CN115483037A - Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and preparation method and application thereof - Google Patents
Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and preparation method and application thereof Download PDFInfo
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- CN115483037A CN115483037A CN202211136289.0A CN202211136289A CN115483037A CN 115483037 A CN115483037 A CN 115483037A CN 202211136289 A CN202211136289 A CN 202211136289A CN 115483037 A CN115483037 A CN 115483037A
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- titanium carbide
- polypyrrole
- sodium alginate
- dimensional titanium
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 102
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 50
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 50
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000004964 aerogel Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 82
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 36
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- 239000000017 hydrogel Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000006228 supernatant Substances 0.000 claims description 25
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 22
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 21
- 239000012498 ultrapure water Substances 0.000 claims description 21
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002356 single layer Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000007772 electrode material Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 39
- 229910052708 sodium Inorganic materials 0.000 description 39
- 239000011734 sodium Substances 0.000 description 39
- 150000002500 ions Chemical class 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and a preparation method and application thereof, and belongs to the technical field of material synthesis. The polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material is prepared by a one-pot method, and after freeze drying, surface calcium carbonate particles of the polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material are completely etched by hydrochloric acid, so that the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material with a three-dimensional porous structure is obtained. The preparation method of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is simple and easy to implement, and when the composite material is used for a supercapacitor electrode, the composite material has high specific capacitance and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material, and a preparation method and application thereof.
Background
The super capacitor is considered to be a product with great development prospect in the field of energy storage due to the advantages of high energy density, rapid charge and discharge rate, high rate performance and the like, but the limited power density and cycle life of the super capacitor are still insufficient to meet the increasing demand of novel energy storage equipment. Supercapacitors are largely classified into two categories, according to the principle of charge storage: electrochemical double layer capacitors and pseudocapacitors. The former stores charges in an electrostatic manner by ion adsorption on the surface of an electrode, and a carbon material with a large surface area is generally adopted as an electrode material; the capacitance of the pseudo capacitor is derived from a rapid and reversible redox reaction process on an interface, and transition metal oxides, sulfides, hydroxides and conductive polymers are generally adopted as electrode materials. The key to obtain high and stable specific capacitance lies in designing electroactive materials, and the prior art often improves the electrochemical performance of electrode materials by controlling the microstructure, such as specific surface area and pores.
Therefore, many researchers have adopted pseudocapacitive materials such as conductive polymers, polypyrrole and the like, wherein the conductive polymers are concerned by the researchers due to the convenience of synthesis and high conductivity. Polypyrrole is widely applied to research of electrode materials of super capacitors because of the advantages of large pseudocapacitance, simple synthesis, low cost and the like. However, polypyrrole causes volume change due to repeated doping/dedoping of ions during high-speed cycling, resulting in poor cycling stability. Therefore, polypyrrole can be compounded with other materials with strong mechanical properties to improve the specific capacitance and stability of the polypyrrole.
In recent years, two-dimensional transition metal carbides and nitrides (also known as MXenes) have gained wide attention due to their excellent electrochemical properties. Its general molecular formula is M n+1 X n T x (n =1,2,3), wherein M represents a transition metalX represents a carbon or nitrogen atom, T represents a surface terminating functional group (-OH, -O, -F); MXenes have electrochemically active centers derived from the rapid conversion of transition metals with different valence states and the rapid redox reaction of surface terminating functional groups with conductivities up to 10000S cm -1 . Of these, two-dimensional titanium carbide has attracted great attention as an electrode material for a supercapacitor. Besides, the material has the excellent characteristics of electrode materials such as high rate performance, high power density, excellent cycling stability and high energy density. However, as with graphene, self-aggregation occurs due to strong van der waals interactions between adjacent two-dimensional titanium carbide nanosheets, which severely hinders penetration of electrolyte ions, and limits the electrochemical performance and practical application of the two-dimensional titanium carbide electrode material. In order to solve the problems, people manufacture a heterostructure electrode material of two-dimensional titanium carbide and other compounds with high specific capacitance so as to increase the interlayer spacing of the two-dimensional titanium carbide and improve the electrochemical performance of the two-dimensional titanium carbide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and a preparation method and application thereof. Therefore, the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material has great potential as a supercapacitor electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is prepared by a one-pot method, freeze drying is carried out, and hydrochloric acid is used for completely etching calcium carbonate particles on the surface of the polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material, so that the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material with a three-dimensional porous structure is obtained.
