CN115483037B - 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
- Publication number
- CN115483037B CN115483037B CN202211136289.0A CN202211136289A CN115483037B CN 115483037 B CN115483037 B CN 115483037B CN 202211136289 A CN202211136289 A CN 202211136289A CN 115483037 B CN115483037 B CN 115483037B
- Authority
- CN
- China
- Prior art keywords
- titanium carbide
- sodium alginate
- polypyrrole
- dimensional titanium
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 124
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 96
- 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 54
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 54
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 54
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000004964 aerogel Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 74
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000004108 freeze drying Methods 0.000 claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 239000006228 supernatant Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 24
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 23
- 239000012498 ultrapure water Substances 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 20
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007772 electrode material Substances 0.000 claims description 13
- 239000002356 single layer Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000084 colloidal system Substances 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000463 material Substances 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 35
- 229910052708 sodium Inorganic materials 0.000 description 35
- 239000011734 sodium Substances 0.000 description 35
- 150000002500 ions Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000011521 glass 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011263 electroactive material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation 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
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000379 polymerizing effect 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
- 238000012546 transfer Methods 0.000 description 2
- 150000003624 transition metals Chemical class 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
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000012795 verification 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
-
- 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
Landscapes
- 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 relates to a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and a preparation method and application thereof, belonging to the technical field of material synthesis. According to the preparation method, a polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material is prepared by adopting a one-pot method, freeze drying is carried out, and hydrochloric acid is adopted to completely etch 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. The preparation method of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material provided by the invention is simple and easy to implement, and the composite material has higher specific capacitance and better cycle stability when being used for the supercapacitor electrode.
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
Super capacitors are considered to be products with great development prospects in the energy storage field 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 the cycle life of the super capacitors are still insufficient to meet the increasing demands of novel energy storage devices. According to the difference of charge storage principles, supercapacitors are mainly divided into two categories: electrochemical double layer capacitors and pseudocapacitors. The former stores charge electrostatically by ion adsorption on the electrode surface, and a carbon material with a large surface area is generally used as the electrode material; the capacitance of pseudocapacitors results from a rapid and reversible redox reaction process at the interface, typically using transition metal oxides, sulfides, hydroxides, and conductive polymers as electrode materials. In order to obtain high and stable specific capacitance, the key point is to design an electroactive material, and the electrochemical performance of the electrode material is often improved by controlling the microstructure, such as specific surface area, pores and other characteristics of the electroactive material.
Accordingly, many researchers have employed pseudocapacitive materials such as conductive polymers, polypyrroles, etc., which have been attracting attention from researchers due to their ease of synthesis and high conductivity. Polypyrrole has the advantages of large pseudo-capacitance, simple synthesis, low cost and the like, and is widely applied to research of supercapacitor electrode materials. However, polypyrrole causes a volume change during high-speed circulation due to repeated doping/dedoping of ions, resulting in deterioration of circulation stability. Therefore, polypyrrole can be compounded with other materials with stronger mechanical properties to improve specific capacitance and stability.
In recent years, two-dimensional transition metal carbides and nitrides (also referred to as mxnes) have received widespread 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 metal, X represents a carbon or nitrogen atom, and T represents a surface termination functional group (-OH, -O, -F); MXenes have electrochemically active centers derived from rapid conversion of transition metals with different valencies and rapid redox reactions of surface terminating functional groups, with conductivities up to 10000S cm -1 . Among them, two-dimensional titanium carbide has attracted great attention as an electrode material for supercapacitors. In addition, it has excellent characteristics of electrode materials such as high rate performance, high power density, excellent cycle stability, high energy density, and the like. However, as with graphene, self-aggregation occurs due to strong van der Waals interactions between adjacent nano-sheets of two-dimensional titanium carbide, so that permeation of electrolyte ions is seriously hindered, and electrochemical performance and practical application of the two-dimensional titanium carbide electrode material are limited. To solve these problems, heterostructure electrode materials of two-dimensional titanium carbide and other high specific capacitance compounds have been fabricated to increase the interlayer spacing of two-dimensional titanium carbide and thus the electrochemical performance thereof。
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, a preparation method and application thereof. Therefore, the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material has great potential as an electrode material of the supercapacitor.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
on the one hand, the invention provides a preparation method of a polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material, which comprises the steps of preparing the polypyrrole/two-dimensional titanium carbide/sodium alginate/calcium carbonate hydrogel composite material by adopting a one-pot method, freeze-drying, and completely etching surface calcium carbonate particles 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.
