CN115346803A - W 18 O 49 Carbon paper composite electrode material and preparation method thereof - Google Patents
W 18 O 49 Carbon paper composite electrode material and preparation method thereof Download PDFInfo
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- CN115346803A CN115346803A CN202210927414.3A CN202210927414A CN115346803A CN 115346803 A CN115346803 A CN 115346803A CN 202210927414 A CN202210927414 A CN 202210927414A CN 115346803 A CN115346803 A CN 115346803A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 126
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000007772 electrode material Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 30
- 239000004917 carbon fiber Substances 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 21
- 239000010937 tungsten Substances 0.000 claims abstract description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- PTKRHFQQMJPPJN-UHFFFAOYSA-N dipotassium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium;sulfuric acid Chemical compound [K+].[K+].OS(O)(=O)=O.[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O PTKRHFQQMJPPJN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 33
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- -1 tungsten alkoxides Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
- H01G11/32—Carbon-based
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a W 18 O 49 A/carbon paper composite electrode material and a preparation method thereof belong to the technical field of electrode materials of super capacitors. The invention takes carbon paper as a current collector, W 18 O 49 The oxide nano-sheet grows on the surface of the carbon fiber of the carbon paper current collector in situ to form W 18 O 49 A carbon paper composite electrode material. Placing carbon paper cleaned by ultrasonic in acetone for ultrasonic treatment for 10-20 min, then placing the carbon paper in a potassium dichromate-sulfuric acid solution for pretreatment, and washing the carbon paper by water to obtain pretreated carbon paper; ultrasonically dissolving a tungsten source in an alcohol solution to obtain a tungsten source-alcohol precursor solution; adding the pretreated carbon paper into a tungsten source-alcohol solution,sealing and reacting at 120-180 ℃ for 12-24 h, cooling to room temperature, carrying out solid-liquid separation, washing and drying the solid to obtain W 18 O 49 Carbon paper composite electrode material, W 18 O 49 The oxide nanosheets grow in situ on the surface of the carbon fibers of the carbon paper current collector. Invention W 18 O 49 The carbon paper composite electrode material has high capacitance and good cycle performance, and can solve the problems of unstable structure, poor rate performance and the like of the existing electrode material.
Description
Technical Field
The invention relates to a W 18 O 49 A/carbon paper composite electrode material and a preparation method thereof belong to the technical field of electrode materials of super capacitors.
Background
The super capacitor is one of electrochemical energy storage devices which are widely applied at present, the power density of the super capacitor is far higher than that of a storage battery, the energy density is about 10-100 times of that of a traditional capacitor, and the super capacitor has the advantages of long cycle life, high power density, high charging and discharging speed and the like. The solar energy hybrid power generation system is widely applied to the fields of solar energy systems, wind power generation systems, new energy automobiles, smart power grids and the like. The development of high-performance super capacitors with large capacity, high energy density, high power density and long life cycle is imperative.
Stoichiometric ratio of tungsten oxide other than oxygen deficient sites (WO) 3-X ) E.g. WO 2.90 (W 20 O 58 )、WO 2.83 (W 24 O 68 )、WO 2.80 (W 5 O 14 )、WO 2.72 (W 18 O 49 ) And the like. The oxides of tungsten are widely applied to various devices such as field emission devices, photocatalysis, gas sensors, electrochromic devices and the like due to unique performances such as photochromism, gasochromism, photocatalysis and the like. Wherein W is monoclinic phase 18 O 49 In WO already reported 2.625-3 The oxide with the most oxygen defects in the range is also the only oxide of tungsten known to date in non-stoichiometric proportions in pure form. Oblique phase W 18 O 49 Is the only known tungsten oxide that has the most oxygen defects and exists in pure form. W 18 O 49 Sharing W by ordered corners/edgesO 6 The grid network connected by the frame forms an open structure consisting of triangular, quadrangular and hexagonal tunnels. The inherent clearance of this structure is such that W 18 O49 is H + Good host for regulation and diffusion. Thereby having better electrochemical performance.
