CN114694977B - Super-capacitor electrode material and preparation method thereof - Google Patents
Super-capacitor electrode material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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Classifications
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the technical field of super capacitors, in particular to a super capacitor electrode material and a preparation method thereof, wherein the electrode material comprises an inner core and an outer shell, the inner core is an aggregate of an integrated core-shell type nano-load electrode material, the outer shell is a carbonized product obtained by carbonizing an organic carbon source, and the aggregate of the integrated core-shell type nano-load electrode material comprises 15-25% of nano-load electrode active material and 50-80% of modified LaMnO according to weight percentage 3 Perovskite fiber, 1-10% of conductive agent and 1-10% of thickening agent. The super capacitor electrode material provided by the invention has excellent cycle performance, excellent capacitance and stability, and the capacity attenuation rate of a monomer after 1000 hours or 100 ten thousand times of high-temperature load is lower than 10%, and the internal resistance increase rate is lower than 40%.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a super capacitor electrode material and a preparation method thereof.
Background
Supercapacitors are an energy storage device interposed between a conventional capacitor and a battery, and may be classified into an electric double layer type supercapacitor and a pseudo-capacitor type supercapacitor according to the energy storage mechanism. The double-layer super capacitor stores energy by polarizing electrolyte and then utilizing an electric double-layer structure composed of electrodes and electrolyte, and because the energy storage process only generates reversible ion adsorption on two porous electrodes, the double-layer super capacitor can be repeatedly charged and discharged millions of times.
The electrode material is one of key materials for determining the electrical performance of the supercapacitor, and the electrode active materials commonly used for the double-layer supercapacitor mainly comprise active carbon, active carbon fiber, graphene, carbon nano tubes and the like. Wherein, the microstructure of the active carbon and the active carbon fiber contains non-graphitized amorphous carbon components, and the graphene and the carbon nano tube are easy to generate self-agglomeration phenomenon, so that the conductivity of the electrode active materials is lower.
Therefore, in preparing an electrode from an electrode active material, it is generally necessary to add a conductive agent such as metal powder, conductive carbon black, furnace black, acetylene black, ketjen black, or conductive graphite to improve the conductivity of the electrode. For example, chinese patent CN2017103249310 discloses a method for preparing an electrode for a supercapacitor, which uses acid gas soluble in water to demulsify PTFE emulsion added in slurry, so that PTFE spherical particles suspended in the emulsion are demulsified and then stretched into fiber shape, thus obtaining a high-performance supercapacitor electrode with stable coating structure, and through the synergistic effect of colloidal particle-shaped binder and PTFE fiber, the interfacial adhesion between the electrode coating and the current collector is ensured, and the structural stability inside the electrode coating is improved, so that the prepared electrode has better processability, and powder removal is not easy to occur in the processing processes of slitting, winding and the like, thereby improving the high-temperature load reliability and cycle life of the supercapacitor; the electrode material has excellent cycle performance, but has high capacitance and stability, and has high transmission resistance in the charge transfer process, thereby affecting the charge storage performance of the capacitor electrode material.
Disclosure of Invention
The invention aims to provide a super-capacitor electrode material and a preparation method thereof, which not only have excellent cycle performance, but also have obviously improved capacitance and stability, and have smaller transmission resistance in the charge transfer process, so that the charge storage performance of the capacitor electrode material is enhanced.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the electrode material comprises an inner core and an outer shell, wherein the inner core is an aggregate of an integrated core-shell type nano-load electrode material, and the outer shell is a carbonized product obtained by carbonizing an organic carbon source;
the aggregate of the integrated core-shell type nano-load electrode material comprises, by weight, 15-25% of nano-load electrode active material and 50-80% of modified LaMnO 3 Perovskite fiber, 1-10% of conductive agent and 1-10% of thickening agent;
the organic carbon source is at least one selected from glucose, sucrose, citric acid, polyethylene glycol and polyvinyl alcohol.