The preparation method of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is characterized by comprising the following steps of:
(1) Weighing sodium alginate, adding the sodium alginate 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 ammonium persulfate solution, magnetically stirring to form black gel, and standing in a refrigerator at 4 ℃ until pyrrole is completely polymerized;
(2) 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 single-layer two-dimensional titanium carbide to the calcium carbonate particles is as follows:0.1-0.5 g, 0.2-0.3 g, 20-30 mg, 1-120 mg, wherein the mass and volume ratio of the sodium alginate, the ultrapure water and the ammonium persulfate solution is 0.1-0.5 g, 5-15 mL, 0.1-1.5 mL, and the concentration of the ammonium persulfate solution is 1.5-2.5 mol L -1 。
The preparation method is characterized in that the magnetic stirring time is 2-5 h, and the concentration of the hydrochloric acid is 0.1-1 mol L -1 The etching time is 1-3 h.
The preparation method comprises the following specific steps of: weighing lithium fluoride, dissolving in hydrochloric acid solution, slowly adding titanium aluminum carbide under magnetic stirring, etching at room temperature, centrifugally washing with ultrapure water for several times until the pH of the supernatant is 6.8-7.2, collecting multilayer two-dimensional titanium carbide supernatant, introducing nitrogen for bubbling, performing ultrasonic treatment, centrifuging, collecting single-layer two-dimensional titanium carbide colloid supernatant, continuously introducing nitrogen, and storing in a refrigerator at 4 ℃. The two-dimensional titanium carbide colloid concentration calculating method comprises the following steps: a certain volume of supernatant is measured in a culture dish, the mass is weighed after freeze drying, and the concentration is calculated.
According to the preparation method, the mass and volume ratio of the lithium fluoride, the hydrochloric acid solution and the titanium aluminum carbide is as follows: 0.1-2 g, 15-25 mL, 0.1-2 g, preferably lithium fluoride, hydrochloric acid solution and titanium aluminum carbide, wherein the mass to volume ratio of the hydrochloric acid solution to the titanium aluminum carbide is 1g, 20mL and 1g, and the concentration of the hydrochloric acid solution is 5-10 mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The etching time is 20-30 h, and the nitrogen introducing time is 15-30 min.
The preparation method comprises the following steps of: weighing equal volume of equal concentration calcium chloride solution and sodium carbonate solution, mixing, placing in mixed solution of water and glycol, magnetically stirring, sequentially centrifuging with ethanol, methanol and acetone to remove unreacted ions and glycol, collecting precipitate, namely calcium carbonate particles, and oven drying.
The concentration 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 30-60 mL; the water and glycolThe volume ratio of the powder to the powder is 1:2-15, 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 the use of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material as an electrode material of a supercapacitor.
The principle of the invention is as follows: polypyrrole has higher specific capacitance, and polypyrrole and sodium alginate can form three-dimensional network structure aerogel, and the electrochemical performance is reduced because of easy agglomeration among sheets of two-dimensional titanium carbide nano sheets, so that the interval among sheets can be increased by dispersing the two-dimensional titanium carbide nano sheets in an aerogel network, thereby improving the electrochemical performance. And finally, taking the calcium carbonate particles as a sacrificial template, so that the 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 easy to implement, 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 supercapacitor electrode.
Drawings
FIG. 1 is a scanning electron micrograph of titanium aluminum carbide (A), two-dimensional titanium carbide (B), calcium carbonate particles (C) and a particle diameter distribution diagram (D) of the calcium carbonate particles prepared in example 1;
fig. 2 is a scanning electron microscope image 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/two-dimensional titanium carbide/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 scan rate;
FIG. 6 is a cyclic voltammogram of polypyrrole/two dimensional titanium carbide/sodium alginate-2 prepared in example 1 at different sweep rates;
FIG. 7 is a graph showing the relative contribution of capacitance control and diffusion control to current at different scan rates for polypyrrole/two dimensional titanium carbide/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;
FIG. 9 is a constant current charge-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 diagram 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 internal marks of balanced circuit diagram;
FIG. 11 is a graph showing the cyclic stability of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 prepared in example 1.