Further, W 18 O 49 Has strong anisotropic growth behavior in the direction, and is easy to form three-dimensional nano structures, such as nanowires, nanorods, nanobelts and the like. A large number of exposed oxygen vacancies on the surface have a large surface-to-volume ratio in a one-dimensional structure, so that the electrochemical performance is improved. W 18 O 49 Coating the W on the surface of the carbon fiber by adopting a microwave-assisted solvothermal method to coat the carbon fiber composite material 18 O 49 The nano material is only assisted by microwaves, the method is single, and the prepared nano material is paved on a carbon fiber layer, so that the prepared nano material cannot have good gaps to increase the specific surface area, thereby increasing the wettability of the electrolyte and the immersion of H + ions. The core-shell composite structure of the carbon fiber @ tungsten oxide nano-particles is prepared by firstly heating and soaking WO in a vacuum furnace at high temperature under the action of carrier gas 3 The carbon fiber of the suspension is annealed in the air at low temperature to obtain the composite material, the reaction time in the preparation process is long, high temperature is needed, and the prepared nano material cannot be directionally nucleated and grow, so that the application is limited. W with electrochromic Properties 18 O 49 /WO 3 Depositing tungsten oxide on the surface of clean transparent conductive glass by using a direct-current reactive sputtering method for the composite film, and annealing to obtain WO 3 The layer is then doped hydrothermally, the preparation process is relatively complicated, and the material obtained by the annealing process is relatively uneven. W for lithium sulfur battery electrodes 18 O 49 The nano-rod-carbon composite material is prepared by firstly carrying out hydrothermal treatment and then annealing to obtain W 18 O 49 The process is complicated and needs an annealing process to prepare W by using the nanorod-carbon composite material as the positive electrode material of the lithium-sulfur battery electrode 18 O 49 The appearance is rod-shaped, the specific surface area is smaller, and the mutual linkage is not tight; the addition of the conductive agent and the binder during the manufacturing process of the electrode material affects the theoretical active contact area of the battery.
Disclosure of Invention
Aiming at W in the prior art 18 O 49 The invention provides a W-type electrode material with the problems of poor cycle life and poor rate capability 18 O 49 The carbon paper composite electrode material is prepared by growing W on the surface of carbon fiber of carbon paper current collector in situ 18 O 49 Oxide nanosheet, W 18 O 49 The oxide nanosheet grows uniformly, contains more oxygen defects and can improve the electrochemical performance of the electrode material, W 18 O 49 The oxide nanosheets are deposited on the carbon fiber framework in situ, so that the contact area is increased, and the circulation stability and the rate capability are enhanced; therefore, W 18 O 49 The carbon paper composite electrode material has high specific capacity, good cycle performance and mechanical performance, and shows good rate capability and cycle performance when being applied to a super capacitor as an electrode.
W 18 O 49 The carbon paper composite electrode material uses carbon paper as current collector, W 18 O 49 The oxide nano-sheet grows on the surface of the carbon fiber of the carbon paper current collector in situ to form W 18 O 49 Carbon paper composite electrode material, W 18 O 49 The length of the oxide nanosheet is 100-300nm and W 18 O 49 The thickness of the oxide nanosheet layer is 5-20nm.
W is 18 O 49 The preparation method of the carbon paper composite electrode material comprises the following specific steps:
(1) Placing the carbon paper which is sequentially subjected to ultrasonic cleaning by water and ethanol in acetone for ultrasonic treatment for 10-20 min, then placing the carbon paper in a potassium dichromate-sulfuric acid solution for pretreatment, and finally washing the carbon paper by water to obtain pretreated carbon paper (hydrophilic carbon paper);
(2) Ultrasonically dissolving a tungsten source in an alcohol solution to obtain a tungsten source-alcohol precursor solution;
(3) Adding the pretreated carbon paper into a tungsten source-alcohol solution, carrying out sealing reaction at the temperature of 120-180 ℃ for 12-24 h, cooling to room temperature, carrying out solid-liquid separation, washing and drying the solid to obtain W 18 O 49 Carbon paper composite electrode material, W 18 O 49 Sodium oxideThe rice flakes grow on the surface of the carbon fiber of the carbon paper current collector in situ.
The invention realizes W by reasonably controlling the reaction time and the reaction temperature 18 O 49 Uniformly distributing on the carbon paper; the tungsten source is dissolved in the alcohol solution, under the condition of heating and heat preservation, two tungsten alkoxides are subjected to polycondensation through polycondensation reaction to form tungsten oxide and ether molecules connected by an oxygen bridge, and a carbon fiber framework is used as a substrate to uniformly grow in the nucleation process.
