and an electrolyte interface is increased, the transmission path of electrolyte ions is shortened in the charging and discharging process of the capacitor, and meanwhile, rich reactive sites are provided for electrochemical reaction, so that the charge storage density and the energy density of the supercapacitor are improved. And after the porous carbon is doped with sulfur and phosphorus elements, the specific surface area, the electrolyte wettability and the electron conduction capacity of the porous carbon can be improved, and the actual specific capacitance and the multiplying power performance of the supercapacitor are obviously improved.
Drawings
Fig. 1 is a CV curve of a graphene-reinforced aluminum-based supercapacitor current collector prepared in example 2 at different scan rates.
Fig. 2 is a constant current charge-discharge curve of the graphene-reinforced aluminum-based supercapacitor current collector prepared in example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Washing aluminum foil with 4% sodium hydroxide solution and water, adding into chemical etching solution, wherein the mass fraction of HCl in the chemical etching solution is 6%, and the mass fraction of H is 2 SO 4 Is 2% of Al by mass 2 (SO 4 ) 3 The mass fraction of the aluminum foil is 4%, the aluminum foil is subjected to chemical corrosion at 35 ℃ for 30 s, the aluminum foil is taken out, washed with water, dried and cut into wafers, and the aluminum foil current collector is prepared;
420mg of 5-nitrothiophene-2-carboxylic acid, 100mg of phloroglucinol and 14mg of p-toluenesulfonic acid are added into 10mL of toluene, reflux reaction is carried out for 24h at 120 ℃, reduced pressure distillation and acetone washing are carried out, the crude product is placed into a reaction kettle, 30mL methanol and 60mg Pd/C catalyst are added, hydrogen with the flow rate of 5 mL/min is introduced into the reaction kettle, the pressure of the reaction kettle is controlled to be 0.1 MPa, room temperature reaction is carried out for 2h, the filtrate is subjected to reduced pressure distillation after filtration, and is washed by water and acetone and dried, thus obtaining benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylic ester).
Adding 50mg graphene oxide and 90mg benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate) into 20mL dimethyl sulfoxide, stirring for 12h, then adding 110mg pentaerythritol spiro phosphoryl dichloride and 30mg pyridine, reacting at 40 ℃ for 48h under nitrogen atmosphere, filtering, washing with water and ethanol, and drying to obtain porous polymer coated graphene;
carbonizing porous polymer coated graphene in a resistance furnace at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain porous carbon coated graphene;
adding porous carbon coated graphene, conductive agent acetylene black and binder polyvinylidene fluoride into ethanol according to the mass ratio of 8:1:1, stirring to be sticky, coating the sticky mixture on the surface of an aluminum foil current collector, and controlling a porous carbon coating on the surface of the aluminum foil current collectorThe loading of the graphene coating is 10mg/cm 2 And pressing by a tablet press to obtain the graphene reinforced aluminum-based supercapacitor current collector.
Example 2
Washing aluminum foil with 4% sodium hydroxide solution and water, adding into chemical etching solution with HCl mass fraction of 8% and H 2 SO 4 Is 2% of Al by mass 2 (SO 4 ) 3 The mass fraction of the aluminum foil is 6%, chemical corrosion is carried out at 15 ℃ for 90 s, the aluminum foil is taken out, washed with water, dried and cut into wafers, and the aluminum foil current collector is prepared;
560mg of 5-nitrothiophene-2-carboxylic acid, 100mg of phloroglucinol and 20mg of p-toluenesulfonic acid are added into 20mL of toluene, reflux reaction is carried out for 36h at 110 ℃, reduced pressure distillation and acetone washing are carried out, the crude product is placed into a reaction kettle, 20mL methanol and 50mg of Pd/C catalyst are added, hydrogen with the flow rate of 5 mL/min is introduced into the reaction kettle, the pressure of the reaction kettle is controlled to be 0.15 MPa, room temperature reaction is carried out for 1h, the filtrate is subjected to reduced pressure distillation after filtration, washing with water and acetone is carried out, and drying is carried out, thus obtaining the benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylic acid ester).
