CN114694977A - Super capacitor electrode material and preparation method thereof - Google Patents
Super capacitor electrode material and preparation method thereof Download PDFInfo
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- CN114694977A CN114694977A CN202210429758.1A CN202210429758A CN114694977A CN 114694977 A CN114694977 A CN 114694977A CN 202210429758 A CN202210429758 A CN 202210429758A CN 114694977 A CN114694977 A CN 114694977A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 107
- 239000003990 capacitor Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 229910002328 LaMnO3 Inorganic materials 0.000 claims abstract description 35
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000006258 conductive agent Substances 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 239000002135 nanosheet Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 11
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 14
- 229960004793 sucrose Drugs 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 229910018916 CoOOH Inorganic materials 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 238000001291 vacuum drying Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010351 charge transfer process Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- -1 tetraethylammonium tetrafluoroborate Chemical compound 0.000 description 1
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- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—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 a nano load electrode active material, 50-80% of modified LaMnO3 perovskite fiber, 1-10% of a conductive agent and 1-10% of a thickening agent in percentage by weight. The super-capacitor electrode material provided by the invention has excellent cycle performance, and is excellent in capacitance and stability, the capacity decay rate of a monomer is lower than 10% after the monomer is subjected to high-temperature load for 1000 hours or is circulated for 100 ten thousand times, 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
The super capacitor is an energy storage device between a conventional capacitor and a battery, and can be divided into a double-layer super capacitor and a pseudo-capacitor super capacitor according to different energy storage mechanisms. The double-layer type super capacitor stores energy by using an electric double-layer structure consisting of electrodes and an electrolyte after the electrolyte is polarized, and reversible ion adsorption occurs on the two porous electrodes in the energy storage process, so that the double-layer type super capacitor can be repeatedly charged and discharged for millions of times.
The electrode material is one of the key materials determining the electrical performance of the supercapacitor, and the commonly used electrode active materials of the double-layer type supercapacitor mainly comprise active carbon, active carbon fibers, graphene, carbon nanotubes and the like. Wherein the microstructure of the activated carbon and the activated carbon fiber contains non-graphitized amorphous carbon components, and the graphene and the carbon nano tube are easy to generate self-aggregation phenomenon, so that the electrical conductivity of the electrode active materials is low.
Therefore, when an electrode active material is prepared as an electrode, 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 breaks the emulsion of PTFE added in slurry with a water-soluble acidic gas, and spreads PTFE spherical particles suspended in the emulsion into fibers after breaking the emulsion, thereby obtaining a high-performance supercapacitor electrode with a stable coating structure, wherein the colloidal particle binder and the PTFE fibers cooperate to ensure the interfacial adhesion between the electrode coating and a current collector and improve the structural stability inside the electrode coating, so that the prepared electrode has good processability, and is not easy to be subjected to powder removal in the processing processes of slitting, winding and the like, thereby improving the high-temperature load reliability and cycle life of the supercapacitor; although the electrode material has excellent cycle performance, the capacitance and stability are high, and the transfer resistance in the charge transfer process is high, so that the charge storage performance of the capacitor electrode material is influenced.
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 remarkably 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 purpose, the invention provides the following technical scheme:
a super-capacitor 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 15-25% of nano-load electrode active material and 50-80% of modified LaMnO in percentage by weight3Perovskite 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-loading electrode active material comprises the following steps:
1) dissolving an 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 to a tubular furnace, heating to 800-900 ℃ and keeping the temperature for 2-5h, naturally cooling, adding into a sodium hydroxide solution, stirring at 70-90 ℃ for overnight, repeatedly washing after centrifugal separation to be neutral, and freeze-drying to obtain a porous carbon nanosheet;
2) ultrasonically dispersing porous carbon nano-sheets in deionized water, and respectively adding K2PdCl4And CuCl2.2H2O, after stirring, NaBH is added dropwise into the mixture4Violently stirring for 1-3h at room temperature, centrifugally cleaning and drying to obtain a pretreated porous carbon nanosheet;
3) measuring a proper amount of deionized water to dissolve Ni (NO)3)2.6H2O、Co(NO3)2.6H2O、NH4Stirring Cl and urea solution for 30-50min to prepare reaction liquid, placing the pretreated porous carbon nanosheet into a high-pressure reaction kettle, and then addingAnd reacting the stirred reaction solution at the temperature of 120-150 ℃ for 3-8h, naturally cooling to room temperature, and performing centrifugal separation and drying to obtain the required nano load electrode active material.