The water in the step (1) is deionized water, ultrapure water or distilled water.
The concentration of potassium dichromate in the potassium dichromate-sulfuric acid solution is 0.5-3 mol/L, and the concentration of sulfuric acid is 0.5-2 mol/L.
The tungsten source in the step (2) is WCl 6 、NaWO 4 、WCl 5 、W(CO) 6 、W(C 2 H 5 O) 6 (ii) a The alcoholic solution is methanol, ethanol or propanol.
The concentration of the tungsten source in the tungsten source-alcohol precursor solution is 1-8 g/L.
The solid-liquid ratio g: mL of the carbon paper pretreated in the step (3) to the tungsten source-alcohol solution is 0.08-1.
The invention grows W on the surface of the carbon fiber of the carbon paper in situ 18 O 49 Preparation of carbon paper/W from oxide nanosheets 18 O 49 Composite electrode material, W 18 O 49 The oxide nanosheets contain more oxygen defects, have larger current carriers and thus have better electrochemical performance, and W grows in situ on the carbon fiber framework of the carbon paper 18 O 49 The oxide nano-sheet enables the composite electrode to have higher conductivity, improves rate capability and prolongs cycle life. The invention grows W in situ by a one-step solvent method 18 O 49 The oxide nanosheets are directly used as electrode plates on a carbon fiber framework of carbon paper for electrochemical test, so that W can be increased 18 O 49 The oxygen defects of the oxide and no foreign substances (such as a polymer binder and a conductive agent) are introduced to affect the theoretical active contact area of the electrode sheet of the battery.
The invention has the beneficial effects that:
(1) Invention W 18 O 49 The oxide nanosheets are grown on the carbon fiber framework of the carbon paper in situ and directly used as electrode slices, so that the problem that in the electrode manufacturing process, the contact area of active substances and electrolyte is reduced due to the addition of a high-molecular binder and a conductive agent is solved, and the loss of electrochemical performance caused by the full reaction of the active substances is reduced;
(2) In-situ growth of W on the carbon fiber skeleton of the carbon paper 18 O 49 The oxide nano-sheet and the nano-composite material have uniform shape and compact coating, and the carbon paper is used as a matrix (current collector) to increase W 18 O 49 The contact area of the active material, thereby increasing electrochemical performance;
(3) Invention W 18 O 49 The carbon paper composite electrode material can directly act on a super capacitor, does not need a binder and a conductive agent, and does not introduce foreign substances while improving the conductive performance so as to enhance the electrochemical performance; compared with the method of directly coating on the current collector, the stability is stronger;
(4) Invention W 18 O 49 W in/carbon paper composite electrode material 18 O 49 The size of the oxide nanosheet is nanoscale, the nanosheets are connected with one another through whiskers, and the oxide nanosheet has a large specific surface area and high conductivity; the carbon paper used as the current collector substrate has better flexibility and processability, so that the composite electrode material can be used in flexible devices.
Drawings
FIG. 1 is a scanning electron micrograph (500 times) of unreacted carbon paper;
FIG. 2 is a scanning electron micrograph (8500 times) of a single carbon fiber of unreacted carbon paper;
FIG. 3 shows W prepared in example 1 18 O 49 Scanning electron microscopy (150 x) of the/carbon paper composite electrode material;
FIG. 4 shows W prepared in example 1 18 O 49 Scanning electron microscopy (2000 x) of carbon fibers of the/carbon paper composite electrode material;
FIG. 5 shows W prepared in example 1 18 O 49 Carbon of carbon paper composite electrode materialFiber detail scanning electron microscopy (50000 times);
FIG. 6 shows W prepared in example 1 18 O 49 X-ray diffraction patterns of the carbon paper composite electrode material and the carbon paper;
FIG. 7 shows W prepared in example 2 18 O 49 A cyclic voltammogram of the carbon paper composite electrode material at different scanning speeds;
FIG. 8 shows W prepared in example 2 18 O 49 Impedance diagram of the/carbon paper composite electrode material;
FIG. 9 shows W prepared in example 2 18 O 49 A constant current charge-discharge diagram of the carbon paper composite electrode material.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
The carbon paper is carbon fiber paper and has the characteristics of high mechanical strength, good air permeability, low resistivity, small chemical corrosion and the like; the carbon paper is made of PAN carbon fiber, has high tensile strength and high modulus fiber, the resistivity is 5m omega cm, the density is 0.44g/cm, and the thickness is 0.19mm;
carbon paper used in examples of the present invention: the individual carbon fibers were 10 μm in diameter (see fig. 1 and 2).
