CN113277554A - Bismuth oxide/titanium carbide composite material and preparation method thereof - Google Patents
Bismuth oxide/titanium carbide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN113277554A CN113277554A CN202110557195.XA CN202110557195A CN113277554A CN 113277554 A CN113277554 A CN 113277554A CN 202110557195 A CN202110557195 A CN 202110557195A CN 113277554 A CN113277554 A CN 113277554A
- Authority
- CN
- China
- Prior art keywords
- titanium carbide
- bismuth oxide
- composite material
- bismuth
- carbide composite
- 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.)
- Pending
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 189
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 109
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002715 modification method Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000004729 solvothermal method Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
- H01G11/46—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Abstract
The invention relates to a bismuth oxide/titanium carbide composite material and a preparation method thereof, wherein the preparation method comprises the steps of taking titanium carbide as a substrate, adding a soluble bismuth source, ethanol and ethylene glycol to form a liquid-phase reaction system to obtain a suspension, heating the suspension at 120-160 ℃ for 5-12 h, and calcining the obtained product at 300-400 ℃ for 2-3 h in an inert atmosphere to obtain the bismuth oxide/titanium carbide composite material. In the bismuth oxide/titanium carbide composite material, bismuth oxide is uniformly dispersed among layers and on the surface of titanium carbide, and in the bismuth oxide/titanium carbide composite material, the distance between titanium carbide layers is increased compared with unmodified titanium carbide, the specific capacitance of the composite material is remarkably improved, the electrochemical performance is improved, and the bismuth oxide/titanium carbide composite material has a wide application prospect in the field of super capacitors.
Description
Technical Field
The invention relates to a titanium carbide modification technology, in particular to a bismuth oxide/titanium carbide composite material and a preparation method thereof.
Background
Titanium carbide (Ti)3C2Tx) The graphene is a two-dimensional transition metal carbide, has high specific surface area, high hydrophilicity, good conductivity and high chemical stability, has a layered structure similar to graphene, can provide high electric double layer capacitance, reaction plane and pseudocapacitance due to the characteristics, and has wide application prospect as an electrode material of a super capacitor. The theoretical capacitance of bismuth oxide reaches up to 1370F/g, the potential window is suitable, the cost is low, and the bismuth oxide is nontoxic, and is a pseudocapacitance material with excellent comprehensive performance.
The intrinsic structure and the capacitance performance of the electrode material are key factors determining the performance of the super capacitor, for example, the large specific capacitance, the high rate performance and the good cycling stability are the guarantee that the super capacitor obtains excellent electrochemical performance. However, conventional titanium carbide has a problem of general capacitance performance, which is generally related to factors such as specific surface area and pseudocapacitance. In the prior art, the capacitive performance is improved by modifying titanium carbide.
At present, the modification methods of titanium carbide materials include ion intercalation modification method, electrochemical deposition method, emulsion polymerization method and other methods. Among them, the ion intercalation method increases the interlayer distance by inserting ions into the interlayer of titanium carbide to weaken the interlayer adhesion, and has a disadvantage that the sensitivity of ion intercalation is related to the surrounding environment, which limits the amount of substances inserted into titanium carbide. The electrochemical deposition method is easy to realize and flexible in process, but voltage and current can be unstable, so that the prepared material is not uniform, and the performance is influenced. The emulsion polymerization method has high polymerization reaction speed, can prepare high molecular weight conductive polymer and titanium carbide composite, for example, CN111883366A discloses a polypyrrole nanosphere @ titanium carbide composite material, and the preparation method utilizes a low-temperature chemical oxidation methodCompounding PPy and ultrathin titanium carbide to obtain Ti3C2The @ PPy composite nanosphere material is used as an electrode material of a supercapacitor. However, the method needs the processes of demulsification, washing, dehydration, drying and the like, and the process is difficult to control.