Detailed Description
The present invention will be further described with reference to the accompanying 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 24 hours, the supernatant was washed with ultrapure water by centrifugation several times until the pH of the supernatant was 7. And then the multilayer two-dimensional titanium carbide water is usedThe solution was sonicated for 1 hour after bubbling with nitrogen for 20min. The supernatant was collected as a monolayer of two-dimensional titanium carbide colloid by centrifugation at 3500rpm for 1h. Collecting the supernatant in a glass bottle, continuously introducing nitrogen for 20min, and then storing in a refrigerator at 4 ℃ for standby. The two-dimensional titanium carbide colloid concentration calculating method comprises the following steps: 10mL of supernatant was weighed into a petri dish, and the supernatant was freeze-dried to give a mass concentration of about 4.87mg mL -1 . As shown in fig. 1 (a) and (B) which are scanning electron microscope images of the titanium aluminum carbide block and the single-layer two-dimensional titanium carbide nano-sheet respectively, it can be seen that the single-layer two-dimensional titanium carbide nano-sheet has been successfully prepared; FIG. 1 (C) shows synthesized calcium carbonate particles, and it can be seen from FIG. 1 (D) that the particle diameter of the calcium carbonate particles is in the range of 0.6 to 1.4. Mu.m.
(2) Will equal 0.1mol L -1 Calcium chloride and 0.1mol L -1 The sodium carbonate solution is placed in water and glycol (volume ratio is 1:5) and magnetically stirred for 30min. 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) 10mL of ultrapure water is measured and put in a 30mL glass sample bottle, 0.3g of sodium alginate is added, after magnetic stirring is uniform, 270mg of pyrrole is added and stirring is uniform, and sol is formed. Then, 5mL of the two-dimensional titanium carbide colloid (about 24.35 mg) obtained in the step (1) is measured, and 0, 10, 50 and 100mg of the calcium carbonate particles prepared in the step (2) are respectively weighed and dissolved in the sol, and magnetically stirred for 3 hours. 1mL of 2.28mg L was then slowly added dropwise -1 The ammonium persulfate solution was stirred for 10s to form a black hydrogel. Placing the hydrogel in a refrigerator at 4deg.C for completely polymerizing pyrrole, freeze drying at-58 deg.C for 24 hr, and placing in 0.5mol L -1 Soaking in hydrochloric acid solution for 2 hours 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 different masses of 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 the masses of added calcium carbonate of 0, 10, 50 and 100 mg).
Fig. 2 (a), (B), (C) and (D) are scanning electron microscope images of polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2 and 3), respectively. From fig. 2 (a), it can be seen that when no calcium carbonate particles are added to the aerogel, the voids on the aerogel surface are less; as the content of calcium carbonate particles increases, the pore size of the aerogel surface becomes progressively larger, as: fig. 2 (B) (C) (D). In particular, it can be seen from FIG. 2 (D) that the aerogel surface has larger cavities, probably because of agglomeration due to too much calcium carbonate particles content, so that the larger cavities remain after etching.
Fig. 3 shows X-ray powder diffraction patterns of polypyrrole, two-dimensional titanium carbide, sodium alginate, polypyrrole/two-dimensional titanium carbide/sodium alginate-2 and titanium aluminum carbide, wherein the peak of polypyrrole at 2θ=15° to 35 ° is an amorphous characteristic peak of polypyrrole. In diffraction peaks of the titanium aluminum carbide precursor and the two-dimensional titanium carbide, the titanium aluminum carbide corresponds to (002), (004), (104) and (110) crystal planes (JCPDS No. 52-0875) in 2θ=9.55 °,19.00 °,38.75 °,60.34 °, respectively. Notably, the diffraction peaks of the two-dimensional titanium carbide at the (002) and (004) crystal planes were shifted to lower angles than before etching, indicating that the aluminum layer in the titanium aluminum carbide could 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 the removal of the aluminum layer and the successful preparation of the two-dimensional titanium carbide. The broad peak of sodium alginate at 2θ=13.50°, 22.50 ° is a characteristic peak of amorphous polymer structure with lower sodium alginate crystallinity. Diffraction peaks of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at 2θ=6.07°, 17.49 ° correspond to (002), (004) crystal planes of two-dimensional titanium carbide, respectively; the diffraction peak at 2θ=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 and sodium alginate. In summary, the successful preparation of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 is described.