W 18 O 49 Carbon paper composite electrode material, which takes carbon paper as a current collector, W 18 O 49 The oxide nano-sheet grows on the surface of the carbon fiber of the carbon paper current collector in situ to form W 18 O 49 Carbon paper composite electrode material, W 18 O 49 The length of the oxide nano-sheet is 100-300nm, W 18 O 49 The thickness of the oxide nano-sheet layer is 5-20nm.
Example 1: w-shaped steel plate 18 O 49 The preparation method of the carbon paper composite electrode material comprises the following specific steps:
(1) Cutting to a thickness of 0.19mm and an area of 2cm 2 Washing (1 cm × 2 cm) carbon paper with deionized water and ethanol in 35KHz ultrasonic wave for 30min, subjecting the carbon paper to acetone ultrasonic treatment for 10min, washing with deionized water, and placing in potassium dichromatePretreating in a sulfuric acid solution for 20min, washing by deionized water, and drying to obtain pretreated carbon paper; wherein the concentration of potassium dichromate in the potassium dichromate-sulfuric acid solution is 1mol/L, and the concentration of sulfuric acid is 0.5mol/L;
(2) WCl 6 Ultrasonic dissolving in ethanol to obtain yellow and transparent WCl 6 Ethanol solution; wherein WCl 6 WCl in ethanol solution 6 The concentration is 3g/L;
(3) Addition of pretreated carbon paper to WCl 6 In ethanol solution, sealing and reacting at 150 deg.C for 24 hr, cooling to room temperature, separating solid and liquid, washing the solid with anhydrous ethanol for 3 times, and vacuum drying to obtain W 18 O 49 A/carbon paper composite electrode material; wherein the carbon paper and WCl are pretreated 6 The solid-liquid ratio g of the ethanol solution is that mL is 0.5;
prepared W 18 O 49 The electrochemical performance of the carbon paper composite electrode material as a supercapacitor electrode is characterized as follows: the test is carried out by adopting a three-electrode system electrochemical workstation, wherein the electrolyte is 1mol/L sulfuric acid aqueous solution, the counter electrode is a Pt sheet, the reference electrode is an Ag/AgCl electrode, and the working electrode is W 18 O 49 A carbon paper composite electrode;
FIGS. 1 and 2 show carbon paper after washing and before reaction, the carbon fibers are staggered and about 10 μm; rough surface of carbon fiber increases W 18 O 49 The adhesive force of (2);
W 18 O 49 scanning electron microscopy (150X) of the/carbon paper composite electrode material is shown in FIG. 3 18 O 49 Completely attached to the carbon paper and mutually connected; the scanning electron microscope image (2000 times) of single carbon fiber is shown in FIG. 4, and the carbon fiber is uniformly coated with a layer of W 18 O 49 An active substance having aggregated sea urchin-like globules on carbon fibers;
w prepared in this example 18 O 49 The detail scanning electron microscope picture (50000 times) of the carbon fiber of the carbon paper composite electrode material shows that the surface substance is formed by burr-shaped materials in the shape of a piece, and the burr-shaped materials are mutually connected, so that the conduction of electrons is facilitated, and the electrochemical performance is enhanced;
w prepared in this example 18 O 49 The X-ray diffraction pattern of the/carbon paper composite electrode material is shown in FIG. 6, and the product has a peak near 23 degrees except the peak of the carbon paper, which indicates W 18 O 49 Deposited on carbon paper to form W 18 O 49 A/carbon paper composite electrode material;
the results of this example are shown in FIG. 7, which is a cyclic voltammogram (20 to 200 mV/S) for samples at different scan rates. Significant oxidation and reduction peaks can be observed, indicating that the electrode material has pseudocapacitive properties. The redox peaks at low scan rates indicate that a strong redox reaction of the electrode material has occurred. With the increase of the scanning rate, the curve shape is not obviously changed, and the cyclic voltammetry curve still maintains the original shape, which shows that the material still has good capacitance performance under the high scanning rate; the AC impedance plot measured under the three-electrode system is shown in FIG. 8, indicating W 18 O 49 The carbon paper composite electrode material has smaller impedance which is about 1.8 omega; the constant-current charge-discharge curve of the material under different current densities is shown in FIG. 9, which shows that the material has good charge-discharge reversibility, the curve does not present a linear shape, but has obvious bending, and the fact that the electrode presents Faraday pseudo-capacitance behavior is verified; the current density of the electrode is 0.5mAcm -2 Then reaches 600mFg -1 The specific capacitance value of (2).