Furthermore, in the step 1), the use ratio of the MCM-22 molecular sieve, the cane sugar, the deionized water, the concentrated sulfuric acid and the sodium hydroxide solution is 20-50 g: 14.5-32.2 g: 60-100 mL: 1-6 mL: 200-500 mL;
the concentration of the sodium hydroxide solution is 4-6 mol/L.
Furthermore, in the step 1), before the tube furnace is used, nitrogen is required to be introduced for 0.5-1.0h to remove redundant air in the tube.
Further, in the step 2), the porous carbon nanosheet, the deionized water and the K2PdCl4、CuCl2.2H2O、NaBH4The dosage proportion is 50-100 g: 3-10L: 120-180 mL: 100-150 mL: 50-80 mL;
said K2PdCl4In a concentration of 12-16mol/L, CuCl2.2H2The concentration of O is 4-8mol/L, NaBH4The concentration of (B) is 0.22-0.28 mol/L.
Furthermore, in the step 3), the deionized water is 150-300mL and contains 4-10mmol of Ni (NO)3)2.6H2O, 4-10mmol of Co (NO)3)2.6H2O, 20-40mmol of NH4Cl and 80-150mmol urea.
Further, the modified LaMnO3The perovskite fiber is prepared by the following steps:
1) mixing Co (NO)3)2.6H2Dissolving O and 2-methylimidazole in deionized water, quickly mixing the two, pouring into a container, and adding LaMnO3Placing the perovskite fiber in a container, standing for 4-10h at room temperature, repeatedly and alternately washing with deionized water and ethanol, and drying to obtain pretreated LaMnO3Perovskite fibers;
2) mixing Ni (NO)3)2.6H2Dissolving O in absolute ethyl alcohol by ultrasonic wave, and carrying out pretreatment on LaMnO3The perovskite fiber is immersed in the prepared solution and stands at room temperature 1Washing with deionized water repeatedly for 0-15h, and drying to obtain modified LaMnO3Perovskite fibers.
Further, in step 1), the Co (NO)3)2.6H2O, 2-methylimidazole, deionized water and LaMnO3The dosage proportion of the perovskite fiber is 20-40 g: 50-80 g: 1.5-3.0L: 200 and 500 g.
Further, in step 2), the Ni (NO)3)2.6H2The dosage proportion of O and absolute ethyl alcohol is 3-10 g: 100 and 180 mL.
A preparation method of a super capacitor electrode material comprises the following steps:
1) loading nano electrode active material and modified LaMnO3Mixing perovskite fiber, a conductive agent and a thickening agent, adding water to adjust the viscosity of the slurry to 3000-6000cP, filtering the slurry, introducing acid gas with the pressure of 0.2-0.8MPa into the filtered slurry, and then vacuumizing to obtain the slurry;
2) according to the mass ratio of (1-10): (300-500), dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-load electrode active material to the organic carbon source to be (80-120): (1-5), uniformly mixing, granulating at the temperature of 100-180 ℃, and drying to obtain an electrode material precursor with the particle size of 10-50 microns;
3) and moving the electrode material precursor to a rotary furnace, and carbonizing at the temperature of 500-700 ℃ under the protection of inert gas for 3-10h to obtain the required supercapacitor electrode material.
Still further, the acid gas is selected from at least one of sulfur dioxide, carbon dioxide, hydrogen sulfide.