In addition to the disadvantages of the above-mentioned methods themselves, by attempting the existing titanium carbide modification schemes, the following problems have been found to exist: (1) the existing modification technology such as an ion intercalation modification method can increase the interlayer spacing and improve the electric double layer capacitance performance of titanium carbide, but the improvement on the pseudo-capacitance performance is small. (2) The existing modification methods of titanium carbide, such as ion intercalation modification, electrochemical deposition method, emulsion polymerization method and the like, are difficult to realize effective regulation and control of the spacing of titanium carbide layers, so that the electrochemical performance of the titanium carbide is single. (3) The existing load modification methods such as an electrochemical deposition method and an emulsion polymerization method are difficult to uniformly disperse load materials among layers and on the surface of titanium carbide, and the particle size of the load materials cannot be effectively regulated, so that the overall performance is not uniform. (4) The existing modification technologies, such as electrochemical deposition method and emulsion polymerization method, can effectively improve the structure and electrochemical properties of titanium carbide, but still need to be improved in production cost and production period.
Patent application CN110586149A discloses a variety of bismuth molybdate/titanium carbide heterojunction two-dimensional photocatalytic materials, the preparation method comprises: preparing massive titanium carbide; preparing titanium carbide nanosheets by using dimethyl sulfoxide; the two-dimensional photocatalytic material is prepared through a hydrothermal reaction. However, the photocatalytic material is used for generating photoproduction electrons and holes under the excitation of illumination, the electrons have strong reducing capability and can react with dissolved oxygen in water to generate superoxide radicals and hydroxyl radicals; the photogenerated holes have strong oxidizing property and can react with water to generate hydroxyl radicals, and the generated active radicals and the photogenerated holes have oxidizing capability and can attack pollution, so that pollutants are completely removed. Obviously, the action mechanism of the photocatalytic material is irrelevant to the performance of the capacitor, and actually, the photocatalytic material and the capacitor material have no mutual common knowledge in reality.
Disclosure of Invention
The invention aims to overcome the defects of the existing titanium carbide as a capacitor material and provides a preparation method of a bismuth oxide/titanium carbide composite material.
The inventor considers that the easy stacking of titanium carbide sheets and the small pseudocapacitance performance are main reasons for restricting the performance of titanium carbide in the super capacitor. Therefore, the inventor seeks a simple and efficient modification method capable of remarkably improving stacking among titanium carbide layers and improving pseudo capacitance, so that the high-performance titanium carbide composite material has a wider application prospect in the field of supercapacitors.
The invention provides a preparation method of a bismuth oxide/titanium carbide composite material, which preferably takes bismuth nitrate pentahydrate as a bismuth source, titanium carbide as a matrix and ethylene glycol and ethanol as a solvent and a dispersant to form a liquid phase reaction system. The amorphous bismuth oxide/titanium carbide composite precursor is formed by low-temperature heating. And (2) carrying out heat treatment crystallization at a lower calcining temperature in an inert atmosphere to obtain the bismuth oxide/titanium carbide composite material, wherein the lamellar structure of the titanium carbide is clear, and spherical bismuth oxide with the particle size of 5-150 nm is uniformly loaded between layers and on the surface of the titanium carbide.
The method creatively loads the bismuth oxide between the layers and on the surface of the titanium carbide, effectively improves the lamination stacking of the titanium carbide and promotes the double-electric-layer capacitance and the pseudo capacitance. The bismuth oxide/titanium carbide composite precursor is formed by heating the system at low temperature and high pressure, so that the bismuth oxide is uniformly dispersed among titanium carbide layers and on the surface of the titanium carbide layers, the bismuth oxide can be crystallized into a spherical shape by calcining at 300-400 ℃ in an inert atmosphere, and the effective regulation and control of the spacing between the titanium carbide layers and the nano size of the bismuth oxide can be realized by controlling the loading amount. As can be seen from the above description, the preparation method has the advantages of simple process, wide raw material sources and the like.
The specific scheme is as follows:
a preparation method of a bismuth oxide/titanium carbide composite material comprises the steps of taking titanium carbide as a substrate, adding a soluble bismuth source, ethanol and ethylene glycol to form a liquid phase reaction system to obtain a suspension, heating the suspension at 120-160 ℃ for 5-12 hours, and calcining the obtained product at 300-400 ℃ for 2-3 hours in an inert atmosphere to obtain the bismuth oxide/titanium carbide composite material.
Further, the soluble bismuth source is bismuth nitrate pentahydrate, and the molar ratio of bismuth elements in the titanium carbide and the bismuth nitrate pentahydrate is 1-30, preferably 3-10, and more preferably 4-6.