Example 2: w 18 O 49 The preparation method of the carbon paper composite electrode material comprises the following specific steps:
(1) Cutting to a thickness of 0.19mm and an area of 1cm 2 Washing (1 cm multiplied by 1 cm) carbon paper with deionized water and ethanol in 35KHz ultrasonic waves for 20min, performing acetone ultrasonic treatment on the carbon paper for 15min, washing with deionized water, pretreating in a potassium dichromate/sulfuric acid solution for 15min, washing with deionized water, and drying to obtain pretreated carbon paper; wherein the concentration of potassium dichromate in the potassium dichromate-sulfuric acid solution is 1.5mol/L, and the concentration of sulfuric acid is 0.8mol/L;
(2) WCl 6 Ultrasonic dissolving in ethanol to obtain yellow and transparent WCl 6 Ethanol solution; wherein WCl 6 Second aspectWCl in alcoholic solution 6 The concentration is 4g/L;
(3) Addition of pretreated carbon paper to WCl 6 In ethanol solution, sealing and reacting at 160 deg.C for 20h, cooling to room temperature, separating solid and liquid, washing the solid with anhydrous ethanol for 3 times, and vacuum drying to obtain W 18 O 49 A/carbon paper composite electrode material; wherein the carbon paper and WCl are pretreated 6 The solid-liquid ratio g of the ethanol solution is 0.3;
prepared W 18 O 49 The electrochemical performance of the carbon paper composite electrode material as a super capacitor electrode is characterized as follows: the test is carried out by adopting a three-electrode system electrochemical workstation, wherein the electrolyte is 1mol/L sulfuric acid aqueous solution, the counter electrode is a Pt sheet, the reference electrode is an Ag/AgCl electrode, and the working electrode is W 18 O 49 A carbon paper composite electrode;
the cyclic voltammetry curves (20 to 200 mV/S) of the sample at different scanning rates can observe obvious oxidation peaks and reduction peaks, and the electrode material of the cyclic voltammetry curve has pseudocapacitance characteristics; the redox peak at low scanning rate indicates that the electrode material has a strong redox reaction; with the increase of the scanning rate, the curve shape is not obviously changed, and the cyclic voltammetry curve still keeps the original shape, which shows that the material still has good capacitance performance under the high scanning rate; the alternating current impedance measured under a three-electrode system is 2.0 omega, and a constant current charging and discharging curve under different current densities does not present a linear shape but has obvious bending, so that the electrode is proved to present a Faraday pseudo-capacitance behavior; the current density of the electrode is 0.5mAcm -2 Then reaches 560mFg -1 The specific capacitance value of (2).