Further, the preparation method of the nano-supported electrode active material comprises the following steps:
1) Dissolving MCM-22 molecular sieve and sucrose in deionized water, dropwise adding concentrated sulfuric acid, stirring, standing, pre-carbonizing at 160-180 ℃ for 18-25h, transferring the obtained product into a tube furnace, heating to 800-900 ℃ and keeping the temperature for 2-5h, naturally cooling, adding into sodium hydroxide solution, stirring at 70-90 ℃ overnight, repeatedly washing to neutrality after centrifugal separation, and freeze-drying to obtain porous carbon nano-sheets;
2) Dispersing porous carbon nano-sheets in deionized water by ultrasonic wave, and respectively adding K 2 PdCl 4 And CuCl 2 .2H 2 O, dropwise adding NaBH after stirring 4 Stirring vigorously for 1-3h at room temperature, centrifugally cleaning, and drying to obtain pretreated porous carbon nano-sheets;
3) Proper amount of deionized water is measured to dissolve Ni (NO) 3 ) 2 .6H 2 O、Co(NO 3 ) 2 .6H 2 O、NH 4 And (3) preparing a reaction solution by stirring a solution of Cl and urea for 30-50min, placing the pretreated porous carbon nano-sheet in a high-pressure reaction kettle, then adding the stirred reaction solution, reacting for 3-8h at 120-150 ℃, naturally cooling to room temperature, and obtaining the required nano-supported electrode active material after centrifugal separation and drying.
Further, in the step 1), the dosage proportion of the MCM-22 molecular sieve, the sucrose, the deionized water, the concentrated sulfuric acid and the sodium hydroxide solution is 20-50g:14.5-32.2g:60-100mL:1-6mL:200-500mL;
the concentration of the sodium hydroxide solution is 4-6mol/L.
Furthermore, in the step 1), before the tube furnace is used, nitrogen is introduced into the tube furnace for 0.5-1.0h to remove redundant air in the tube.
Further, in the step 2), the porous carbon nano-sheet, deionized water and K 2 PdCl 4 、CuCl 2 .2H 2 O、NaBH 4 The dosage proportion of (2) is 50-100g:3-10L:120-180mL:100-150mL:50-80mL;
the K is 2 PdCl 4 Is 12-16mol/L, cuCl 2 .2H 2 The concentration of O is 4-8mol/L, naBH 4 The concentration of (2) is 0.22-0.28mol/L.
Further, in the step 3), deionized water is 150-300mL and contains 4-10mmol of Ni (NO) 3 ) 2 .6H 2 O, 4-10mmol Co (NO) 3 ) 2 .6H 2 O, 20-40mmol NH 4 Cl and 80-150mmol urea.
Further, the modified LaMnO 3 The preparation method of the perovskite fiber comprises the following steps:
1) Co (NO) 3 ) 2 .6H 2 Dissolving O, 2-methylimidazole in deionized water, rapidly mixing, pouring into a container, and adding LaMnO 3 Placing perovskite fiber in a container, standing at room temperature for 4-10h, repeatedly and alternately washing with deionized water and ethanol, and oven drying to obtain pretreated LaMnO 3 Perovskite fibers;
2) Ni (NO) 3 ) 2 .6H 2 Dissolving O ultrasonic in absolute ethyl alcohol, pretreating LaMnO 3 Immersing perovskite fibers in the prepared solution, standing for 10-15h at room temperature, repeatedly washing with deionized water, and drying to obtain modified LaMnO 3 Perovskite fibers.
Still further, in step 1), the Co (NO) 3 ) 2 .6H 2 O, 2-methylimidazole, deionized water and LaMnO 3 The dosage proportion of the perovskite fiber is 20-40g:50-80g:1.5-3.0L:200-500g.
Still further, in step 2), the Ni (NO) 3 ) 2 .6H 2 The dosage ratio of O to absolute ethyl alcohol is 3-10g:100-180mL.
A method for preparing a supercapacitor electrode material, the method comprising the steps of:
1) Nanometer load electrode active material and modified LaMnO 3 Mixing perovskite fiber, conductive agent and thickener, adding water to adjust viscosity of slurry to 3000-6000cP, filtering the slurry, introducing acid gas with pressure of 0.2-0.8MPa into the filtered slurry, and vacuumizing to obtain slurry；
2) The mass ratio is (1-10): (300-500), dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-supported electrode active material to the organic carbon source to be (80-120): (1-5) granulating at 100-180 ℃ after uniformly mixing, and drying to obtain an electrode material precursor with the particle size of 10-50 mu m;
3) And (3) transferring the electrode material precursor into a rotary furnace, carbonizing at 500-700 ℃ under the protection of inert gas for 3-10h, and obtaining the required super capacitor electrode material.