Adding 50mg graphene oxide and 120mg of benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate) into 30mL of dimethyl sulfoxide, stirring for 12h, then adding 150mg of pentaerythritol spiro phosphoryl dichloride and 38mg of pyridine, reacting for 48h at 50 ℃ in a nitrogen atmosphere, filtering, washing with water and ethanol, and drying to obtain porous polymer coated graphene;
carbonizing porous polymer coated graphene in a resistance furnace at 800 ℃ for 3 hours in nitrogen atmosphere to obtain porous carbon coated graphene;
adding porous carbon coated graphene, conductive agent acetylene black and binder polyvinylidene fluoride into ethanol according to the mass ratio of 8:1:1, stirring to be sticky, coating the sticky mixture on the surface of an aluminum foil current collector, and controlling the loading amount of the porous carbon coated graphene on the surface of the aluminum foil current collector to be 10mg/cm 2 And pressing by a tablet press to obtain the graphene reinforced aluminum-based supercapacitor current collector.
Example 3
Dividing aluminum foil by massWashing with 4% sodium hydroxide solution and water, adding into chemical etching solution with HCl mass fraction of 5% and H 2 SO 4 3% by mass of Al 2 (SO 4 ) 3 The mass fraction of the aluminum foil is 4%, the aluminum foil is subjected to chemical corrosion at 20 ℃ for 60 s, the aluminum foil is taken out, washed with water, dried and cut into wafers, and the aluminum foil current collector is prepared;
560mg of 5-nitrothiophene-2-carboxylic acid, 100mg of phloroglucinol and 20mg of p-toluenesulfonic acid are added into 15mL of toluene, reflux reaction is carried out for 18h at 120 ℃, reduced pressure distillation and acetone washing are carried out, the crude product is placed into a reaction kettle, 30mL methanol and 60mg Pd/C catalyst are added, 8 mL/min hydrogen is introduced into the reaction kettle, the pressure of the reaction kettle is controlled to be 0.1 MPa, room temperature reaction is carried out for 2h, the filtrate is subjected to reduced pressure distillation after filtration, washing with water and acetone is carried out, and drying is carried out, thus obtaining the benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylic acid ester).
Adding 50mg graphene oxide and 150mg of benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate) into 40mL of dimethyl sulfoxide, stirring for 8h, then adding 210mg of pentaerythritol spiro phosphoryl dichloride and 65mg of pyridine, reacting at 50 ℃ for 72h under nitrogen atmosphere, filtering, washing with water and ethanol, and drying to obtain porous polymer coated graphene;
carbonizing porous polymer coated graphene in a resistance furnace at 800 ℃ for 3 hours in nitrogen atmosphere to obtain porous carbon coated graphene;
adding porous carbon coated graphene, conductive agent acetylene black and binder polyvinylidene fluoride into ethanol according to the mass ratio of 8:1:1, stirring to be sticky, coating the sticky mixture on the surface of an aluminum foil current collector, and controlling the loading amount of the porous carbon coated graphene on the surface of the aluminum foil current collector to be 10mg/cm 2 And pressing by a tablet press to obtain the graphene reinforced aluminum-based supercapacitor current collector.
Example 4
Washing aluminum foil with 4% sodium hydroxide solution and water, adding into chemical etching solution, wherein the mass fraction of HCl in the chemical etching solution is 6%, and H is 2 SO 4 Is 1% by mass of Al 2 (SO 4 ) 3 Mass fraction of (2)At 5%, and at 20 ℃, carrying out chemical corrosion on the aluminum foil at 60 s, taking out the aluminum foil, washing the aluminum foil with water, drying the aluminum foil, and cutting the aluminum foil into wafers to prepare an aluminum foil current collector;
500mg of 5-nitrothiophene-2-carboxylic acid, 100mg of phloroglucinol and 18mg of p-toluenesulfonic acid are added into 20mL of toluene, reflux reaction is carried out for 36h at 110 ℃, reduced pressure distillation and acetone washing are carried out, the crude product is placed into a reaction kettle, 30mL methanol and 70 mg Pd/C catalyst are added, hydrogen with the flow rate of 5 mL/min is introduced into the reaction kettle, the pressure of the reaction kettle is controlled to be 0.1 MPa, room temperature reaction is carried out for 1h, the filtrate is subjected to reduced pressure distillation after filtration, and is washed by water and acetone and dried, thus obtaining benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylic ester).