Further, the inert gas is selected from at least one of nitrogen, helium, neon and argon.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the carbon nanosheet formed by carbonizing sucrose by taking the layered molecular sieve MCM-22 as a hard template, sucrose as a carbon source and concentrated sulfuric acid as a catalyst retains the porous structure of the molecular sieve template, so that a large number of holes and folds exist in the carbon nanosheet, and on one hand, the carbon nanosheet has a high specific surface area, which is beneficial to increasing the electrochemical active sites on the surface of the material and reducing the charge transfer resistance of an electrode, so that the capacitance and the stability of the electrode material are improved due to smaller diffusion resistance and larger ion transfer efficiency;
the porous carbon nanosheet is used as a carrier, the small-sized PdCu alloy nanoparticles are stably loaded on the carrier at room temperature through a one-step chemical reduction method, and the rich defects in the porous carbon nanosheet are utilized, so that the strong coupling effect between the PdCu alloy nanoparticles and the porous carbon nanosheet of the carrier can be remarkably enhanced, the PdCu alloy nanoparticles are not easy to fall off, and a large number of convex microspheres exist on the surface of the carrier due to the fact that a large number of alloy nanoparticles are attached to the surface of the carrier, so that the contact and wetting effects of an electrode surface agent and an electrolyte are further increased, the band gap energy of the surface energy of an electrode material is reduced, the resistance of an electrochemical reaction is smaller, the conductivity is improved, and the electrode material has higher capacitance characteristic and good electrochemical stability;
meanwhile, a simple hydrothermal method is adopted, the morphology of the pretreated porous carbon nanosheets is treated by introducing chloride ions, after hydrothermal reaction, nanowires randomly growing are presented on the surfaces of the pretreated porous carbon nanosheets regulated and controlled by the chloride ions, the formed nanowires are small in size, the top ends of the nanowires are mutually crosslinked, and enough space is reserved at the bottom ends of the nanowires, so that migration movement of electrolyte particles is facilitated, more active sites are provided for electrode reaction, the formed nanowires can also play a role in separation, aggregation and self-aggregation of the pretreated porous carbon nanosheets can be prevented, and further reduction of transmission resistance of ions and the like in electrode materials is facilitated, so that the charge storage performance of the electrode materials is remarkably enhanced.
2. In the invention, by the methods of in-situ growth and sacrificial template etching, in LaMnO3Two-dimensional nano-sheet arrays are constructed on the perovskite fibers, and in the electrochemical activation process of the nano-sheet arrays, Co (OH)2Is converted into a CoOOH, and then the mixture is converted into a CoOOH,so as to expose hydrogen vacancy, CoOOH can be used as an active site of cation intercalation to accommodate metal ion intercalation, thereby being helpful for improving the capacitance of the capacitor device, enabling the capacitor device to have high energy density, enabling the capacitor device to have ultra-long cycle life and extremely high cycle stability, and enabling the capacitor device to have excellent cycle performance after ten thousand cycles without capacity attenuation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A super-capacitor 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 15 percent of nano-load electrode active material and 80 percent of modified LaMnO according to weight percentage3Perovskite fiber, 3% of conductive agent and 2% of thickening agent.
The preparation method of the nano load electrode active material comprises the following steps:
1) 20g of MCM-22 molecular Sieve (SiO)2/Al2O3Purchased from Nanjing Xiancheng nanomaterial Co., Ltd.) and 14.5g of sucrose are dissolved in 60mL of deionized water, 1mL of concentrated sulfuric acid is added dropwise and stirred for 10h at room temperature, the solution is stood for 3h and then pre-carbonized at 160 ℃ for 18h, the obtained product is transferred to a tube furnace, 0.5h of nitrogen is introduced to remove excess air in the tube, the temperature is raised to 800 ℃ at the rate of 5 ℃/min, the temperature is kept for 2h, the solution is naturally cooled and then added into 200mL of sodium hydroxide solution with the concentration of 4mol/L, the solution is stirred overnight at 70 ℃, repeatedly washed to be neutral after centrifugal separation, and freeze-dried to obtain the productTo porous carbon nanosheets;
2) 50g of porous carbon nanosheet is placed in 3L of deionized water, ultrasonic dispersion is carried out for 1h at 300W, and 120mL of K with the concentration of 12mmol/L are respectively added2PdCl4And 100mL of CuCl with a concentration of 4mmol/L2.2H2O, stirring for 20min, and then dropwise adding 50mL of NaBH with the concentration of 0.22mol/L4Then, vigorously stirring for 1h at room temperature at 1000r/min, respectively centrifugally cleaning for three times by using deionized water and ethanol, and drying for 8h in vacuum drying at 60 ℃ to obtain a pretreated porous carbon nanosheet;
3) measuring 150mL of deionized water to dissolve Ni (NO) containing 4mmol3)2.6H2O, 4mmol of Co (NO)3)2.6H2O, 20mmol of NH4And Cl and 80mmol of urea are stirred for 30min to prepare reaction liquid, the prepared pretreated porous carbon nanosheet is placed in a high-pressure reaction kettle, the stirred reaction liquid is added, the reaction is carried out for 3h at 120 ℃, the reaction is naturally cooled to room temperature, the reaction liquid is taken out and subjected to centrifugal separation, and the required nano load electrode active material can be obtained after drying.