Example 3: w 18 O 49 The preparation method of the carbon paper composite electrode material comprises the following specific steps:
(1) Cutting to a thickness of 0.19mm and an area of 2cm 2 Washing (1 cm × 2 cm) carbon paper with deionized water and ethanol in 35KHz ultrasonic wave for 25min, subjecting the carbon paper to acetone ultrasonic treatment for 15min, washing with deionized water, pretreating in potassium dichromate/sulfuric acid solution for 25min, washing with deionized water, and drying to obtain pretreated paperCarbon paper; wherein the concentration of potassium dichromate in the potassium dichromate-sulfuric acid solution is 1mol/L, and the concentration of sulfuric acid is 1.5mol/L;
(2) Mixing WCl 6 Ultrasonic dissolving in ethanol to obtain yellow and transparent WCl 6 Ethanol solution; wherein WCl 6 WCl in ethanol solution 6 The concentration is 5g/L;
(3) Addition of pretreated carbon paper to WCl 6 In ethanol solution, sealing and reacting at 180 deg.C for 18h, cooling to room temperature, separating solid and liquid, washing solid with anhydrous ethanol for 4 times, and vacuum drying to obtain W 18 O 49 A/carbon paper composite electrode material; wherein the carbon paper and WCl are pretreated 6 The solid-liquid ratio g of the ethanol solution is 0.5;
prepared W 18 O 49 The electrochemical performance of the carbon paper composite electrode material as a supercapacitor electrode is characterized as follows: the test is carried out by adopting a three-electrode system electrochemical workstation, wherein the electrolyte is 1mol/L sulfuric acid aqueous solution, the counter electrode is a Pt sheet, the reference electrode is an Ag/AgCl electrode, and the working electrode is W 18 O 49 A carbon paper composite electrode;
the cyclic voltammetry curves (20 to 200 mV/S) of the sample at different scanning rates can observe obvious oxidation peaks and reduction peaks, and the electrode material of the cyclic voltammetry curves has pseudo-capacitance characteristics; the redox peak at low scanning rate indicates that the electrode material has a strong redox reaction; with the increase of the scanning rate, the curve shape is not obviously changed, and the cyclic voltammetry curve still keeps the original shape, which shows that the material still has good capacitance performance at high scanning rate; the alternating current impedance measured under a three-electrode system is 3 omega, and a constant current charge-discharge curve under different current densities does not present a linear shape but an obvious bend, so that the fact that the electrode presents Faraday pseudo-capacitance behavior is verified; the current density of the electrode is 0.5mAcm -2 Then reaches 450mFg -1 The specific capacitance value of (c).
Example 4: w 18 O 49 The preparation method of the carbon paper composite electrode material comprises the following specific steps:
(1) Cutting to a thickness of 0.19mm and an area of 2cm 2 Washing (1 cm multiplied by 2 cm) carbon paper with deionized water and ethanol in ultrasonic waves with the intensity of 35KHz for 20min, performing ultrasonic treatment on the carbon paper with acetone for 15min, washing with deionized water, then placing the carbon paper in a potassium dichromate/sulfuric acid solution for pretreatment for 20min, washing with deionized water, and drying to obtain pretreated carbon paper; wherein the concentration of potassium dichromate in the potassium dichromate-sulfuric acid solution is 2.5mol/L, and the concentration of sulfuric acid is 1.0mol/L;
(2) Mixing W (CO) 6 Dissolving in ethanol with ultrasound to obtain yellow transparent W (CO) 6 Ethanol solution; wherein W (CO) 6 W (CO) in ethanol solution 6 The concentration is 7g/L;
(3) Adding pretreated carbon paper to W (CO) 6 In ethanol solution, sealing and reacting at 140 deg.C for 24 hr, cooling to room temperature, separating solid and liquid, washing the solid with anhydrous ethanol for 3 times, and vacuum drying to obtain W 18 O 49 A carbon paper composite electrode material; wherein the carbon paper is pretreated with W (CO) 6 The solid-liquid ratio g of the ethanol solution is 0.6;
prepared W 18 O 49 The electrochemical performance of the carbon paper composite electrode material as a super capacitor electrode is characterized as follows: the test is carried out by adopting a three-electrode system electrochemical workstation, wherein the electrolyte is 1mol/L sulfuric acid aqueous solution, the counter electrode is a Pt sheet, the reference electrode is an Ag/AgCl electrode, and the working electrode is W 18 O 49 A carbon paper composite electrode;
the cyclic voltammetry curves (20 to 200 mV/S) of the sample at different scanning rates can observe obvious oxidation peaks and reduction peaks, and the electrode material of the cyclic voltammetry curve has pseudocapacitance characteristics; the redox peak at low scanning rate indicates that the electrode material has a strong redox reaction; with the increase of the scanning rate, the curve shape is not obviously changed, and the cyclic voltammetry curve still keeps the original shape, which shows that the material still has good capacitance performance under the high scanning rate; the alternating current impedance measured under a three-electrode system is 3.5 omega, and a constant current charge-discharge curve under different current densities does not present a linear shape but has obvious bending, so that the electrode is proved to present a Faraday pseudo-capacitance behavior; the current density of the electrode is 0.5mAcm -2 When it reaches380mFg -1 The specific capacitance value of (c).