Further, the preparation method of the bismuth oxide/titanium carbide composite material comprises the following steps:
step S10, weighing titanium carbide, soluble bismuth source bismuth nitrate pentahydrate, glycol and ethanol, stirring and performing ultrasonic treatment to form suspension;
step S20, transferring the suspension prepared in the previous step into a high-pressure reaction kettle, and heating for 5-12 hours at 120-160 ℃ to obtain an amorphous bismuth oxide/titanium carbide composite precursor;
and step S30, calcining the composite precursor for 2-3 hours at 300-400 ℃ in an inert atmosphere to obtain the bismuth oxide/titanium carbide composite material.
Further, in step S10, the molar ratio of bismuth element in the titanium carbide and the bismuth nitrate pentahydrate is 1 to 30; the volume ratio of the ethanol to the glycol solvent is 1-4;
optionally, the volume of the mixed solvent composed of ethylene glycol and ethanol in the suspension is: the mass of titanium carbide is 1000 mL: 7-8 g.
Further, in step S20, the suspension prepared in the previous step is transferred to a high-pressure reaction kettle and heated at 130-150 ℃ for 5-12 hours.
Further, in step S30, the composite precursor is calcined for 2-3 hours at 320-370 ℃ under an inert atmosphere.
The bismuth oxide/titanium carbide composite material is prepared by the preparation method, wherein bismuth oxide is uniformly dispersed among layers and on the surface of titanium carbide, and the distance between titanium carbide layers in the bismuth oxide/titanium carbide composite material is increased compared with unmodified titanium carbide.
The invention also discloses a bismuth oxide/titanium carbide composite material, wherein in the bismuth oxide/titanium carbide composite material, bismuth oxide is uniformly dispersed among layers and on the surface of titanium carbide, the bismuth oxide is in a nano-sphere shape, and the particle size of the bismuth oxide is 5-150 nm.
The invention also protects an electrode comprising the bismuth oxide/titanium carbide composite material.
The invention also protects a super capacitor comprising the electrode.
Has the advantages that:
firstly, the invention provides a preparation method of a bismuth oxide/titanium carbide composite material, which adopts a soluble bismuth source, and loads bismuth oxide between layers and on the surface of titanium carbide to prevent the stacking between the titanium carbide layers, increase the specific surface area, improve the double electric layer capacitance of the titanium carbide, and simultaneously the bismuth oxide can also provide a large pseudo capacitance.
Secondly, the method can realize effective regulation and control of the spacing between the titanium carbide layers and the grain size of the bismuth oxide by controlling the load capacity of the bismuth oxide, thereby developing diversified products.
In addition, in the composite material prepared by the invention, bismuth oxide can be uniformly distributed between layers and on the surface of titanium carbide, so that the uniformity of the overall performance is realized.
In a word, the preparation method provided by the invention has the advantages of wide raw material source, short preparation period and low cost.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is an XRD diffraction spectrum of the bismuth oxide/titanium carbide composite material and titanium carbide prepared in example 1.
Fig. 2 is an SEM photograph of the bismuth oxide/titanium carbide composite material prepared in example 1.
FIG. 3 is a cyclic voltammogram of the bismuth oxide/titanium carbide composite prepared in example 1.
Fig. 4 is a constant current charge and discharge curve diagram of the bismuth oxide/titanium carbide composite material prepared in example 1.
Fig. 5 is an SEM photograph of the bismuth oxide/titanium carbide composite material prepared in example 2.
Fig. 6 is an SEM photograph of the bismuth oxide/titanium carbide composite material prepared in example 3.
Fig. 7 is an SEM photograph of untreated titanium carbide of comparative example 1.
Fig. 8 is an SEM photograph of titanium carbide treated in comparative example 1.
Fig. 9 is an SEM photograph of the bismuth oxide/titanium carbide composite material prepared in comparative example 2.
Fig. 10 is an SEM photograph of the bismuth oxide/titanium carbide composite material prepared in comparative example 3.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
A preparation method of a bismuth oxide/titanium carbide composite material comprises the following steps:
(1) 0.5g of titanium carbide and 0.26g of bismuth nitrate pentahydrate are weighed respectively, added into a mixed solution consisting of 13mL of ethylene glycol and 52mL of ethanol, and subjected to magnetic stirring and ultrasonic treatment for 10min to form a suspension.