Still further, the acid gas is selected from at least one of sulfur dioxide, carbon dioxide, and hydrogen sulfide.
Still further, the inert gas is at least one selected from the group consisting of nitrogen, helium, neon, and argon.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, the layered molecular sieve MCM-22 is used as a hard template, sucrose is used as a carbon source, concentrated sulfuric acid is used as a catalyst, and the carbon nano-sheet formed by carbonizing sucrose maintains the porous structure of the molecular sieve template, so that a large number of holes and folds exist in the carbon nano-sheet, on one hand, the carbon nano-sheet has high specific surface area, is beneficial to increasing electrochemical active sites on the surface of a material, and reduces the charge transfer resistance of an electrode, so that the capacitance and stability of the electrode material are improved due to smaller diffusion resistance and larger ion transfer efficiency;
in addition, the porous carbon nano-sheet is used as a carrier, small-size PdCu alloy nano-particles are stably loaded on the carrier at room temperature by a one-step chemical reduction method, and the strong coupling effect between the PdCu alloy nano-particles and the porous carbon nano-sheet of the carrier can be remarkably enhanced by utilizing the abundant defects in the porous carbon nano-sheet, so that the PdCu alloy nano-particles are not easy to fall off, and a large number of raised microspheres are arranged on the surface of the carrier due to the fact that a large number of alloy nano-particles are attached to the surface of the carrier, so that the contact and wetting effect of an electrode surface agent and electrolyte are further increased, the band gap energy of the surface of an electrode material is reduced, the resistance of electrochemical reaction is small, the conductivity is improved, and the electrode material has high capacitance characteristic and good electrochemical stability;
meanwhile, a simple hydrothermal method is adopted, the appearance of the pretreated porous carbon nano sheet is treated by introducing chloride ions, after hydrothermal reaction, the surface of the pretreated porous carbon nano sheet regulated by the chloride ions presents nano wires which grow irregularly, the formed nano wires are small in size, the top ends are crosslinked with each other, the bottom ends have enough space, the migration movement of electrolyte particles is facilitated, more active sites are provided for the electrode reaction, the formed nano wires can also play a role of partition, aggregation and self aggregation of the pretreated porous carbon nano sheet can be prevented, so that the transmission resistance of ions and the like in an electrode material is further reduced, and the charge storage performance of the electrode material is remarkably enhanced.
2. In the invention, the LaMnO is prepared by in-situ growth and sacrificial template etching 3 The perovskite fiber is provided with a two-dimensional nano-sheet array, and Co (OH) is used in the electrochemical activation process of the nano-sheet array 2 The CoOOH can be used as an activation site for cation intercalation to accommodate metal ion intercalation, so that the capacitance of the capacitor device is improved, the capacitor device has high energy density, the capacitor device has ultra-long cycle life and extremely high cycle stability, and the capacitance is hardly attenuated after up to ten thousands of cycles, so that the capacitor device has excellent cycle performance.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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
The electrode material comprises an inner core and an outer shell, wherein the inner core is an aggregate of an integrated core-shell type nano-load electrode material, and the outer shell is a carbonized product obtained by carbonizing glucose;
the aggregate of the integrated core-shell type nano-load electrode material comprises, by weight, 15% of nano-load electrode active material and 80% of modified LaMnO 3 Perovskite fiber, 3% of conductive agent and 2% of thickener.