A preparation method of a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is characterized by comprising the following steps:
(1) Weighing sodium alginate, adding into ultrapure water, magnetically stirring, adding pyrrole, uniformly stirring to form sol, adding single-layer two-dimensional titanium carbide and calcium carbonate particles, magnetically stirring, slowly dropwise adding an ammonium persulfate solution, magnetically stirring to form black gel, and standing in a refrigerator at 4 ℃ until pyrrole is completely polymerized;
(2) And (3) freeze-drying, soaking in hydrochloric acid solution to completely etch calcium carbonate particles, repeatedly cleaning with ultrapure water, and freeze-drying to obtain the three-dimensional porous polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material.
According to the preparation method, the mass ratio of the sodium alginate to the pyrrole to the monolayer two-dimensional titanium carbide to the calcium carbonate particles is as follows: 0.1-0.5g -1 。
In the preparation method, the magnetic stirring time is 2-5 h, and the concentration of the hydrochloric acid is 0.1-1 mol L -1 And the etching time is 1-3 h.
The preparation method comprises the following specific preparation processes of the single-layer two-dimensional titanium carbide: weighing lithium fluoride, dissolving the lithium fluoride in a hydrochloric acid solution, slowly adding titanium aluminum carbide under magnetic stirring, etching at room temperature, centrifugally washing with ultrapure water for a plurality of times until the pH of the centrifugal supernatant is 6.8-7.2, collecting multilayer two-dimensional titanium carbide supernatant, introducing nitrogen gas for bubbling, performing ultrasonic treatment, centrifuging, collecting monolayer two-dimensional titanium carbide colloid supernatant, continuously introducing nitrogen gas to obtain monolayer two-dimensional titanium carbide, and storing in a refrigerator at 4 ℃. The method for calculating the concentration of the two-dimensional titanium carbide colloid comprises the following steps: measuring a certain volume of supernatant in a culture dish, freeze-drying, weighing the supernatant, and calculating the concentration.
The preparation method comprises the steps of,The mass to volume ratio of the hydrochloric acid solution to the titanium aluminum carbide is as follows: 0.1-2g, 15-25mL, preferably the mass-to-volume ratio of lithium fluoride, hydrochloric acid solution and titanium aluminum carbide is 1g -1 (ii) a The etching time is 20-30 h, and the nitrogen gas is introduced for 15-30 min.
The preparation method comprises the following specific preparation processes of the calcium carbonate particles: weighing calcium chloride solution and sodium carbonate solution with equal volume and concentration, mixing, placing in mixed solution of water and glycol, magnetically stirring, continuously centrifuging and washing with ethanol, methanol and acetone in sequence to remove unreacted ions and glycol, collecting precipitate, namely calcium carbonate particles, and drying.
In the preparation method, the concentrations of the calcium chloride solution and the sodium carbonate solution are both 0.05-0.2 mol L -1 Preferably 0.1mol L -1 The volumes of the calcium chloride solution and the sodium carbonate solution are both 30-60 mL; the volume ratio of the water to the ethylene glycol is 1-15, the magnetic stirring time is 20-40 min, and the drying temperature is 50-100 ℃.
In a second aspect, the invention provides a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material, which is prepared by any one of the preparation methods.
In a third aspect, the invention provides application of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material as a supercapacitor electrode material.
The principle of the invention is as follows: polypyrrole has higher specific capacitance, polypyrrole and sodium alginate can form aerogel with a three-dimensional network structure, and two-dimensional titanium carbide nanosheets are easy to agglomerate between the lamellae, so that the electrochemical performance is reduced, and the two-dimensional titanium carbide nanosheets are dispersed in the aerogel network, so that the distance between the lamellae can be increased, and the electrochemical performance is improved. And finally, calcium carbonate particles are used as a sacrificial template, three-dimensional porous aerogel can be formed, and the three-dimensional porous aerogel network can promote the transfer of electrolyte ions and improve the electrochemical performance of the composite material.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method is simple and feasible, and the prepared polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material has higher specific capacitance and better cycle stability when being used for the electrode of the supercapacitor.