The modified LaMnO3The perovskite fiber is prepared by the following steps:
1) 20g of Co (NO)3)2.6H2Dissolving O and 50g 2-methylimidazole in 1.5L deionized water, quickly mixing the two, pouring into a container, and adding 200g LaMnO3Placing the perovskite fiber in a container, standing for 4h at room temperature, repeatedly and alternately washing with deionized water and ethanol, and drying in a 60 ℃ oven for 10h to obtain the pretreated LaMnO3Perovskite fibers;
2) 3gNi (NO)3)2.6H2Dissolving O in 100mL of absolute ethanol by ultrasonic waves, and carrying out pretreatment on LaMnO3Immersing the perovskite fiber in the prepared solution, standing for 10h at room temperature, repeatedly washing with deionized water, and drying in a 60 ℃ oven for 10h to obtain the modified LaMnO3Perovskite fibers.
A preparation method of a super capacitor electrode material comprises the following steps:
1) loading the nano electrode active material,Modified LaMnO3Mixing perovskite fiber, a conductive agent and a thickening agent, adding water to adjust the viscosity of the slurry to 3000cP, filtering the slurry, introducing acidic gas carbon dioxide with the pressure of 0.2MPa into the filtered slurry, and then vacuumizing to obtain the slurry;
2) according to the mass ratio of 1: 300, dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-load electrode active material to the organic carbon source to be 80: 1, uniformly mixing, granulating at 100-DEG C, and drying to obtain an electrode material precursor with the particle size of 10 mu m;
3) and (3) moving the electrode material precursor into a rotary furnace, and carbonizing at 500 ℃ for 10h under the protection of inert gas nitrogen to obtain the required supercapacitor electrode material.
Example 2
A super-capacitor 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 15-25% of nano-load electrode active material and 50-80% of modified LaMnO in percentage by weight3Perovskite fiber, 1-10% of conductive agent and 1-10% of thickening agent.
The preparation method of the nano load electrode active material comprises the following steps:
1) 30g of MCM-22 molecular Sieve (SiO)2/Al2O3The molar ratio of 27, purchased from Nanjing Xiancheng nanomaterial Co., Ltd.) and 26g of sucrose 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 stood still for 7h and then pre-carbonized at 170 ℃ for 20h, the obtained product is transferred to a tube furnace, 0.8h of nitrogen is introduced to remove excess air in the tube, the temperature is raised to 850 ℃ at the rate of 8 ℃/min, the temperature is kept constant for 3h, the solution is naturally cooled and then added into 350mL of 5mol/L sodium hydroxide solution, the solution is stirred at 80 ℃ overnight, the solution is repeatedly washed to neutrality after centrifugal separation, and porous carbon nanosheets are obtained after freeze drying;
2) 80g of porous carbon nano-sheet is placed in 6L of deionized water, ultrasonic dispersion is carried out for 2h by 400W, and 160mL of K with the concentration of 15mmol/L is respectively added2PdCl4And 130mL of CuCl with a concentration of 5mmol/L2.2H2O, stirring for 30min, and then dropwise adding 70mL of NaBH with the concentration of 0.25mol/L4Then, vigorously stirring at room temperature for 2h at 2000r/min, respectively centrifugally cleaning with deionized water and ethanol for three times, and drying in vacuum drying at 70 ℃ for 12h to obtain a pretreated porous carbon nanosheet;
3) 230mL of deionized water was weighed out to dissolve Ni (NO) containing 8mmol3)2.6H2O, 6mmol of Co (NO)3)2.6H2O, 30mmol NH4And Cl and 120mmol of urea are stirred for 40min to prepare reaction liquid, the prepared pretreated porous carbon nanosheet is placed in a high-pressure reaction kettle, the stirred reaction liquid is added, the reaction is carried out for 5h at 135 ℃, the reaction is naturally cooled to room temperature, the reaction liquid is taken out and subjected to centrifugal separation, and the required nano load electrode active material can be obtained after drying.
The modified LaMnO3The perovskite fiber is prepared by the following steps:
1) mixing 30gCo (NO)3)2.6H2Dissolving O and 70g 2-methylimidazole in 2.5L deionized water, quickly mixing the two, pouring into a container, and adding 400g LaMnO3Placing the perovskite fiber in a container, standing for 7h at room temperature, repeatedly and alternately washing with deionized water and ethanol, and drying in a 70 ℃ oven for 13h to obtain the pretreated LaMnO3Perovskite fibers;
2) 8gNi (NO)3)2.6H2Dissolving O in 150mL of absolute ethanol by ultrasonic waves, and carrying out pretreatment on LaMnO3Immersing the perovskite fiber 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 the modified LaMnO3A perovskite fiber.