The preparation method of the nano-supported electrode active material comprises the following steps:
1) 20g of MCM-22 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio of (2) is 27, and 14.5g of sucrose purchased from Nanjing Xianfeng nano materials limited company) is dissolved in 60mL of deionized water, 1mL of concentrated sulfuric acid is added dropwise and stirred for 10 hours at room temperature, the solution is kept still for 3 hours and then is pre-carbonized for 18 hours at 160 ℃, the obtained product is transferred into a tube furnace, nitrogen is introduced for 0.5 hour to remove redundant air in the tube, the temperature is raised to 800 ℃ at the speed of 5 ℃/min, the temperature is kept constant for 2 hours, the natural cooling is carried out, the obtained product is added into 200mL of sodium hydroxide solution with the concentration of 4mol/L, the obtained product is stirred overnight at 70 ℃, and is repeatedly washed to be neutral after centrifugal separation, and the porous carbon nano sheet is obtained after freeze drying;
2) 50g of porous carbon nano-sheet is taken and placed in 3L of deionized water, and is dispersed for 1h by 300W ultrasonic, 120mL of K with the concentration of 12mmol/L is added respectively 2 PdCl 4 And 100mL of CuCl with a concentration of 4mmol/L 2 .2H 2 O, stirring for 20min, and then dropwise adding 50mL of NaBH with the concentration of 0.22mol/L 4 Then stirring vigorously at 1000r/min for 1h at room temperature, respectively centrifugally cleaning three times by using deionized water and ethanol, and drying for 8h in vacuum drying at 60 ℃ to obtain pretreated porous carbon nano-sheets;
3) 150mL of deionized water was measured to dissolve the Ni (NO) containing 4mmol 3 ) 2 .6H 2 O, 4mmol Co (NO) 3 ) 2 .6H 2 O, 20mmol NH 4 Cl and 80mmol urea solution are stirred for 30min, a reaction solution is prepared, the prepared pretreated porous carbon nano-sheet is placed in a high-pressure reaction kettle, then the stirred reaction solution is added for reaction for 3h at 120 ℃, and the reaction solution is naturally cooled to room temperatureTaking out, centrifugally separating, and drying to obtain the required nano-supported electrode active material.
The modified LaMnO 3 The preparation method of the perovskite fiber comprises the following steps:
1) 20gCo (NO) 3 ) 2 .6H 2 O, 50g of 2-methylimidazole were dissolved in 1.5L of deionized water, and the two were rapidly mixed, poured into a container, and 200g of LaMnO was added 3 Placing perovskite fiber in a container, standing at room temperature for 4h, repeatedly and alternately washing with deionized water and ethanol, and drying in oven at 60deg.C for 10h to obtain pretreated LaMnO 3 Perovskite fibers;
2) Will 3gNi (NO) 3 ) 2 .6H 2 O ultrasonic dissolving in 100mL absolute ethanol, pretreating LaMnO 3 Immersing perovskite fibers in the prepared solution, standing for 10 hours at room temperature, repeatedly washing with deionized water, and drying in a 60 ℃ oven for 10 hours to obtain modified LaMnO 3 Perovskite fibers.
A method for preparing a supercapacitor electrode material, the method comprising the steps of:
1) Nanometer load electrode active material and modified LaMnO 3 Mixing perovskite fibers, a conductive agent and a thickening agent, adding water to adjust the viscosity of the slurry to 3000cP, filtering the slurry, introducing acid gas carbon dioxide with the pressure of 0.2MPa into the filtered slurry, and vacuumizing to obtain the slurry;
2) The mass ratio is 1:300, dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-supported electrode active material to the organic carbon source to be 80:1, granulating at 100 ℃ after uniformly mixing, and drying to obtain an electrode material precursor with the particle size of 10 mu m;
3) And (3) transferring the electrode material precursor into a rotary furnace, carbonizing under the protection of inert gas nitrogen, wherein the carbonizing temperature is 500 ℃, and the carbonizing time is 10 hours, so that the required super capacitor electrode material can be obtained.
Example 2
The electrode material comprises an inner core and an outer shell, wherein the inner core is an aggregate of an integrated core-shell type nano-load electrode material, and the outer shell is a carbonized product obtained by carbonizing glucose;
the aggregate of the integrated core-shell type nano-load electrode material comprises, by weight, 15-25% of nano-load electrode active material and 50-80% of modified LaMnO 3 Perovskite fiber, 1-10% of conductive agent and 1-10% of thickening agent.