Drawings
FIG. 1 is a scanning electron micrograph of titanium aluminum carbide (A), two-dimensional titanium carbide (B) and calcium carbonate particles (C) prepared in example 1, and a particle size distribution diagram (D) of the calcium carbonate particles;
fig. 2 is a scanning electron micrograph of polypyrrole/two-dimensional titanium carbide/sodium alginate-n prepared in example 1, where n =0 (a), 1 (B), 2 (C), 3 (D);
FIG. 3 is an X-ray powder diffraction pattern of polypyrrole prepared in comparative example 1 and two-dimensional titanium carbide, sodium alginate, polypyrrole/two-dimensional titanium carbide/sodium alginate-2, titanium aluminum carbide prepared in example 1;
FIG. 4 is an X-ray photoelectron spectrum of polypyrrole/titanium carbide two-dimensional/sodium alginate-2 prepared in example 1;
FIG. 5 shows polypyrrole prepared in comparative example 1 and two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) prepared in example 1 at 100mV s -1 Cyclic voltammograms at the scan rate;
FIG. 6 is a cyclic voltammogram of polypyrrole/titanium carbide bidimensional/sodium alginate-2 prepared in example 1 at different sweep rates;
FIG. 7 is the relative contribution rate of capacitance control and diffusion control to current at different scan rates for polypyrrole/titanium carbide bidimensional/sodium alginate-2 prepared in example 1;
FIG. 8 shows polypyrrole prepared in comparative example 1 and two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) prepared in example 1 at 1Ag -1 Constant current charge-discharge curve at current density of (a);
FIG. 9 is a constant current charge and discharge curve of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 prepared in example 1 at different current densities;
fig. 10 is an electrochemical ac impedance plot of polypyrrole prepared in comparative example 1 and two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) prepared in example 1, with balanced circuit diagrams labeled inside;
FIG. 11 is a graph of the cycling stability of polypyrrole/titanium carbide two-dimensional/sodium alginate-2 prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following drawings and examples, but the present invention is not limited to the following examples.
Example 1:
the preparation method of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material comprises the following steps:
(1) 1g of lithium fluoride was dissolved in 20mL of 9mol L -1 To the hydrochloric acid solution, 1g of titanium aluminum carbide powder was then slowly added with magnetic stirring. After etching at 35 ℃ for 24h, the supernatant was washed by centrifugation with ultrapure water several times until the pH of the supernatant was 7. Then the multilayer two-dimensional titanium carbide aqueous solution is subjected to ultrasonic treatment for 1 hour after being bubbled with nitrogen for 20min. Centrifuging at 3500rpm for 1h, and collecting supernatant of monolayer two-dimensional titanium carbide colloid. The supernatant was collected in a glass bottle and nitrogen was continuously purged for 20min and then stored in a refrigerator at 4 ℃ until use. The method for calculating the concentration of the two-dimensional titanium carbide colloid comprises the following steps: weighing 10mL of supernatant in a culture dish, freeze-drying, and weighing to obtain a concentration of about 4.87mg mL -1 . As shown in fig. 1 (a) (B) scanning electron microscope images of bulk titanium aluminum carbide and monolayer two-dimensional titanium carbide nanosheets, it can be seen that monolayer two-dimensional titanium carbide nanosheets have been successfully prepared; FIG. 1 (C) shows the synthesized calcium carbonate particles, and it can be seen from FIG. 1 (D) that the particle size of the calcium carbonate particles is in the range of 0.6 to 1.4. Mu.m.
(2) Equal volume of 0.1mol L -1 Calcium chloride and 0.1mol L -1 The sodium carbonate solution was placed in water and ethylene glycol (volume ratio 1. Subsequently, the synthesized calcium carbonate particles were collected by centrifugal washing with ethanol, methanol, and acetone at 10000rpm in order to remove unreacted ions and ethylene glycol, and then dried at 60 ℃ for use.