As shown in FIG. 4, the X-ray photoelectron spectrum of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 shows that fluorine, oxygen, titanium, nitrogen and carbon elements exist in the composite material.
(4) Dispersing the obtained polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3) into ultrapure water to obtain 1mg mL -1 Respectively, 5. Mu.L of the dispersion of (C) was dispensed by a pipetteAnd drying the surface of the electrode by using an infrared lamp to obtain the polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2 and 3) modified electrode. Then the polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3) modified electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, and 2mol L of the electrode is used as a counter electrode -1 H of (2) 2 SO 4 As electrolyte, cyclic voltammetry test and constant current charge and discharge test were performed on polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3) by an electrochemical workstation.
The polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material prepared in this example 1 has the following performance verification:
as shown in FIG. 5, polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3) was at 100mV s -1 The maximum enclosed area of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 is seen from figure 5, indicating the best capacitive behavior. In addition, the closed area of the curve is an irregular rectangle, which indicates that the electrode material has pseudocapacitive behavior and electric double layer capacitive behavior at the same time.
Fig. 6 shows cyclic voltammograms of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at different scanning speeds, and the closed area of the curve gradually increases with the increase of the scanning speed, but the shape remains unchanged, which indicates that the composite material has good reversibility and rate capability.
Fig. 7 shows the relative contribution rate of the capacitance control and the diffusion control of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 to the current at different scanning rates, and the relative contribution at different scanning rates can be calculated by the formula (a). As the scan rate increases, the contribution of capacitance control increases, indicating that the dominant diffusion control of the polypyrrole/two-dimensional titanium carbide/sodium alginate-2 electrode at low scan rates gradually translates into capacitance control.
FIG. 8 shows polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3) at 1A g -1 Constant current charge-discharge curve under current density of (2), polypyrrole/two-dimensional titanium carbide/sodium alginate-2 has longest chargeDischarge time, which indicates the maximum specific capacitance. The current density of 1Ag can be calculated by the formula (b) -1 Specific capacitances of polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3) were 246 and F g, respectively -1 、299F g -1 、475F g -1 、174F g -1 。
Fig. 9 shows constant current charge and discharge curves of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 at different current densities, wherein the curve shape is not strictly symmetrical triangle, and particularly, the discharge curve is slightly trailing at low current densities. The electrode material has both pseudocapacitance and double-layer capacitance characteristics.
Fig. 10 shows electrochemical ac impedance diagrams of polypyrrole, two-dimensional titanium carbide, polypyrrole/two-dimensional titanium carbide/sodium alginate-n (n=0, 1,2, 3), and the inset shows a balanced circuit diagram. In a low frequency region, the gradient of polypyrrole/two-dimensional titanium carbide/sodium alginate-2 is maximum, which shows that the Warburg expansion impedance is minimum, and the mass transfer capability is faster.
As shown in FIG. 11, which is a graph of cyclic stability of polypyrrole/two-dimensional titanium carbide/sodium alginate-2, the retention rate of capacitance was 81% after 1500 cycles of charge and discharge. The polypyrrole/two-dimensional titanium carbide/sodium alginate-2 aerogel has higher stability.
i(V)＝k 1 v+k 2 v 1/2 (a)
In the formula a, i (V) represents the response current at a specific potential, V represents the scan rate, k 1 、k 2 Representing the capacitance control and diffusion control coefficients, respectively.
In formula b, cs (F g -1 ) Representing the specific capacitance, I (a) representing the current, Δt(s) representing the discharge time, m (g) representing the mass of the electroactive material, Δv (V) representing 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 20 hours, the supernatant was washed with ultrapure water by centrifugation several times until the pH of the supernatant was about 6.8. The aqueous solution of the multilayer two-dimensional titanium carbide was then bubbled with nitrogen for 15 minutes and then sonicated for 1 hour. The supernatant was collected as a monolayer of two-dimensional titanium carbide colloid by centrifugation at 3500rpm for 1h. Collecting the supernatant in a glass bottle, continuously introducing nitrogen for 20min, and then storing in a refrigerator at 4 ℃ for standby.