The preparation method of the nano-supported electrode active material comprises the following steps:
1) 30g of MCM-22 molecular sieve (SiO 2 /Al 2 O 3 The molar ratio of (2) is 27, sucrose which is purchased from Nanjing Xianfeng nano materials Co., ltd.) and 26g are dissolved in 80mL of deionized water, 5mL of concentrated sulfuric acid is added dropwise and stirred at room temperature for 15h, the solution is kept still for 7h and then is carbonized for 20h at 170 ℃, the obtained product is transferred into a tube furnace, nitrogen is introduced for 0.8h to remove redundant air in the tube, the temperature is raised to 850 ℃ at the speed of 8 ℃/min, the temperature is kept constant for 3h, the solution is naturally cooled and then is added into 350mL of sodium hydroxide solution with the concentration of 5mol/L, the solution is stirred at 80 ℃ for overnight, the solution is repeatedly washed to be neutral after centrifugal separation, and the porous carbon nano sheet is obtained after freeze drying;
2) Placing 80g porous carbon nano-sheet in 6L deionized water, performing ultrasonic dispersion for 2h at 400W, and adding 160mL K with concentration of 15mmol/L respectively 2 PdCl 4 And 130mL of CuCl with a concentration of 5mmol/L 2 .2H 2 O, stirring for 30min, and then dropwise adding 70mL of NaBH with the concentration of 0.25mol/L 4 Then stirring vigorously at 2000r/min for 2h at room temperature, centrifugally cleaning for three times by using deionized water and ethanol respectively, and drying for 12h in vacuum drying at 70 ℃ to obtain pretreated porous carbon nano-sheets;
3) 230mL of deionized water was measured to dissolve the Ni (NO) containing 8mmol 3 ) 2 .6H 2 O, 6mmol Co (NO) 3 ) 2 .6H 2 O, 30mmol NH 4 Stirring solution of Cl and 120mmol urea for 40min to obtain reaction solution, placing the prepared pretreated porous carbon nanosheets in a high-pressure reaction kettle, adding the stirred reaction solution, reacting at 135 ℃ for 5h, naturally cooling to room temperature, taking out, centrifuging, separating, and drying to obtain the final productThe electrode active material is nano-supported.
The modified LaMnO 3 The preparation method of the perovskite fiber comprises the following steps:
1) 30gCo (NO) 3 ) 2 .6H 2 O, 70g of 2-methylimidazole were dissolved in 2.5L of deionized water, and the two were rapidly mixed, poured into a container, and 400g of LaMnO was added 3 Placing perovskite fiber in a container, standing at room temperature for 7h, repeatedly and alternately washing with deionized water and ethanol, and drying in a 70 ℃ oven for 13h to obtain pretreated LaMnO 3 Perovskite fibers;
2) Will be 8gNi (NO) 3 ) 2 .6H 2 O ultrasonic dissolving in 150mL absolute ethanol, pretreating LaMnO 3 Immersing perovskite fibers in the prepared solution, standing for 13h at room temperature, repeatedly washing with deionized water, and drying in a 70 ℃ oven for 12h to obtain modified LaMnO 3 Perovskite fibers.
A method for preparing a supercapacitor electrode material, the method comprising the steps of:
1) Nanometer load electrode active material and modified LaMnO 3 Mixing perovskite fibers, a conductive agent and a thickening agent, adding water to adjust the viscosity of the slurry to 5000cP, filtering the slurry, introducing acid gas sulfur dioxide with the pressure of 0.6MPa into the filtered slurry, and vacuumizing to obtain the slurry;
2) The mass ratio is 3:400, dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-supported electrode active material to the organic carbon source to be 100:3, granulating at 130 ℃ after uniformly mixing, and drying to obtain an electrode material precursor with the particle size of 35 mu m;
3) And (3) transferring the electrode material precursor into a rotary furnace, carbonizing under the protection of inert gas helium, wherein the carbonizing temperature is 600 ℃, and the carbonizing time is 6 hours, so that the required super capacitor electrode material can be obtained.
Example 3
The electrode material comprises an inner core and an outer shell, wherein the inner core is an aggregate of an integrated core-shell type nano-load electrode material, and the outer shell is a carbonized product obtained by carbonizing glucose;
the aggregate of the integrated core-shell type nano-load electrode material comprises 25% of nano-load electrode active material and 60% of modified LaMnO by weight percent 3 Perovskite fiber, 8% of conductive agent and 7% of thickening agent.