A preparation method of a super capacitor electrode material comprises the following steps:
1) loading nano electrode active material and modified LaMnO3Perovskite fiber, electrically conductiveMixing the thickening agent and the agent, adding water to adjust the viscosity of the slurry to 5000cP, filtering the slurry, introducing acidic gas sulfur dioxide with the pressure of 0.6MPa into the filtered slurry, and then vacuumizing to obtain the slurry;
2) according to the mass ratio of 3: 400, dispersing an organic carbon source in water, adding slurry, and controlling the mass ratio of the nano-load electrode active material to the organic carbon source to be 100: 3, uniformly mixing, granulating at 130 ℃, and drying to obtain an electrode material precursor with the particle size of 35 microns;
3) and (3) moving the electrode material precursor into a rotary furnace, and carbonizing at 600 ℃ for 6h under the protection of inert gas helium to obtain the required supercapacitor electrode material.
Example 3
A super-capacitor 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 percent of nano-load electrode active material and 60 percent of modified LaMnO in percentage by weight3Perovskite fiber, 8% of conductive agent and 7% of thickening agent.
The preparation method of the nano load electrode active material comprises the following steps:
1) 50g of MCM-22 molecular Sieve (SiO)2/Al2O3The molar ratio of 27, purchased from Nanjing Xiancheng nanomaterial Co., Ltd.) and 32.2g of sucrose are dissolved in 100mL of deionized water, 6mL of concentrated sulfuric acid is added dropwise and stirred at room temperature for 20h, the solution is stood for 10h and then pre-carbonized at 180 ℃ for 25h, the obtained product is transferred to 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 added into 500mL of 6mol/L sodium hydroxide solution, the solution is stirred at 90 ℃ overnight, the solution is repeatedly washed to be neutral after centrifugal separation, and freeze drying is carried out to obtain the porous carbon nanosheet;
2) 100g of porous carbon nanosheet is placed in 10L of deionized waterIn the process, 500W ultrasonic dispersion is carried out for 3h, and 180mL of K with the concentration of 16mmol/L is respectively added2PdCl4And 150mL of CuCl with a concentration of 8mmol/L2.2H2O, after stirring for 50min, 80mL of NaBH with the concentration of 0.28mol/L is added dropwise4Then, vigorously stirring at room temperature for 3h at 3000r/min, respectively centrifugally cleaning with deionized water and ethanol for three times, and drying in vacuum drying at 80 ℃ for 15h to obtain a pretreated porous carbon nanosheet;
3) 300mL of deionized water was weighed to dissolve Ni (NO) containing 10mmol3)2.6H2O, 10mmol of Co (NO)3)2.6H2O, 40mmol NH4And Cl and 150mmol of urea solution are stirred for 50min to prepare reaction liquid, the prepared pretreated porous carbon nanosheet is placed in a high-pressure reaction kettle, the stirred reaction liquid is added, the reaction is carried out for 8h at 150 ℃, the reaction is naturally cooled to room temperature, the reaction liquid is taken out and subjected to centrifugal separation, and the required nano load electrode active material can be obtained after drying.
The modified LaMnO3The perovskite fiber is prepared by the following steps:
1) mixing 40gCo (NO)3)2.6H2Dissolving O and 80g 2-methylimidazole in 3.0L deionized water, quickly mixing the two, pouring into a container, and adding 500g LaMnO3Placing the perovskite fiber in a container, standing for 10h at room temperature, repeatedly and alternately washing with deionized water and ethanol, and drying in an oven at 80 ℃ for 15h to obtain pretreated LaMnO3Perovskite fibers;
2) will be 10gNi (NO)3)2.6H2Dissolving O in 180mL of absolute ethanol by ultrasonic wave, and carrying out pretreatment on LaMnO3Immersing the perovskite fiber 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 the modified LaMnO3Perovskite fibers.