(3) Measuring 10mL of ultrapure water into a 30mL glass sample bottle, adding 0.3g of sodium alginate, and performing magnetic fieldAfter stirring uniformly, 270mg of pyrrole was added and stirred uniformly to form a sol. Then, 5mL of the two-dimensional titanium carbide colloid (about 24.35 mg) obtained in the step (1) was weighed, 0, 10, 50, and 100mg of the calcium carbonate particles prepared in the step (2) were respectively weighed and dissolved in the above sol, and the mixture was magnetically stirred for 3 hours. Then, 1mL of 2.28mg L was slowly added dropwise -1 Ammonium persulfate solution, stirring for 10s to form black hydrogel. Placing hydrogel in refrigerator at 4 deg.C for polymerization, freeze drying at-58 deg.C for 24 hr, and placing in 0.5mol L -1 And (2) soaking the calcium carbonate particles in a hydrochloric acid solution for 2h to completely etch the calcium carbonate particles, repeatedly cleaning the calcium carbonate particles by using ultrapure water, and freeze-drying the calcium carbonate particles to obtain the three-dimensional porous polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material (according to the different mass of the calcium carbonate particles, a sample is named as polypyrrole/two-dimensional titanium carbide/sodium alginate-n, wherein n =0, 1,2 and 3 respectively represent that the mass of the added calcium carbonate is 0, 10, 50 and 100 mg).
Fig. 2 (a), (B), (C) and (D) are scanning electron micrographs of polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2 and 3), respectively. As can be seen from fig. 2 (a), when no calcium carbonate particles are added to the aerogel, there are fewer voids on the surface of the aerogel; as the content of calcium carbonate particles increases, the pore size of the aerogel surface gradually becomes larger, such as: FIG. 2 (B) (C) (D). In particular, it can be seen from fig. 2 (D) that the aerogel surface has large cavities, probably because the calcium carbonate particles are too much to agglomerate, so that large cavities are left after etching.
As shown in fig. 3, the X-ray powder diffraction pattern of polypyrrole, two-dimensional titanium carbide, sodium alginate, polypyrrole/two-dimensional titanium carbide/sodium alginate-2, and titanium aluminum carbide shows that the peak of polypyrrole at 2 θ =15 ° to 35 ° is a characteristic peak of amorphous polypyrrole. In the diffraction peaks of the titanium aluminum carbide precursor and the two-dimensional titanium carbide, the titanium aluminum carbide at 2 θ =9.55 °,19.00 °,38.75 °,60.34 ° corresponds to (002), (004), (104) and (110) crystal planes of the titanium aluminum carbide (JCPDS No. 52-0875), respectively. It is noted that the diffraction peaks of the two-dimensional titanium carbide in the (002) and (004) crystal planes are shifted to lower angles than before etching, indicating that the aluminum layer in the titanium aluminum carbide can be successfully removed by etching. In addition, the diffraction peak of the two-dimensional titanium carbide at 38.75 ° corresponding to the (104) crystal plane disappeared, indicating that the removal of the aluminum layer was associated with the successful production of the two-dimensional titanium carbide. The broad peak of sodium alginate at 2 θ =13.50 ° and 22.50 ° is a characteristic peak of an amorphous polymer structure in which the crystallinity of sodium alginate is low. Diffraction peaks of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at 2 theta =6.07 degrees and 17.49 degrees respectively correspond to (002) and (004) crystal faces of the two-dimensional titanium carbide; the diffraction peak at 2 θ =13.5 ° is a characteristic peak of sodium alginate, while the diffraction peak at 22.50 ° is due to the superposition of two broad peaks of polypyrrole with sodium alginate. In conclusion, the successful preparation of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 is demonstrated.
As shown in fig. 4, which is an X-ray photoelectron spectrum of polypyrrole/two-dimensional titanium carbide/sodium alginate-2, it can be seen that fluorine, oxygen, titanium, nitrogen, and carbon elements exist in the composite material.