The preparation method of the nano-supported electrode active material comprises the following steps:
1) 50g of MCM-22 molecular sieves (SiO 2 /Al 2 O 3 The molar ratio of (2) is 27, and the sucrose which is purchased from Nanjing Xianfeng nano materials Co., ltd.) and 32.2g are dissolved in 100mL of deionized water, then 6mL of concentrated sulfuric acid is added dropwise and stirred for 20h at room temperature, the solution is kept still for 10h and then is carbonized for 25h at 180 ℃, the obtained product is transferred into a tube furnace, 1.0h of nitrogen is introduced to remove redundant air in the tube, the temperature is raised to 900 ℃ at the speed of 10 ℃/min, the temperature is kept constant for 5h, the solution is naturally cooled and then is added into 500mL of sodium hydroxide solution with the concentration of 6mol/L, the solution is stirred overnight at 90 ℃, and the solution is repeatedly washed to be neutral after centrifugal separation, and the porous carbon nano sheet is obtained after freeze drying;
2) 100g of porous carbon nano-sheet is taken and placed in 10L of deionized water, and is dispersed for 3 hours by 500W ultrasonic, 180mL of K with the concentration of 16mmol/L is added respectively 2 PdCl 4 And 150mL of CuCl with a concentration of 8mmol/L 2 .2H 2 O, stirring for 50min, and then dropwise adding 80mL of NaBH with the concentration of 0.28mol/L 4 Then stirring vigorously at 3000r/min for 3 hours at room temperature, centrifugally cleaning for three times with deionized water and ethanol respectively, and drying for 15 hours in vacuum drying at 80 ℃ to obtain pretreated porous carbon nano-sheets;
3) 300mL of deionized water was measured to dissolve 10mmol of Ni (NO) 3 ) 2 .6H 2 O, 10mmol Co (NO) 3 ) 2 .6H 2 O, 40mmol NH 4 And (3) preparing a solution of Cl and 150mmol of urea, stirring for 50min, preparing a reaction solution, placing the prepared pretreated porous carbon nanosheets in a high-pressure reaction kettle, then adding the stirred reaction solution, reacting for 8h at 150 ℃, naturally cooling to room temperature, taking out, centrifuging, separating, and drying to obtain the required nano-supported electrode active material.
The modified LaMnO 3 The preparation method of the perovskite fiber comprises the following steps:
1) 40gCo (NO) 3 ) 2 .6H 2 O, 80g of 2-methylimidazole were dissolved in 3.0L of deionized water, and the two were rapidly mixed, poured into a container, and 500g of LaMnO was added 3 Placing perovskite fiber in a container, standing at room temperature for 10h, repeatedly and alternately washing with deionized water and ethanol, and drying in an oven at 80deg.C for 15h to obtain pretreated LaMnO 3 Perovskite fibers;
2) Will 10gNi (NO) 3 ) 2 .6H 2 O ultrasonic dissolving in 180mL absolute ethanol, pretreating LaMnO 3 Immersing perovskite fibers in the prepared solution, standing for 15h at room temperature, repeatedly washing with deionized water, and drying in an oven at 80 ℃ for 15h to obtain modified LaMnO 3 Perovskite fibers.
A method for preparing a supercapacitor electrode material, the method comprising the steps of:
1) Nanometer load electrode active material and modified LaMnO 3 Mixing perovskite fibers, a conductive agent and a thickening agent, adding water to adjust the viscosity of the slurry to 6000cP, filtering the slurry, introducing acid gas carbon dioxide with the pressure of 0.8MPa into the filtered slurry, and vacuumizing to obtain the slurry;
2) The mass ratio is 7:500, dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-supported electrode active material to the organic carbon source to be 120:5, granulating at 180 ℃ after uniformly mixing, and drying to obtain an electrode material precursor with the particle size of 50 mu m;
3) And (3) transferring the electrode material precursor into a rotary furnace, carbonizing under the protection of inert gas nitrogen, wherein the carbonizing temperature is 700 ℃, and the carbonizing time is 10 hours, so that the required super capacitor electrode material can be obtained.
Comparative example 1: the preparation method of the super capacitor electrode material provided in this comparative example is substantially the same as that of example 1, and the main difference is that the nano-loaded electrode active material used in this comparative example omits the operation of step 1), and performs the operations of steps 2) to 3) using a common carbon nano-sheet.
Comparative example 2: the preparation method of the super capacitor electrode material provided in this comparative example is substantially the same as that of example 1, and the main difference is that the nano-supported electrode active material used in this comparative example omits the operation of step 2).