(2) An equal volume of 30mL of 0.05mol L -1 Calcium chloride and 0.05mol L -1 The sodium carbonate solution is placed in water and glycol (volume ratio is 1:2) and magnetically stirred for 20min. 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) 5mL of ultrapure water is measured and put into a 30mL glass sample bottle, 0.1g of sodium alginate is added, and after magnetic stirring is uniform, 200mg of pyrrole is added and stirring is uniform, so that sol is formed. Then, 5mL of the two-dimensional titanium carbide colloid (about 24.35 mg) obtained in the step (1) was measured, and 1mg of the calcium carbonate particles prepared in the step (2) were respectively weighed and dissolved in the sol, and magnetically stirred for 2 hours. 1mL of 2.28mg L was then slowly added dropwise -1 The ammonium persulfate solution was stirred for 10s to form a black hydrogel. Placing the hydrogel in a refrigerator at 4deg.C for completely polymerizing pyrrole, freeze drying at-58 deg.C for 24 hr, and placing in 0.1mol L -1 Soaking in hydrochloric acid solution for 1h 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. The polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material prepared in this example 2 has similar properties as those of 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 are 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 30 hours, the supernatant was washed with ultrapure water by centrifugation several times until the pH of the supernatant was 7.2. The aqueous solution of the multilayer two-dimensional titanium carbide was then subjected to ultrasonic treatment for 1 hour after bubbling with nitrogen gas for 30 minutes. The supernatant was collected as a monolayer of two-dimensional titanium carbide colloid by centrifugation at 3500rpm for 1h. Collecting the supernatant in a glass bottle, continuously introducing nitrogen for 20min, and then storing in a refrigerator at 4 ℃ for standby.
(2) An equal volume of 60mL of 0.2mol L -1 Calcium chloride and 0.2mol L -1 The sodium carbonate solution was mixed, placed in water and ethylene glycol (volume ratio 1:15) and magnetically stirred for 40min. 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) 15mL of ultrapure water is measured and put in a 30mL glass sample bottle, 0.5g of sodium alginate is added, after magnetic stirring is uniform, 300mg of pyrrole is added and stirring is uniform, and sol is formed. Then, 5mL of the two-dimensional titanium carbide colloid (about 24.35 mg) obtained in the step (1) was measured, 120mg of the calcium carbonate particles prepared in the step (2) were respectively weighed and dissolved in the sol, and the solution was magnetically stirred for 5 hours. 1mL of 2.28mg L was then slowly added dropwise -1 The ammonium persulfate solution was stirred for 10s to form a black hydrogel. Placing the hydrogel in refrigerator at 4deg.C for complete polymerization, freeze drying at-58 deg.C for 24 hr, and placing in 1mol L -1 Soaking in hydrochloric acid solution for 3 hours 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. The polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material prepared in this example 3 had similar properties as those described above to 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) Under ice bath conditions, 270mg of pyrrole was weighed and dissolved in 10mL of ultrapure water, and stirred well. 1mL of 2.28mg L was slowly added dropwise -1 The ammonium persulfate solution was placed in a refrigerator at 4℃for reaction for 24 hours. The product is treated with ultrapure water,Repeatedly washing with absolute ethanol, and drying in oven at 60deg.C.
(2) The polypyrrole obtained was dispersed in ultrapure water to obtain 1mg mL -1 And (3) transferring 5 mu L of the dispersion liquid to the surface of the electrode by using a liquid transferring gun, and drying by using an infrared lamp to obtain the polypyrrole modified electrode. Then the polypyrrole modified electrode is used as a working electrode, the saturated calomel electrode is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, and 2mol L -1 H of (2) 2 SO 4 And (3) performing cyclic voltammetry test and constant current charge and discharge test on polypyrrole as electrolyte through an electrochemical workstation. According to the constant current charge-discharge test chart of polypyrrole in FIG. 8, the current density of polypyrrole at 1Ag can be calculated by the formula (b) -1 The time specific capacitance was 45F g -1 。
Comparative example 2:
the preparation of the two-dimensional titanium carbide nano-sheet 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 24 hours, the supernatant was washed with ultrapure water by centrifugation several times until the pH of the supernatant was about 7. The aqueous solution of the multilayer two-dimensional titanium carbide was further subjected to ultrasonic treatment for 1 hour after bubbling with nitrogen for 20 minutes. The mixture was centrifuged at 3500rpm for 1 hour, and a single layer of two-dimensional titanium carbide colloid was collected as a supernatant. The supernatant was collected in a glass bottle, continuously purged with nitrogen for 20min, and then stored in a refrigerator at 4 ℃. The two-dimensional titanium carbide colloid concentration calculating method comprises the following steps: 10mL of supernatant was weighed into a petri dish, and the supernatant was freeze-dried to give a mass concentration of about 4.87mg mL -1 。
(2) The obtained two-dimensional titanium carbide was dispersed in ultrapure water to obtain 1mg mL -1 And (3) transferring 5 mu L of the dispersion liquid to the surface of the electrode by using a liquid transferring gun, and drying by using an infrared lamp to obtain the two-dimensional titanium carbide modified electrode. Then the 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 -1 H of (2) 2 SO 4 And (3) carrying out cyclic voltammetry test and constant current charge and discharge test on the two-dimensional titanium carbide serving as electrolyte through an electrochemical workstation. According to FIG. 8, the constant of two-dimensional titanium carbideThe current charge-discharge test chart can be calculated to obtain the two-dimensional titanium carbide with the current density of 1A g through the formula (b) -1 Time specific capacitance of 62F g -1 。
The foregoing is only a preferred embodiment of the invention, it being 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 present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (9)
1. The preparation method of the 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, freeze-drying, and completely etching surface calcium carbonate particles 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;
specifically, the preparation method comprises the following steps:
(1) Weighing sodium alginate, adding the sodium alginate 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 ammonium persulfate solution, magnetically stirring to form black gel, and standing in a refrigerator at 4 ℃ until pyrrole is completely polymerized;
(2) 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;
the mass ratio of the sodium alginate to the pyrrole to the single-layer two-dimensional titanium carbide to the calcium carbonate particles is 0.1-0.5 g to 0.2-0.3 g to 20-30 mg to 1-120 mg, the mass ratio of the sodium alginate to the ultrapure water to the ammonium persulfate solution to the volume ratio is 0.1-0.5 g to 5-15 mL to 0.1-1.5 mL, and the concentration of the ammonium persulfate solution is 1.5-2.5 mol L ‒1 ；
The magnetic stirring time is 2-5 h, and the concentration of the hydrochloric acid is 0.1-1 mol L ‒1 The etching time is 1-3 h.
2. The preparation method according to claim 1, wherein the preparation process of the single-layer two-dimensional titanium carbide specifically comprises the following steps: weighing lithium fluoride, dissolving in hydrochloric acid solution, slowly adding titanium aluminum carbide under magnetic stirring, etching at room temperature, centrifugally washing with ultrapure water for several times until the pH of the supernatant is 6.8-7.2, collecting multilayer two-dimensional titanium carbide supernatant, introducing nitrogen for bubbling, performing ultrasonic treatment, centrifuging, collecting single-layer two-dimensional titanium carbide colloid supernatant, continuously introducing nitrogen, and storing in a refrigerator at 4 ℃.
3. The preparation method according to claim 2, wherein the mass to volume ratio of the lithium fluoride, the hydrochloric acid solution and the titanium aluminum carbide is 0.1-2 g:15-25 mL:0.1-2 g, and the concentration of the hydrochloric acid solution is 5-10 mol L ‒1 The method comprises the steps of carrying out a first treatment on the surface of the The etching time of the titanium aluminum carbide is 20-30 h, and the time of introducing nitrogen is 15-30 min.
4. The method of claim 2, wherein the mass to volume ratio of lithium fluoride, hydrochloric acid solution, and titanium aluminum carbide is 1g:20ml:1g.
5. The preparation method according to claim 1, wherein the preparation process of the calcium carbonate particles specifically comprises: measuring an equal volume of a calcium chloride solution and a sodium carbonate solution with equal concentration, placing the calcium chloride solution and the sodium carbonate solution into a mixed solution of water and glycol, magnetically stirring the mixture for 20 to 40 minutes, sequentially and continuously centrifugally washing the mixture by ethanol, methanol and acetone, collecting precipitates, namely calcium carbonate particles, and drying the precipitates.