(2) And transferring the prepared suspension to a 100mL Teflon container, finally putting the suspension into a stainless steel high-pressure reaction kettle, heating the suspension for 5 hours at 160 ℃, taking out the suspension after the heating, and washing and drying the suspension to form the amorphous bismuth oxide/titanium carbide composite precursor.
(3) The composite precursor is at N2Calcining for 2h at 300 ℃ in the atmosphere to obtain the bismuth oxide/titanium carbide composite material.
The XRD test and the electron microscope test were performed on the samples, and the results are shown in fig. 1 and fig. 2, respectively. Fig. 1 shows XRD diffraction spectra of bismuth oxide/titanium carbide composite material and titanium carbide, and it can be seen from fig. 1 that a diffraction peak (ICDD # 71-2274) of bismuth oxide appears in the product, a peak located at about 9 ° is a (002) characteristic peak of titanium carbide, the corresponding interplanar spacing is 0.988nm, and the interplanar spacing of the (002) peak in the bismuth oxide/titanium carbide composite material is 1.004nm, which is 0.016nm greater than that before modification of titanium carbide, indicating that the interplanar spacing of the titanium carbide layer is increased.
FIG. 2 is an SEM photograph of the bismuth oxide/titanium carbide composite material, and it can be seen from FIG. 2 that a small amount of spherical bismuth oxide of 5-30 nm is uniformly loaded between layers and on the surface of titanium carbide, and the lamellar structure of titanium carbide is obvious.
A three-electrode system is adopted for evaluating electrochemical performance, a 6M KOH solution is taken as electrolyte, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as a counter electrode, and bismuth oxide/titanium carbide composite material and titanium carbide are taken as working electrodes. Fig. 3 and 4 are a cyclic voltammetry curve and a constant current charge and discharge curve of the bismuth oxide/titanium carbide composite material, respectively, and it can be seen from fig. 3 and 4 that the bismuth oxide/titanium carbide composite material has good electrochemical performance. When the current density is 0.2A/g, the specific capacitance of the titanium carbide is 64.8F/g, the specific capacitance of the bismuth oxide/titanium carbide composite material is 136.1F/g, and the specific capacitance is increased by 71.3F/g.
Example 2
A preparation method of a bismuth oxide/titanium carbide composite material comprises the following steps:
(1) 0.5g of titanium carbide and 0.45g of bismuth nitrate pentahydrate are weighed respectively, added into a mixed solution consisting of 13mL of ethylene glycol and 52mL of ethanol, and subjected to magnetic stirring and ultrasonic treatment for 10min to form a suspension.
(2) And transferring the prepared suspension to a 100mL Teflon container, finally putting the suspension into a stainless steel high-pressure reaction kettle, heating the suspension for 5 hours at 160 ℃, taking out the suspension after the heating, washing, drying and treating to form the amorphous bismuth oxide/titanium carbide composite precursor.
(3) The composite precursor is at N2Calcining for 2h at 300 ℃ in the atmosphere to obtain the bismuth oxide/titanium carbide composite material.
The distance between the (002) peak and the corresponding crystal face of the bismuth oxide/titanium carbide composite material prepared in the embodiment is 1.013nm, which is 0.025nm higher than that of the titanium carbide before modification, and shows that the distance between the titanium carbide layers is increased.
FIG. 5 is an SEM photograph of the bismuth oxide/titanium carbide composite material, and it can be seen from FIG. 5 that a large amount of 5-30 nm spherical bismuth oxide is mainly and uniformly distributed between titanium carbide layers, a small amount of 80-150 nm coarse spherical bismuth oxide is mainly distributed on the surface of a titanium carbide sheet, and the titanium carbide sheet has an obvious structure.
A three-electrode system is adopted for evaluating electrochemical performance, a 6M KOH solution is taken as electrolyte, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as a counter electrode, and bismuth oxide/titanium carbide composite material and titanium carbide are taken as working electrodes. When the current density is 0.2A/g, the specific capacitance of the titanium carbide is 64.8F/g, the specific capacitance of the bismuth oxide/titanium carbide composite material is 183F/g, and the specific capacitance is increased by 118.2F/g after modification.