Comparative example 3: the preparation method of the super capacitor electrode material provided in this comparative example is substantially the same as that of example 1, and the main difference is that the nano-supported electrode active material used in this comparative example omits the operation of step 3).
Comparative example 4: the supercapacitor electrode material provided in this comparative example was prepared in substantially the same manner as in example 1, with the main difference that the unmodified LaMnO used in this comparative example was 3 Perovskite fibers.
Control group: the preparation method of the super capacitor electrode material provided by the control group is approximately the same as that of the embodiment 1, and the main difference is that the control group adopts common carbon nano-sheets and unmodified LaMnO 3 Perovskite fibers.
Performance test 1:
the electrode materials prepared in examples 1-3, comparative examples 1-4 and the control group were cut and striped to prepare a phi 22 x 45 welding pin type supercapacitor cell, the cell was sealed and assembled after being injected with tetraethylammonium tetrafluoroborate electrolyte to prepare a phi 22 x 45 welding pin type supercapacitor, and the test experiments of high temperature durability and monomer electrical properties after 100 ten thousand cycles at the temperature of 2.7V65 ℃ were carried out on the cell, and specific data are shown in table 1.
TABLE 1 Performance test results
According to the test results of table 1, the initial capacity of the monomer of the phi 22 x 45 welding needle type super capacitor assembled by the electrode material provided by the invention is larger than 143F, the direct current internal resistance is lower than 14mΩ, the capacity attenuation rate of the monomer after 1000 hours or 100 ten thousand times of high temperature load is lower than 10%, and the internal resistance increase rate is lower than 40%; the electrode is found to have no obvious degradation effect after the monomer subjected to high-temperature load for 1000 hours or after 100 ten thousand times is disassembled, so that the super capacitor assembled by the electrode material has the advantages of excellent cycle life and high-temperature durability.
Performance test 2:
the electrical property testing method comprises the following steps: the pre-prepared carbon nanotube yarn composite material was assembled into a supercapacitor, PVA-H2SO4 gel (5 g PVA dissolved in 50mL molar concentration of 1mol/L H SO 4) was used as electrolyte and membrane, CHI660E electrochemical workstation was used, and specific capacitance and energy density were calculated from the cyclic voltammogram obtained at a scan rate of 0.01V/s, and specific data are shown in Table 2.
TABLE 2 specific capacitance and energy Density calculated for the electrode Material set of examples 1-3, comparative examples 1-4 and control for the supercapacitor at 0.01V/s scan rate
As shown by the test results in Table 2, the capacitor assembled by the electrode material provided by the invention has beneficial electrochemical performance, high specific capacitance and high energy density, and has wide market application prospect.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. The super-capacitor electrode material is characterized by comprising an inner core and an outer shell, wherein the inner core is an aggregate of an integrated core-shell type nano-load electrode material, and the outer shell is a carbonized product obtained by carbonizing an organic carbon source;
the aggregate of the integrated core-shell type nano-load electrode material comprises, by weight, 15-25% of nano-load electrode active material and 50-80% of modified LaMnO 3 Perovskite fiber, 1-10% of conductive agent and 1-10% of thickening agent;
the organic carbon source is at least one selected from glucose, sucrose, citric acid, polyethylene glycol and polyvinyl alcohol;
the preparation method of the nano-supported electrode active material comprises the following steps:
1) Dissolving MCM-22 molecular sieve and sucrose in deionized water, dropwise adding concentrated sulfuric acid, stirring, standing, pre-carbonizing at 160-180 ℃ for 18-25h, transferring the obtained product into a tube furnace, heating to 800-900 ℃ and keeping the temperature for 2-5h, naturally cooling, adding into sodium hydroxide solution, stirring at 70-90 ℃ overnight, repeatedly washing to neutrality after centrifugal separation, and freeze-drying to obtain porous carbon nano-sheets;