(4) The obtained polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) was dispersed in ultrapure water to obtain 1mg mL -1 The dispersion liquid of (1) was transferred by a pipette in an amount of 5. Mu.L, and applied to the surface of an electrode, and dried by an infrared lamp, to obtain a polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) modified electrode. Then, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) modified electrode is used as a working electrode, saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and 2mol L of polypyrrole/two-dimensional titanium carbide/sodium alginate-n modified electrode is used as a working electrode, 2mol of polypyrrole/two-dimensional titanium carbide/sodium alginate-n modified electrode is used as a counter electrode, and 2mol of polypyrrole/two-dimensional titanium alginate-n modified electrode is used as a working electrode -1 H of (A) to (B) 2 SO 4 And (3) performing cyclic voltammetry test and constant current charge and discharge test on polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2 and 3) serving as an electrolyte through an electrochemical workstation.
The performance of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material prepared in this example 1 is verified as follows:
FIG. 5 shows polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) at 100mV s -1 The maximum enclosed area of polypyrrole/titanium carbide/sodium alginate-2 can be seen from fig. 5, indicating that it has the best capacitance behavior. In addition, the closed area of the curve is an irregular rectangle, which indicates that the electrode material has both pseudo-capacitance behavior and double-layer capacitance behavior.
Fig. 6 is a cyclic voltammetry curve of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at different scanning speeds, and as the scanning speed increases, the closed area of the curve also gradually increases, but the shape remains unchanged, which indicates that the composite material has good reversibility and rate performance.
Fig. 7 shows relative contribution rates of capacitance control and diffusion control to current of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at different scanning rates, and the relative contribution rates at different scanning rates can be calculated through formula (a). As the scan rate increased, the contribution of capacitance control also increased, indicating that the dominant diffusion control of polypyrrole/titanium carbide/sodium alginate-2 electrodes gradually shifted to capacitance control at low scan rates.
In FIG. 8, the content of polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) is 1ag -1 The polypyrrole/two-dimensional titanium carbide/sodium alginate-2 has the longest charge-discharge time, which shows that the polypyrrole/two-dimensional titanium carbide/sodium alginate-2 has the largest specific capacitance. The current density at 1Ag can be calculated by the formula (b) -1 The specific capacitance of polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3) was 246 fg -1 、299F g -1 、475F g -1 、174F g -1 。
Fig. 9 is a constant current charge and discharge curve of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at different current densities, wherein the curve shape is not a strictly symmetrical triangle, and the discharge curve is slightly trailing particularly at low current densities. The electrode material is proved to have both pseudo-capacitance and double-layer capacitance characteristics.
Fig. 10 is an electrochemical ac impedance diagram of polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n =0, 1,2, 3), and the inset is a balanced circuit diagram. In a low-frequency area, the slope of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 is the largest, which shows that the expanded Warburg impedance is the smallest, and the polypyrrole/two-dimensional titanium carbide/sodium alginate-2 has a faster mass transfer capacity.
As shown in fig. 11, which is a graph of the cycle stability of polypyrrole/two-dimensional titanium carbide/sodium alginate-2, after 1500 cycles of charge and discharge, the capacitance retention rate was 81%. The polypyrrole/two-dimensional titanium carbide/sodium alginate-2 aerogel is proved to have higher stability.
i(V)＝k 1 v+k 2 v 1/2 (a)
In the formula a, i (V) represents a response current at a specific potential, V represents a scanning rate, and k 1 、k 2 Respectively representing the capacitance control and diffusion control coefficients.
In formula b, cs (F g) -1 ) Represents the specific capacitance, I (A) represents the current, Δ t(s) represents the discharge time, m (g) represents the mass of the electroactive material, and Δ V (V) represents the potential window.