Example 3
A preparation method of a bismuth oxide/titanium carbide composite material comprises the following steps:
(1) 0.5g of titanium carbide and 0.12g of bismuth nitrate pentahydrate are weighed respectively, added into a mixed solution consisting of 13mL of ethylene glycol and 52mL of ethanol, and subjected to magnetic stirring and ultrasonic treatment for 10min to form a suspension.
(2) And transferring the prepared suspension to a 100mL Teflon container, finally putting the suspension into a stainless steel high-pressure reaction kettle, heating the suspension for 5 hours at 160 ℃, taking out the suspension after the heating, and washing and drying the suspension to form the amorphous bismuth oxide/titanium carbide composite precursor.
(3) The composite precursor is at N2Calcining for 2h at 300 ℃ in the atmosphere to obtain the bismuth oxide/titanium carbide composite material.
The distance between the (002) peak of the bismuth oxide/titanium carbide composite material prepared in this example and the corresponding crystal face is 0.995nm, which is 0.007nm greater than that of the titanium carbide before modification, which indicates that the distance between the titanium carbide layers is increased, fig. 6 is an SEM photograph of the bismuth oxide/titanium carbide composite material, and it can be seen from fig. 6 that a small amount of 5-30 nm spherical bismuth oxide is mainly and uniformly distributed between the titanium carbide layers, and a small amount of 80-150 nm coarse spherical bismuth oxide is mainly distributed on the surface of the titanium carbide sheet.
A three-electrode system is adopted for evaluating electrochemical performance, a 6M KOH solution is taken as electrolyte, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as a counter electrode, and bismuth oxide/titanium carbide composite material and titanium carbide are taken as working electrodes. When the current density is 0.2A/g, the specific capacitance of the titanium carbide is 64.8F/g, the specific capacitance of the bismuth oxide/titanium carbide composite material is 91F/g, and the specific capacitance is increased by 26.2F/g.
Comparative example 1
The preparation method of the titanium carbide composite material comprises the following steps:
(1) 0.5g of titanium carbide was weighed, and added to a mixed solution of 13mL of ethylene glycol and 52mL of ethanol, and magnetic stirring and ultrasonic treatment were performed for 10min to form a suspension.
(2) Transferring the prepared suspension to a 100mL Teflon container, finally putting the prepared suspension together into a stainless steel high-pressure reaction kettle, carrying out solvothermal reaction for 5h at 160 ℃, and taking out the suspension after the solvothermal reaction is finished, and washing and drying the suspension.
(3) In N2Calcining for 2h at 300 ℃ in the atmosphere to obtain the treated titanium carbide.
Fig. 7 is an SEM photograph of untreated titanium carbide, and fig. 8 is an SEM photograph of treated titanium carbide of this comparative example, from which it can be seen that the lamellar structure of titanium carbide is not significantly changed, and that both have a lamellar stacking phenomenon. A three-electrode system is adopted for evaluating electrochemical performance, and 6M KOH solution is taken as electrolyte, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as a counter electrode, and titanium carbide is taken as a working electrode. At a current density of 0.2A/g, the specific capacitance of the untreated titanium carbide was 64.8F/g, the specific capacitance of the treated titanium carbide was 53F/g, the specific capacitance was reduced by 11.8F/g, and the electrochemical performance was slightly reduced.
Comparative example 2
The preparation method of the titanium carbide composite material comprises the following steps:
(1) 0.5g of titanium carbide and 0.26g of bismuth nitrate pentahydrate are weighed and added into a mixed solution of 10mL of DMF solvent and 65mL of deionized water, and magnetic stirring and ultrasonic treatment are carried out for 10min to form a suspension.
(2) And transferring the prepared suspension to a 100mL Teflon container, finally putting the suspension into a stainless steel high-pressure reaction kettle together, carrying out solvothermal reaction for 12h at 120 ℃, taking out the suspension after the solvothermal reaction is finished, and carrying out washing and drying treatment to form the amorphous bismuth oxide/titanium carbide composite precursor.
(3) The composite precursor is at N2Calcining for 2h at 300 ℃ in the atmosphere to obtain the titanium carbide composite material.