2) Dispersing porous carbon nano-sheets in deionized water by ultrasonic wave, and respectively adding K 2 PdCl 4 And CuCl 2 .2H 2 O, dropwise adding NaBH after stirring 4 Stirring vigorously for 1-3h at room temperature, centrifugally cleaning, and drying to obtain pretreated porous carbon nano-sheets;
3) Proper amount of deionized water is measured to dissolve Ni (NO) 3 ) 2 .6H 2 O、Co(NO 3 ) 2 .6H 2 O、NH 4 Stirring the solution of Cl and urea for 30-50min to prepare a reaction solution, placing the pretreated porous carbon nano-sheet in a high-pressure reaction kettle, then adding the stirred reaction solution, reacting for 3-8h at 120-150 ℃, naturally cooling to room temperature, and obtaining the required nano-supported electrode active material after centrifugal separation and drying;
the modified LaMnO 3 The preparation method of the perovskite fiber comprises the following steps:
1) Co (NO) 3 ) 2 .6H 2 Dissolving O, 2-methylimidazole in deionized water, rapidly mixing, pouring into a container, and adding LaMnO 3 Placing perovskite fiber in a container, standing at room temperature for 4-10h, repeatedly and alternately washing with deionized water and ethanol, and oven drying to obtain pretreated LaMnO 3 Perovskite fibers;
2) Ni (NO) 3 ) 2 .6H 2 Dissolving O ultrasonic in absolute ethyl alcohol, pretreating LaMnO 3 Immersing perovskite fibers in the prepared solution, standing for 10-15h at room temperature, repeatedly washing with deionized water, and drying to obtain modified LaMnO 3 Perovskite fibers.
2. The supercapacitor electrode material according to claim 1, wherein in step 1), the MCM-22 molecular sieve, sucrose, deionized water, concentrated sulfuric acid, and sodium hydroxide solution are used in an amount ratio of 20-50g:14.5-32.2g:60-100mL:1-6mL:200-500mL;
the concentration of the sodium hydroxide solution is 4-6mol/L.
3. The super capacitor electrode material according to claim 1, wherein in step 1), the tube furnace is required to be filled with nitrogen for 0.5-1.0h to remove redundant air in the tube before use.
4. The supercapacitor electrode material according to claim 1, wherein in step 2), the porous carbon nanoplatelets, deionized water, K 2 PdCl 4 、CuCl 2 .2H 2 O、NaBH 4 The dosage proportion of (2) is 50-100g:3-10L:120-180mL:100-150mL:50-80mL;
the K is 2 PdCl 4 Is 12-16mol/L, cuCl 2 .2H 2 The concentration of O is 4-8mol/L, naBH 4 The concentration of (2) is 0.22-0.28mol/L.
5. The supercapacitor electrode material according to claim 1, wherein in step 3), the deionized water is 150-300mL and contains 4-10mmol of Ni (NO 3 ) 2 .6H 2 O, 4-10mmol Co (NO) 3 ) 2 .6H 2 O, 20-40mmol NH 4 Cl and 80-150mmol urea.
6. The supercapacitor electrode material according to claim 1, wherein in step 1), the Co (NO 3 ) 2 .6H 2 O, 2-methylimidazole, deionized water and LaMnO 3 The dosage proportion of the perovskite fiber is 20-40g:50-80g:1.5-3.0L:200-500g.
7. The supercapacitor electrode material according to claim 1, wherein in step 2), the Ni (NO 3 ) 2 .6H 2 The dosage ratio of O to absolute ethyl alcohol is 3-10g:100-180mL.
8. The method for preparing the supercapacitor electrode material according to claim 1, wherein the method comprises the following steps:
1) Nanometer load electrode active material and modified LaMnO 3 Mixing perovskite fiber, conductive agent and thickener, adding water to adjust the viscosity of slurry to 3000-6000cP, filtering the slurry,introducing acid gas with the pressure of 0.2-0.8MPa into the filtered slurry, and vacuumizing to obtain the slurry;
2) The mass ratio is (1-10): (300-500), dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-supported electrode active material to the organic carbon source to be (80-120): (1-5) granulating at 100-180 ℃ after uniformly mixing, and drying to obtain an electrode material precursor with the particle size of 10-50 mu m;
3) And (3) transferring the electrode material precursor into a rotary furnace, carbonizing at 500-700 ℃ under the protection of inert gas for 3-10h, and obtaining the required super capacitor electrode material.
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| CN110970226A (en) * | 2019-12-19 | 2020-04-07 | 华东理工大学 | Composite electrode material, preparation method and super capacitor |
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