Example 2
The preparation method of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material comprises the following steps:
(1) 0.1g of lithium fluoride was dissolved in 15mL of 5mol L -1 To the hydrochloric acid solution, 0.1g of titanium aluminum carbide powder was then slowly added with magnetic stirring. After etching at 35 ℃ for 20h, the supernatant was washed several times with ultrapure water by centrifugation until the pH of the supernatant was about 6.8. Then the multilayer two-dimensional titanium carbide aqueous solution is subjected to ultrasonic treatment for 1 hour after being bubbled with nitrogen for 15 min. Centrifuging at 3500rpm for 1h, and collecting supernatant of monolayer two-dimensional titanium carbide colloid. The supernatant was collected in a glass bottle and nitrogen was continuously purged for 20min and then stored in a refrigerator at 4 ℃ until use.
(2) An equal volume of 30mL of 0.05mol L -1 Calcium chloride and 0.05mol L -1 The sodium carbonate solution was placed in water and ethylene glycol (volume ratio 1. Subsequently, the synthesized calcium carbonate particles were collected by centrifugal washing with ethanol, methanol, and acetone at 10000rpm in order to remove unreacted ions and ethylene glycol, and then dried at 50 ℃ for use.
(3) Measuring 5mL of ultrapure water into a 30mL glass sample bottle, adding 0.1g of sodium alginate, uniformly stirring by magnetic force, adding 200mg of pyrrole, and uniformly stirring to form sol. Then measuring 5mL of the two-dimensional sample obtained in the step (1)Titanium carbide colloid (about 24.35 mg), then weighing 1mg of calcium carbonate particles prepared in the step (2) respectively and dissolving in the sol, and magnetically stirring for 2h. Then, 1mL of 2.28mg L was slowly added dropwise -1 Ammonium persulfate solution, stirring for 10s to form black hydrogel. Placing hydrogel in refrigerator at 4 deg.C for polymerization, freeze drying at-58 deg.C for 24 hr, and placing in 0.1mol L -1 And soaking in a hydrochloric acid solution for 1h to completely etch the calcium carbonate particles, repeatedly cleaning with ultrapure water, and freeze-drying to obtain the three-dimensional porous polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material. The polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material prepared in this example 2 has similar properties to those of the polypyrrole/two-dimensional titanium carbide/sodium alginate-2 prepared in example 1.
Example 3:
the preparation method of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material comprises the following steps:
(1) 2g of lithium fluoride was dissolved in 25mL of 10mol L -1 To the hydrochloric acid solution, 2g of titanium aluminum carbide powder was then slowly added with magnetic stirring. After etching at 35 ℃ for 30h, the supernatant was washed by centrifugation with ultrapure water several times until the pH of the supernatant was 7.2. Then the multilayer two-dimensional titanium carbide aqueous solution is subjected to ultrasonic treatment for 1 hour after being bubbled with nitrogen for 30min. Centrifuging at 3500rpm for 1h, and collecting supernatant of monolayer two-dimensional titanium carbide colloid. The supernatant was collected in a glass bottle and nitrogen was continuously purged for 20min and then stored in a refrigerator at 4 ℃ until use.
(2) An equal volume of 60mL of 0.2mol L -1 Calcium chloride and 0.2mol L -1 The sodium carbonate solution was mixed and placed in water and ethylene glycol (volume ratio 1. Subsequently, the synthesized calcium carbonate particles were collected by centrifugal washing with ethanol, methanol, and acetone at 10000rpm in order to remove unreacted ions and ethylene glycol, and then dried at 100 ℃ for use.
(3) Weighing 15mL of ultrapure water into a 30mL glass sample bottle, adding 0.5g of sodium alginate, uniformly stirring by magnetic force, adding 300mg of pyrrole, and uniformly stirring to form sol. Then measuring 5mL of the two-dimensional titanium carbide colloid (about 24.35 mg) obtained in the step (1), and respectively measuring 120mg of the calcium carbonate particles prepared in the step (2) to be dissolved on the two-dimensional titanium carbide colloidIn the sol, stirring is carried out for 5 hours by magnetic force. Then, 1mL of 2.28mg L was slowly added dropwise -1 Ammonium persulfate solution, stirring for 10s to form black hydrogel. Placing hydrogel in refrigerator at 4 deg.C for polymerization, freeze drying at-58 deg.C for 24 hr, and placing in 1mol L -1 And soaking in a hydrochloric acid solution for 3 hours to completely etch the calcium carbonate particles, repeatedly cleaning with ultrapure water, and freeze-drying to obtain the three-dimensional porous polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material. The polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material prepared in this example 3 has similar properties to those of the polypyrrole/two-dimensional titanium carbide/sodium alginate-2 prepared in example 1.