Fig. 9 is an SEM photograph of the bismuth oxide/titanium carbide composite material, and it is understood from the figure that the bismuth oxide particle size is not uniform, the whole is large, and the bismuth oxide particle size is mainly distributed on the surface of the titanium carbide and is not uniform. A three-electrode system is adopted for evaluating electrochemical performance, a 6M KOH solution is taken as electrolyte, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as a counter electrode, and titanium carbide composite material and titanium carbide are taken as working electrodes. When the current density is 0.2A/g, the specific capacitance of the titanium carbide is 64.8F/g, the specific capacitance of the titanium carbide composite material is 71F/g, the specific capacitance is increased by 6.2F/g, and the electrochemical performance improvement effect is not obvious.
Comparative example 3
The preparation method of the titanium carbide composite material comprises the following steps:
the method comprises the following steps:
(1) 0.5g of titanium carbide and 0.69g of bismuth nitrate pentahydrate are weighed respectively, added into a mixed solution consisting of 13mL of ethylene glycol and 52mL of ethanol, and subjected to magnetic stirring and ultrasonic treatment for 10min to form a suspension.
(2) And transferring the prepared suspension to a 100mL Teflon container, finally putting the suspension into a stainless steel high-pressure reaction kettle, heating the suspension for 5 hours at 160 ℃, taking out the suspension after the heating, and washing and drying the suspension to form the amorphous bismuth oxide/titanium carbide composite precursor.
(3) The composite precursor is at N2Calcining for 2h at 300 ℃ in the atmosphere to obtain the bismuth oxide/titanium carbide composite material.
FIG. 10 is an SEM photograph of the bismuth oxide/titanium carbide composite material, and it can be seen that the titanium carbide is covered with a large amount of coarse spherical bismuth oxide of 80 to 150nm, so that the interlayer structure is not obvious.
A three-electrode system is adopted for evaluating electrochemical performance, a 6M KOH solution is taken as electrolyte, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as a counter electrode, and bismuth oxide/titanium carbide composite material and titanium carbide are taken as working electrodes. When the current density is 0.2A/g, the specific capacitance of titanium carbide is 64.8F/g, the specific capacitance of the bismuth oxide/titanium carbide composite material is 164.1F/g, and the specific capacitance is increased by 99.3F/g, which shows that when the molar ratio of titanium carbide to bismuth is 2:1, the electric double layer capacitance of the titanium carbide is influenced by excessive bismuth oxide load, so that the capacitance performance is reduced. Thus, when the molar ratio of titanium carbide to bismuth is less than 2:1, the capacitive properties of the material gradually decrease with increasing bismuth source.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a bismuth oxide/titanium carbide composite material is characterized by comprising the following steps: titanium carbide is used as a substrate, a soluble bismuth source, ethanol and glycol are added to form a liquid phase reaction system, a suspension is obtained, then the suspension is heated for 5-12 hours at 120-160 ℃, the obtained product is calcined for 2-3 hours at 300-400 ℃ under inert atmosphere, and the bismuth oxide/titanium carbide composite material is obtained.
2. The method for preparing a bismuth oxide/titanium carbide composite material according to claim 1, wherein: the soluble bismuth source is bismuth nitrate pentahydrate, and the molar ratio of bismuth elements in titanium carbide and the bismuth nitrate pentahydrate is 1-30.
3. The method for preparing a bismuth oxide/titanium carbide composite material according to claim 2, wherein: the method comprises the following steps:
step S10, weighing titanium carbide, soluble bismuth source bismuth nitrate pentahydrate, glycol and ethanol, stirring and performing ultrasonic treatment to form suspension;
step S20, transferring the suspension prepared in the previous step into a high-pressure reaction kettle, and heating for 5-12 hours at 120-160 ℃ to obtain an amorphous bismuth oxide/titanium carbide composite precursor;
and step S30, calcining the composite precursor for 2-3 hours at 300-400 ℃ in an inert atmosphere to obtain the bismuth oxide/titanium carbide composite material.