A preparation method of a super capacitor electrode material comprises the following steps:
1) loading nano electrode active material and modified LaMnO3Mixing perovskite fiber, conductive agent and thickening agent, adding water to regulate viscosity of slurryFiltering the slurry at 6000cP, introducing acid gas carbon dioxide with the pressure of 0.8MPa into the filtered slurry, and then vacuumizing to obtain the slurry;
2) according to the mass ratio of 7: 500, dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-load electrode active material to the organic carbon source to be 120: 5, uniformly mixing, granulating at 180 ℃, and drying to obtain an electrode material precursor with the particle size of 50 microns;
3) and (3) moving the electrode material precursor into a rotary furnace, and carbonizing at 700 ℃ for 10h under the protection of inert gas nitrogen to obtain the required supercapacitor electrode material.
Comparative example 1: the preparation method of the supercapacitor electrode material provided by the comparative example is substantially the same as that of the supercapacitor electrode material provided by the example 1, and the main difference is that the operation of the step 1) is omitted for the nano-load electrode active material used in the comparative example, and the operation of the steps 2) to 3) is performed by using common carbon nanosheets.
Comparative example 2: the preparation method of the electrode material of the super capacitor provided by the comparative example is almost the same as that of the electrode material of the super capacitor in example 1, and the main difference is that the operation of step 2) is omitted for the nano-load electrode active material used in the comparative example.
Comparative example 3: the preparation method of the supercapacitor electrode material provided by the comparative example is substantially the same as that of example 1, and the main difference is that the operation of step 3) is omitted for the nano-loaded electrode active material used in the comparative example.
Comparative example 4: the preparation method of the electrode material of the super capacitor provided by the comparative example is almost the same as that of the electrode material of the super capacitor provided by the example 1, and the main difference is that the unmodified LaMnO used in the comparative example3Perovskite fibers.
Control group: the preparation method of the supercapacitor electrode material provided by the control group is substantially the same as that of the supercapacitor electrode material provided in the embodiment 1, and the main difference is that the control group adopts common carbon nanosheets and unmodified LaMnO3A perovskite fiber.
Performance test 1:
the electrode materials prepared in examples 1 to 3, comparative examples 1 to 4 and a control group were cut into strips, and prepared into Φ 22 × 45 welded-pin type supercapacitor cells, and after tetraethylammonium tetrafluoroborate electrolyte was injected, the cells were sealed and assembled to prepare Φ 22 × 45 welded-pin type supercapacitors, and the supercapacitor cells were subjected to test experiments of high-temperature durability at 2.7V65 ℃ under 1000H and monomer electrical properties after 100 ten thousand cycles, and specific data are shown in table 1.
Table 1 results of performance testing
According to the test results in table 1, the initial capacity of the phi 22 x 45 welding pin type supercapacitor monomer assembled by the electrode material provided by the invention is more than 143F, the direct current internal resistance is lower than 14m omega, the capacity decay rate of the monomer is lower than 10% after the monomer is subjected to high-temperature load for 1000 hours or circulated for 100 ten thousand times, and the internal resistance increase rate is lower than 40%; the monomers after being subjected to high-temperature load for 1000 hours or being circulated for 100 ten thousand times are disassembled, and the electrodes have no obvious degradation effect, so that the super capacitor assembled by the electrode material has excellent cycle life and high-temperature durability.
Performance test 2:
the electrical property test method comprises the following steps: the prepared carbon nanotube yarn composite material is assembled into a super capacitor, PVA-H2SO4 gel (5g of PVA is dissolved in 50mL of 1mol/L H2SO 4) is used as an electrolyte and a diaphragm, a CHI660E electrochemical workstation is adopted, and the specific capacitance and the energy density are calculated according to a cyclic voltammetry curve obtained at a scanning rate of 0.01V/s, wherein the specific data are shown in Table 2.
TABLE 2 specific capacitance and energy density calculated for supercapacitors of the electrode material groups described in examples 1-3, comparative examples 1-4 and control at a scan rate of 0.01V/s
The test results in table 2 show that 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 herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments 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 utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
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 15-25% of nano load electrode active material and 50-80% of modified LaMnO3Perovskite 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.