Comparative example 1:
the preparation of polypyrrole comprises the following steps:
(1) 270mg of pyrrole is weighed and dissolved in 10mL of ultrapure water under the ice bath condition, and the solution is stirred uniformly. Slowly adding 1mL2.28mg L -1 And (4) putting the ammonium persulfate solution in a refrigerator at 4 ℃ for reaction for 24 hours. And repeatedly washing the product with ultrapure water and absolute ethyl alcohol, and drying in an oven at 60 ℃.
(2) The resulting polypyrrole was dispersed in ultrapure water to give 1mg mL -1 Transferring 5 mu L of the dispersion liquid by using a liquid transfer gun, dripping the dispersion liquid on the surface of an electrode, and drying by using an infrared lamp to obtain the polypyrrole modified electrode. Then, taking a polypyrrole modified electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum sheet electrode as a counter electrode, and obtaining 2mol L of the electrode -1 H of (A) to (B) 2 SO 4 And (3) carrying out cyclic voltammetry test and constant current charge and discharge test on the polypyrrole by an electrochemical workstation. According to the constant current charging and discharging test chart of polypyrrole in fig. 8, the polypyrrole can be obtained by calculation according to the formula (b) and the current density is 1Ag -1 Specific capacitance of 45 Fg -1 。
Comparative example 2:
the preparation of the two-dimensional titanium carbide nanosheet comprises the following steps:
(1) 1g of lithium fluoride was dissolved in 20mL 9mol L -1 To the hydrochloric acid solution, 1g of titanium aluminum carbide powder was then slowly added with magnetic stirring. After etching at 35 ℃ for 24h, it was washed by multiple centrifugation with ultrapure water until the pH of the supernatant was about7. And then the multilayer two-dimensional titanium carbide aqueous solution is further subjected to ultrasonic treatment for 1h after bubbling for 20min by nitrogen. Centrifuging at 3500rpm for 1h, and collecting monolayer two-dimensional titanium carbide colloid as supernatant. The supernatant was collected in a glass bottle and nitrogen was continuously purged for 20min and then stored in a refrigerator at 4 ℃. The method for calculating the concentration of the two-dimensional titanium carbide colloid comprises the following steps: weighing 10mL of supernatant in a culture dish, freeze-drying, and weighing to obtain a concentration of about 4.87mg mL -1 。
(2) The obtained two-dimensional titanium carbide was dispersed in ultrapure water to obtain 1mg mL -1 The dispersion liquid is transferred by a liquid transfer gun to obtain 5 mu L of dispersion liquid which is dripped on the surface of the electrode and dried by an infrared lamp, and the two-dimensional titanium carbide modified electrode is obtained. Then, a two-dimensional titanium carbide modified electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and 2mol L of the platinum sheet electrode is used -1 H of (A) to (B) 2 SO 4 And performing cyclic voltammetry test and constant current charge and discharge test on the two-dimensional titanium carbide as electrolyte through an electrochemical workstation. According to the constant current charge-discharge test chart of the two-dimensional titanium carbide in FIG. 8, the current density of the two-dimensional titanium carbide is 1Ag by calculation according to the formula (b) -1 Specific time capacitance of 62 Fg -1 。
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is characterized by adopting a one-pot method to prepare the polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material, freezing and drying the polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material, and completely etching calcium carbonate particles on the surface of the polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material by adopting hydrochloric acid to obtain the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material with a three-dimensional porous structure.
2. A preparation method of a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is characterized by comprising the following steps:
(1) Weighing sodium alginate, adding into ultrapure water, magnetically stirring, adding pyrrole, uniformly stirring to form sol, adding single-layer two-dimensional titanium carbide and calcium carbonate particles, magnetically stirring, slowly dropwise adding an ammonium persulfate solution, magnetically stirring to form black gel, and standing in a refrigerator at 4 ℃ until pyrrole is completely polymerized;
(2) And (3) freeze-drying, soaking in hydrochloric acid solution to completely etch calcium carbonate particles, repeatedly cleaning with ultrapure water, and freeze-drying to obtain the three-dimensional porous polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material.