4. The method for preparing a bismuth oxide/titanium carbide composite material according to claim 3, wherein: in the step S10, the molar ratio of the titanium carbide to the bismuth element in the bismuth nitrate pentahydrate is 1-30; the volume ratio of the ethanol to the glycol solvent is 1-4;
optionally, the volume of the mixed solvent composed of ethylene glycol and ethanol in the suspension is: the mass of titanium carbide is 1000 mL: 7-8 g.
5. The method for producing a bismuth oxide/titanium carbide composite material according to claim 3 or 4, characterized in that: in step S20, the suspension prepared in the previous step is transferred to a high-pressure reaction kettle and heated at 130-150 ℃ for 5-12 h.
6. The method for producing a bismuth oxide/titanium carbide composite material according to claim 3 or 4, characterized in that: step S30, calcining the composite precursor for 2-3 h at 320-370 ℃ in an inert atmosphere.
7. A bismuth oxide/titanium carbide composite material prepared by the preparation method of any one of claims 1 to 6, wherein the preparation method comprises the following steps: in the bismuth oxide/titanium carbide composite material, bismuth oxide is uniformly dispersed among layers and on the surface of titanium carbide, and in the bismuth oxide/titanium carbide composite material, the distance between titanium carbide layers is increased compared with that of unmodified titanium carbide.
8. A bismuth oxide/titanium carbide composite material is characterized in that: in the bismuth oxide/titanium carbide composite material, bismuth oxide is uniformly dispersed among layers and on the surface of titanium carbide, the bismuth oxide is in a nanometer spherical shape, and the particle size of the bismuth oxide is 5-150 nm.
9. An electrode comprising the bismuth oxide/titanium carbide composite material according to claim 7 or 8.
10. A supercapacitor comprising the electrode of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110557195.XA CN113277554A (en) | 2021-05-21 | 2021-05-21 | Bismuth oxide/titanium carbide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110557195.XA CN113277554A (en) | 2021-05-21 | 2021-05-21 | Bismuth oxide/titanium carbide composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113277554A true CN113277554A (en) | 2021-08-20 |
Family
ID=77280787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110557195.XA Pending CN113277554A (en) | 2021-05-21 | 2021-05-21 | Bismuth oxide/titanium carbide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113277554A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491417A (en) * | 2011-11-30 | 2012-06-13 | 江苏技术师范学院 | Method for preparing ball-flower-shaped gamma-bismuth trioxide powder |
| CN105609319A (en) * | 2016-01-29 | 2016-05-25 | 西北师范大学 | Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material |
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| US10014124B1 (en) * | 2017-09-27 | 2018-07-03 | King Saud University | Composite electrode material for supercapacitors |
| CN108704658A (en) * | 2018-06-04 | 2018-10-26 | 西南石油大学 | A kind of preparation method of bismuth oxide and nitrogen carbide nanosheet composite material |
| CN109888203A (en) * | 2019-01-16 | 2019-06-14 | 五邑大学 | Tellurium adulterates MXene composite material and preparation method and application |
| CN109950050A (en) * | 2019-04-17 | 2019-06-28 | 武汉工程大学 | A kind of preparation method based on carbonization melamine foamed plastic@Bi2O3 nanometer sheet electrode material for super capacitor |
| CN109994325A (en) * | 2019-03-29 | 2019-07-09 | 江苏大学 | A kind of preparation method of bismuth oxide/N doping carbon dots hollow porous micro sphere negative electrode material |
| CN110706938A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Preparation method of supercapacitor electrode material |
| CN112479178A (en) * | 2020-12-10 | 2021-03-12 | 哈尔滨理工大学 | Preparation method of lignin carbon/bismuth oxide composite material and pseudo-capacitance performance thereof |
-
2021
- 2021-05-21 CN CN202110557195.XA patent/CN113277554A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491417A (en) * | 2011-11-30 | 2012-06-13 | 江苏技术师范学院 | Method for preparing ball-flower-shaped gamma-bismuth trioxide powder |
| CN105609319A (en) * | 2016-01-29 | 2016-05-25 | 西北师范大学 | Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material |