2. The super capacitor electrode material as claimed in claim 1, wherein the preparation method of the nano load electrode active material is as follows:
1) dissolving an 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 to a tubular furnace, heating to 800-900 ℃ and keeping the temperature for 2-5h, naturally cooling, adding into a sodium hydroxide solution, stirring at 70-90 ℃ for overnight, repeatedly washing after centrifugal separation to be neutral, and freeze-drying to obtain a porous carbon nanosheet;
2) ultrasonically dispersing porous carbon nano-sheets in deionized water, and respectively adding K2PdCl4And CuCl2.2H2O, after stirring, NaBH is added dropwise into the mixture4Violently stirring for 1-3h at room temperature, centrifugally cleaning and drying to obtain a pretreated porous carbon nanosheet;
3) measuring a proper amount of deionized water to dissolve Ni (NO)3)2.6H2O、Co(NO3)2.6H2O、NH4And Cl and urea solution is stirred for 30-50min to prepare reaction liquid, the pretreated porous carbon nanosheet is placed in a high-pressure reaction kettle, then the stirred reaction liquid is added, the reaction is carried out for 3-8h at the temperature of 120-150 ℃, the reaction is naturally cooled to room temperature, and the required nano load electrode active material can be obtained after centrifugal separation and drying.
3. The supercapacitor electrode material according to claim 2, wherein in step 1), the MCM-22 molecular sieve, sucrose, deionized water, concentrated sulfuric acid, and sodium hydroxide solution are used in a ratio of 20-50 g: 14.5-32.2 g: 60-100 mL: 1-6 mL: 200-500 mL;
the concentration of the sodium hydroxide solution is 4-6 mol/L.
4. The electrode material of claim 2, wherein in step 1), nitrogen is introduced into the tube furnace for 0.5-1.0h to remove excess air in the tube before use.
5. The supercapacitor electrode material according to claim 2, wherein in the step 2), the porous carbon nanosheet, deionized water and K are mixed together2PdCl4、CuCl2.2H2O、NaBH4The dosage proportion is 50-100 g: 3-10L: 120-180 mL: 100-150 mL: 50-80 mL;
said K2PdCl4In a concentration of 12-16mol/L, CuCl2.2H2The concentration of O is 4-8mol/L, NaBH4The concentration of (B) is 0.22-0.28 mol/L.
6. The electrode material as claimed in claim 2, wherein in step 3), the deionized water is 150-300mL and contains 4-10mmol of Ni (NO)3)2.6H2O, 4-10mmol of Co (NO)3)2.6H2O, 20-40mmol of NH4Cl and 80-150mmol urea.
7. The supercapacitor electrode material according to claim 1, wherein the modified LaMnO is3The preparation method of the perovskite fiber comprises the following steps:
1) mixing Co (NO)3)2.6H2Dissolving O and 2-methylimidazole in deionized water, quickly mixing the two, pouring into a container, and adding LaMnO3Placing the perovskite fiber in a container, standing for 4-10h at room temperature, repeatedly and alternately washing with deionized water and ethanol, and drying to obtain pretreated LaMnO3Perovskite fibers;
2) mixing Ni (NO)3)2.6H2Dissolving the O in absolute ethyl alcohol by ultrasonic wave to obtain pretreated LaMnO3Perovskite fiber impregnationImmersing in the prepared solution, standing at room temperature for 10-15h, repeatedly washing with deionized water, and drying to obtain modified LaMnO3Perovskite fibers.
8. The supercapacitor electrode material according to claim 7, wherein in the step 1), the Co (NO) is added3)2.6H2The dosage proportion of the O, the 2-methylimidazole, the deionized water and the LaMnO3 perovskite fiber is 20-40 g: 50-80 g: 1.5-3.0L: 200 and 500 g.
9. The supercapacitor electrode material according to claim 7, wherein in step 2), the Ni (NO) is3)2.6H2The dosage proportion of O and absolute ethyl alcohol is 3-10 g: 100 and 180 mL.
10. The method for preparing the electrode material of the supercapacitor according to claim 1, wherein the method comprises the following steps:
1) loading nano electrode active material and modified LaMnO3Mixing perovskite fiber, a conductive agent and a thickening agent, adding water to adjust the viscosity of the slurry to 3000-6000cP, filtering the slurry, introducing acid gas with the pressure of 0.2-0.8MPa into the filtered slurry, and then vacuumizing to obtain the slurry;
2) according to the mass ratio of (1-10): (300-500), dispersing an organic carbon source in water, then adding slurry, and controlling the mass ratio of the nano-load electrode active material to the organic carbon source to be (80-120): (1-5), uniformly mixing, granulating at the temperature of 100-180 ℃, and drying to obtain an electrode material precursor with the particle size of 10-50 microns;
3) and moving the electrode material precursor to a rotary furnace, and carbonizing at the temperature of 500-700 ℃ under the protection of inert gas for 3-10h to obtain the required supercapacitor 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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