6. The process according to claim 5, wherein the concentration of the calcium chloride solution and the sodium carbonate solution is 0.05 to 0.2mol L ‒1 The volumes of the calcium chloride solution and the sodium carbonate solution are 30-60 mL; the volume ratio of the water to the glycol is 1:2-15, and the drying temperature is 50-to-50%100℃。
7. The method according to claim 5, wherein the concentration of the calcium chloride solution and the sodium carbonate solution is 0.1mol L ‒1 。
8. A polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material, characterized in that the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material is prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material as described in claim 8 as an electrode material for super capacitors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211136289.0A CN115483037B (en) | 2022-09-19 | 2022-09-19 | Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211136289.0A CN115483037B (en) | 2022-09-19 | 2022-09-19 | Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115483037A CN115483037A (en) | 2022-12-16 |
| CN115483037B true CN115483037B (en) | 2023-10-31 |
Family
ID=84423496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211136289.0A Active CN115483037B (en) | 2022-09-19 | 2022-09-19 | Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115483037B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473646A (en) * | 2018-10-30 | 2019-03-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method and application of sulphur-polypyrrole-two-dimensional layer carbonization titanium composite material |
| 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 |
-
2022
- 2022-09-19 CN CN202211136289.0A patent/CN115483037B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473646A (en) * | 2018-10-30 | 2019-03-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method and application of sulphur-polypyrrole-two-dimensional layer carbonization titanium composite material |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115483037A (en) | 2022-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102723209B (en) | Preparation method for graphene nanosheet/conducting polymer nanowire composite material | |
| Liu et al. | Rational design of freestanding and high-performance thick electrode from carbon foam modified with polypyrrole/polydopamine for supercapacitors | |
| WO2013010346A1 (en) | Lithium-ion battery negative electrode-use silicon-carbon composite material and preparation method therefor | |
| Ye et al. | Electrochemical growth of polyaniline nanowire arrays on graphene sheets in partially exfoliated graphite foil for high-performance supercapacitive materials | |
| CN111627719B (en) | Conductive polymer hollow sphere PACP @ titanium carbide composite material and preparation method thereof | |
| Alvi et al. | Electrochemical supercapacitors based on graphene-conducting polythiophenes nanocomposite | |
| CN112011094A (en) | Nano cellulose MXene gel and preparation method and application thereof | |
| CN105885410A (en) | Molybdenum sulfide/polypyrrole/polyaniline ternary composite material as well as preparation method and application thereof | |
| CN111710529B (en) | Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof | |
| Darwish et al. | Polyanionic electrically conductive superabsorbent hydrogel based on sodium alginate-g-poly (AM-co-ECA-co-AMPS): Broadband dielectric spectroscopy investigations | |
| CN115483037B (en) | Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite material and preparation method and application thereof | |
| CN108010734A (en) | A kind of micro super capacitor production method based on graphene/carbon nano-tube aeroge | |
| CN109336083B (en) | Method for controllably preparing foam carbon/carbon nanotube composite material by high internal phase emulsion template method | |
| CN114974916B (en) | Fibrous MXene-loaded NiCoS composite material and preparation method and application thereof | |
| CN110491679B (en) | Graphene oxide-polythiophene composite material and supercapacitor based on same | |
| Qi et al. | Electronically conductive MXene clay-polymer composite binders for electrochemical double-layer capacitor electrodes | |
| CN109087820A (en) | Graphene combination electrode material is prepared in situ in sonochemical method | |
| CN116130256A (en) | Preparation method and application of tungsten oxide nanowire/titanium carbide nanosheet composite material | |
| CN110648856B (en) | Graphene material, preparation method thereof and supercapacitor | |
| CN111348689B (en) | A kind of Ni (OH)2Graphene composite material and preparation method thereof | |
| CN111599600B (en) | Preparation method and application of graphene/iron oxyhydroxide/polyaniline supercapacitor positive electrode material | |
| CN112409028A (en) | CC-NiO-CuCoS composite material and preparation method and application thereof | |
| Chang et al. | Surface-hydrophilic-modified carbon aerogels via surface-initiated electrochemically mediated atom transfer radical polymerization for high-performance supercapacitors | |
| CN111363146B (en) | Preparation method of polyaniline/capacitance carbon-based composite material, product and application thereof | |
| Weerasinghe et al. | Performance evaluation of polyaniline-based redox capacitors with respect to polymerization current density. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20221216 Assignee: Jingbaiyuan Semiconductor (Shandong) Co.,Ltd. Assignor: CHANGZHOU University Contract record no.: X2024980014664 Denomination of invention: Polypyrrole/two-dimensional titanium carbide/sodium alginate aerogel composite and its preparation method and application Granted publication date: 20231031 License type: Common License Record date: 20240910 |
|
| EE01 | Entry into force of recordation of patent licensing contract |