Adding 50mg graphene oxide and 200mg benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate) into 40mL dimethyl sulfoxide, stirring for 12h, then adding 275mg pentaerythritol spiro phosphoryl dichloride and 75mg pyridine, reacting at 40 ℃ for 72h under nitrogen atmosphere, filtering, washing with water and ethanol, and drying to obtain porous polymer coated graphene;
carbonizing porous polymer coated graphene in a resistance furnace at 750 ℃ for 3 hours in nitrogen atmosphere to obtain porous carbon coated graphene;
adding porous carbon coated graphene, conductive agent acetylene black and binder polyvinylidene fluoride into ethanol according to the mass ratio of 8:1:1, stirring to be sticky, coating the sticky mixture on the surface of an aluminum foil current collector, and controlling the loading amount of the porous carbon coated graphene on the surface of the aluminum foil current collector to be 10mg/cm 2 And pressing by a tablet press to obtain the graphene reinforced aluminum-based supercapacitor current collector.
Comparative example 1
Adding graphene oxide, an electric conduction agent acetylene black and a binder polyvinylidene fluoride into ethanol according to a mass ratio of 8:1:1, stirring to be sticky, coating the sticky mixture on the surface of an aluminum foil current collector, and controlling the loading amount of porous carbon coated graphene on the surface of the aluminum foil current collector to be 10mg/cm 2 And pressing by a tablet press to obtain the graphene reinforced aluminum-based supercapacitor current collector.
Comparative example 2
90mg of benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate), 110mg of pentaerythritol spiro phosphoryl dichloride and 38mg of pyridine are added into 20mL of dimethyl sulfoxide, reacted for 48 hours at 40 ℃ under the nitrogen atmosphere, filtered, washed with water and ethanol and dried to prepare a porous polymer;
carbonizing porous polymer coated graphene in a resistance furnace at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain porous carbon;
adding porous carbon, conductive agent acetylene black and binder polyvinylidene fluoride into ethanol according to the mass ratio of 8:1:1, stirring to be sticky, coating the sticky mixture on the surface of an aluminum foil current collector, and controlling the loading amount of the porous carbon coated graphene on the surface of the aluminum foil current collector to be 10mg/cm 2 Pressing by a tablet press to obtain the aluminum-based super capacitor current collector.
And assembling a supercapacitor sample with the aluminium-based supercapacitor current collector in a vacuum glove box by taking a polytetrafluoroethylene microporous membrane as a diaphragm and 1 mol/L sodium sulfate as electrolyte. The electrochemical impedance spectrum of the supercapacitor sample is tested by adopting an electrochemical workstation, and the test range is 0.01-1000 Hz. And testing the capacitor charging and discharging performance and the multiplying power performance by adopting a supercapacitor tester.
TABLE 1 super capacitor rate capability test
The graphene reinforced aluminum-based supercapacitor current collector and supercapacitor prepared in the embodiment 2 have specific capacitance of 303.1F/g under the current density of 0.5A/g; a specific capacitance of 276.6F/g at a current density of 1A/g; at a current density of 3A/g, the specific capacitance reached 230.5F/g.
Fig. 1 is a CV curve of the graphene reinforced aluminum-based supercapacitor current collector prepared in example 2 at different scanning rates, and the graphene reinforced aluminum-based supercapacitor current collector has a rectangular shape at a large scanning rate, and has a good double-layer capacitance effect. The constant current charge-discharge curve of fig. 2 shows that the charge-discharge curve has a triangular shape at different current densities, and also exhibits an electric double layer capacitance effect.