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| US10014124B1 (en) * | 2017-09-27 | 2018-07-03 | King Saud University | Composite electrode material for supercapacitors |
| CN108704658A (en) * | 2018-06-04 | 2018-10-26 | 西南石油大学 | A kind of preparation method of bismuth oxide and nitrogen carbide nanosheet composite material |
| CN110706938A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Preparation method of supercapacitor electrode material |
| CN109888203A (en) * | 2019-01-16 | 2019-06-14 | 五邑大学 | Tellurium adulterates MXene composite material and preparation method and application |
| CN109994325A (en) * | 2019-03-29 | 2019-07-09 | 江苏大学 | A kind of preparation method of bismuth oxide/N doping carbon dots hollow porous micro sphere negative electrode material |
| CN109950050A (en) * | 2019-04-17 | 2019-06-28 | 武汉工程大学 | A kind of preparation method based on carbonization melamine foamed plastic@Bi2O3 nanometer sheet electrode material for super capacitor |
| CN112479178A (en) * | 2020-12-10 | 2021-03-12 | 哈尔滨理工大学 | Preparation method of lignin carbon/bismuth oxide composite material and pseudo-capacitance performance thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sayyed et al. | Nano-metal oxide based supercapacitor via electrochemical deposition | |
| Misnon et al. | High performance MnO2 nanoflower electrode and the relationship between solvated ion size and specific capacitance in highly conductive electrolytes | |
| Vijayakumar et al. | Supercapacitor studies on NiO nanoflakes synthesized through a microwave route | |
| Hu et al. | Al-doped α-MnO2 for high mass-loading pseudocapacitor with excellent cycling stability | |
| Salunkhe et al. | Chemical synthesis and electrochemical analysis of nickel cobaltite nanostructures for supercapacitor applications | |
| Babakhani et al. | Anodic deposition of manganese oxide electrodes with rod-like structures for application as electrochemical capacitors | |
| Sun et al. | Efficient utilization of oxygen-vacancies-enabled NiCo2O4 electrode for high-performance asymmetric supercapacitor | |
| TR201605860T1 (en) | HYBRID FOAM CONTAINING METAL OXIDE CLAMPED GRAFENE AND CARBON NANOTUBE. | |
| Kolathodi et al. | MnO2 encapsulated electrospun TiO2 nanofibers as electrodes for asymmetric supercapacitors | |
| Kumar et al. | Ruthenium oxide nanostring clusters anchored Graphene oxide nanocomposites for high-performance supercapacitors application | |
| CN107934965B (en) | Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material | |
| Kim et al. | Synthesis of microsphere silicon carbide/nanoneedle manganese oxide composites and their electrochemical properties as supercapacitors | |
| Oh et al. | Carbon-coated Si/MnO2 nanoneedle composites with optimum carbon layer activation for supercapacitor applications | |
| Purusottam-Reddy et al. | Microstructure and supercapacitive properties of rf-sputtered copper oxide thin films: influence of O 2/Ar ratio | |
| Pan et al. | High-performance asymmetric supercapacitors based on core/shell cobalt oxide/carbon nanowire arrays with enhanced electrochemical energy storage | |
| Iwueke et al. | A novel chemical preparation of Ni (OH) 2/CuO nanocomposite thin films for supercapacitive applications | |
| Kavil et al. | Titania nanotubes dispersed graphitic carbon nitride nanosheets as efficient electrode materials for supercapacitors | |
| Yang et al. | Nitrogen-doped black titania for high performance supercapacitors | |
| Kang et al. | Simple fabrication of nickel sulfide nanostructured electrode using alternate dip-coating method and its supercapacitive properties | |
| Wang et al. | Electrochemical and textural characterization of binary Ru–Sn oxides synthesized under mild hydrothermal conditions for supercapacitors | |
| Dubal et al. | Three‐dimensional arrays of 1D MnO2 nanocrystals for all‐solid‐state asymmetric supercapacitors | |
| Wang et al. | Preparation of mesoporous TiO 2-B nanowires from titanium glycolate and their application as an anode material for lithium-ion batteries | |
| Chavhan et al. | Vertically aligned MnO2 nanosheet electrode of controllable mass loading, counter to nanoparticulate carbon film electrode for use in supercapacitor | |
| Li et al. | Effects of electrode thickness and crystal water on pseudocapacitive performance of layered birnessite MnO2 | |
| Han et al. | Cycling stability of iron-based layered double hydroxide thin-films for battery-type electrode materials |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210820 |