3. The preparation method according to claim 2, wherein the mass ratio of the sodium alginate, the pyrrole, the monolayer two-dimensional titanium carbide and the calcium carbonate particles is 0.1-0.5g -1 。
4. The preparation method according to claim 2, wherein the magnetic stirring time is 2 to 5 hours, and the concentration of the hydrochloric acid is 0.1 to 1mol L -1 And the etching time is 1-3 h.
5. The preparation method according to claim 2, wherein the single-layer two-dimensional titanium carbide is prepared by the following specific steps: weighing lithium fluoride, dissolving the lithium fluoride in a hydrochloric acid solution, slowly adding titanium aluminum carbide under magnetic stirring, etching at room temperature, centrifugally washing with ultrapure water for a plurality of times until the pH of the centrifugal supernatant is 6.8-7.2, collecting multilayer two-dimensional titanium carbide supernatant, introducing nitrogen for bubbling, carrying out ultrasonic treatment, collecting monolayer two-dimensional titanium carbide colloid supernatant after centrifugation, continuously introducing nitrogen, obtaining monolayer two-dimensional titanium carbide, and storing in a refrigerator at 4 ℃.
6. The method of claim 5The mass-to-volume ratio of the lithium fluoride to the hydrochloric acid solution to the titanium aluminum carbide is 0.1 to 2g, and is in the range from 0.1 to 2g to 15 to 25ml, preferably the mass-to-volume ratio of the lithium fluoride to the hydrochloric acid solution to the titanium aluminum carbide is 1g -1 (ii) a The etching time is 20-30 h, and the nitrogen gas introduction time is 15-30 min.
7. The method according to claim 2, wherein the calcium carbonate particles are prepared by a process comprising: weighing equal-volume calcium chloride solution and sodium carbonate solution, placing in a mixed solution of water and ethylene glycol, magnetically stirring, sequentially centrifuging and washing with ethanol, methanol and acetone, collecting precipitate, namely calcium carbonate particles, and drying.
8. The method according to claim 7, wherein the concentration of each of the calcium chloride solution and the sodium carbonate solution is 0.05 to 0.2mol L -1 Preferably 0.1mol L -1 The volumes of the calcium chloride solution and the sodium carbonate solution are both 30-60 mL; the volume ratio of the water to the ethylene glycol is 1-15, the magnetic stirring time is 20-40 min, and the drying temperature is 50-100 ℃.
9. Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. Use of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material according to claim 9 as an electrode material of a supercapacitor.
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| CN110942921A (en) * | 2019-11-26 | 2020-03-31 | 北京科技大学 | Preparation method of novel three-dimensional composite aerogel electrode material |
| CN111422873A (en) * | 2020-03-23 | 2020-07-17 | 北京化工大学 | MXene/sodium alginate derived carbon three-dimensional aerogel and preparation method and application thereof |
| CN111883366A (en) * | 2020-07-28 | 2020-11-03 | 陕西科技大学 | Polypyrrole nanosphere @ titanium carbide composite material and preparation method and application thereof |
| CN113426428A (en) * | 2021-06-28 | 2021-09-24 | 武汉大学 | Polyaniline-sulfur nitrogen MXene/sodium alginate composite gel adsorbent and preparation method and application thereof |
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| CN110942921A (en) * | 2019-11-26 | 2020-03-31 | 北京科技大学 | Preparation method of novel three-dimensional composite aerogel electrode material |
| CN111422873A (en) * | 2020-03-23 | 2020-07-17 | 北京化工大学 | MXene/sodium alginate derived carbon three-dimensional aerogel and preparation method and application thereof |
| CN111883366A (en) * | 2020-07-28 | 2020-11-03 | 陕西科技大学 | Polypyrrole nanosphere @ titanium carbide composite material and preparation method and application thereof |
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