Claims (4)
1. The preparation method of the graphene reinforced aluminum-based supercapacitor current collector is characterized by comprising the following steps of:
step one: washing the aluminum foil with sodium hydroxide solution and water, adding the washed aluminum foil into a chemical etching solution, performing chemical etching, taking out the aluminum foil, washing, drying, and cutting into wafers to prepare an aluminum foil current collector;
step two: adding graphene oxide and benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate) into dimethyl sulfoxide, stirring for 6-12h, and then adding pentaerythritol spiro phosphoryl dichloride and pyridine, wherein the mass of the benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate), the pentaerythritol spiro phosphoryl dichloride and the pyridine are (180-400)%, (220-550)% and (60-150)% of the mass of the graphene oxide in sequence; reacting for 36-72h at 30-50 ℃ in nitrogen atmosphere, filtering, washing and drying to obtain the porous polymer coated graphene;
the benzene-1, 3, 5-tris (5-aminothiophene-2-carboxylate) has the following structural formula:
；
step three: carbonizing porous polymer coated graphene in a resistance furnace at 750-900 ℃ for 2-3h in nitrogen atmosphere to obtain porous carbon coated graphene;
step four: adding porous carbon coated graphene, a conductive agent and a binder into ethanol, stirring to be sticky, coating the sticky on the surface of an aluminum foil current collector, and pressing the sticky with a tablet press to obtain a graphene reinforced aluminum-based supercapacitor current collector;
the preparation method of the benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate) comprises the following steps: adding 5-nitrothiophene-2-formic acid, phloroglucinol and p-toluenesulfonic acid into toluene or xylene solvent, wherein the dosage of the 5-nitrothiophene-2-formic acid and the p-toluenesulfonic acid is (420-560)% and (14-20)% of the mass of the phloroglucinol in sequence; reflux-reacting at 110-125 deg.c for 18-36 hr, decompressing, distilling, washing, adding coarse product into reaction kettle, adding methanol and Pd/C catalyst, introducing hydrogen into the reaction kettle at 5-10 mL/min and 0.1-0.2 MPa; reacting for 1-3h at room temperature, filtering, decompressing, distilling, washing and drying filtrate to obtain benzene-1, 3, 5-tri (5-aminothiophene-2-carboxylate).
2. The preparation method of the graphene reinforced aluminum-based supercapacitor current collector according to claim 1, wherein the mass fraction of HCl in the chemical etching solution in the first step is 5-8%, and the mass fraction of H is 2 SO 4 Is 1-3% of Al by mass 2 (SO 4 ) 3 The mass fraction of (3-6%).
3. The method for preparing the graphene reinforced aluminum-based supercapacitor current collector according to claim 1, wherein the chemical corrosion in the first step is performed at a temperature of 15-35 ℃ for 30-90 s.
4. The preparation method of the graphene reinforced aluminum-based supercapacitor current collector according to claim 1, wherein the loading amount of the porous carbon coated graphene on the surface of the aluminum foil current collector in the fourth step is 5-15mg/cm 2 。
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| CN106252096A (en) * | 2016-08-29 | 2016-12-21 | 刘思志 | A kind of ultracapacitor |
| CN107924768A (en) * | 2015-08-26 | 2018-04-17 | 纳米技术仪器公司 | Porous particle and production method as the interconnection 3D graphenes of electrode of super capacitor active material |
| CN109326455A (en) * | 2018-10-31 | 2019-02-12 | 南京林业大学 | A kind of hydrophily polythiophene grafted graphene oxide electrode material for super capacitor and preparation method thereof |
| CN112758919A (en) * | 2020-12-28 | 2021-05-07 | 西安交通大学 | Nitrogen and sulfur double-doped graphene, preparation method thereof and method for preparing supercapacitor material by using same |
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| CN106252096A (en) * | 2016-08-29 | 2016-12-21 | 刘思志 | A kind of ultracapacitor |
| CN109326455A (en) * | 2018-10-31 | 2019-02-12 | 南京林业大学 | A kind of hydrophily polythiophene grafted graphene oxide electrode material for super capacitor and preparation method thereof |
| CN112758919A (en) * | 2020-12-28 | 2021-05-07 | 西安交通大学 | Nitrogen and sulfur double-doped graphene, preparation method thereof and method for preparing supercapacitor material by using same |
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