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (7)
1. W 18 O 49 The carbon paper composite electrode material is characterized in that: using carbon paper as current collector, W 18 O 49 The oxide nano-sheet grows on the surface of the carbon fiber of the carbon paper current collector in situ to form W 18 O 49 Carbon paper composite electrode material, W 18 O 49 The length of the oxide nano-sheet is 100-300nm, W 18 O 49 The thickness of the oxide nano-sheet layer is 5-20nm.
2. W according to claim 1 18 O 49 The preparation method of the carbon paper composite electrode material is characterized by comprising the following steps: the method comprises the following specific steps:
(1) Placing the carbon paper subjected to ultrasonic cleaning in acetone for ultrasonic treatment for 10-20min, then placing the carbon paper in a potassium dichromate-sulfuric acid solution for pretreatment, and washing the carbon paper by water to obtain pretreated carbon paper;
(2) Ultrasonically dissolving a tungsten source in an alcohol solution to obtain a tungsten source-alcohol precursor solution;
(3) Adding the pretreated carbon paper into a tungsten source-alcohol solution, sealing and reacting at the temperature of 120-180 ℃ for 12-24h, cooling to room temperature, carrying out solid-liquid separation, washing the solid, and drying to obtain W 18 O 49 Carbon paper composite electrode material, W 18 O 49 The oxide nanosheets grow in situ on the surface of the carbon fibers of the carbon paper current collector.
3. W according to claim 1 18 O 49 The preparation method of the carbon paper composite electrode material is characterized by comprising the following steps: the water in the step (1) is deionized water, ultrapure water or distilled water.
4. According to claim 1W is described 18 O 49 The preparation method of the carbon paper composite electrode material is characterized by comprising the following steps: the concentration of potassium dichromate in the potassium dichromate-sulfuric acid solution is 0.5 to 3mol/L, and the concentration of sulfuric acid is 0.5 to 2mol/L.
5. W according to claim 1 18 O 49 The preparation method of the carbon paper composite electrode material is characterized by comprising the following steps: the tungsten source in the step (2) is WCl 6 、NaWO 4 、WCl 5 、W(CO) 6 、W(C 2 H 5 O) 6 Or (NH) 4 ) 10 W 12 O 41 ·5H 2 O; the alcoholic solution is methanol, ethanol or propanol.
6. W according to claim 1 or 5 18 O 49 The preparation method of the carbon paper composite electrode material is characterized by comprising the following steps: the concentration of the tungsten source in the tungsten source-alcohol precursor solution is 1 to 8g/L.
7. W according to claim 1 18 O 49 The preparation method of the carbon paper composite electrode material is characterized by comprising the following steps: and (3) the solid-liquid ratio g/mL of the pretreated carbon paper to the tungsten source-alcohol solution is 0.08 to 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116505002A (en) * | 2023-06-29 | 2023-07-28 | 杭州德海艾科能源科技有限公司 | Graphite felt electrode for all-vanadium redox flow battery, and activation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120005789A (en) * | 2010-07-09 | 2012-01-17 | 포항공과대학교 산학협력단 | Cathod catalyst for fuel cell, method of preparing same, and fuel cell system including same |
| CN103426649A (en) * | 2013-08-21 | 2013-12-04 | 吉林大学 | Preparation method for different carbon fibers / cobalt hydroxide electrode and solid-liquid composite electrode system |
| CN105355875A (en) * | 2015-11-05 | 2016-02-24 | 盐城工学院 | Tungsten oxide nanowire wound composite material, preparation method and application |
| CN106449166A (en) * | 2016-11-08 | 2017-02-22 | 东华大学 | Preparation method of super capacitor based on single-wall carbon nanotube/tungsten oxide nanowire composite film electrodes |
| CN107523988A (en) * | 2017-07-21 | 2017-12-29 | 西北大学 | A kind of W18O49Coat carbon fibre composite and preparation method thereof |
| CN109706476A (en) * | 2019-02-28 | 2019-05-03 | 陕西科技大学 | A kind of carbon cloth surfaces growth in situ W18O49The preparation method of self-supporting electrode material |
| CN113943018A (en) * | 2021-10-25 | 2022-01-18 | 昆明理工大学 | Sea urchin-shaped W growing on foamed nickel in situ18O49Method for preparing micron array |
-
2022
- 2022-08-03 CN CN202210927414.3A patent/CN115346803A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120005789A (en) * | 2010-07-09 | 2012-01-17 | 포항공과대학교 산학협력단 | Cathod catalyst for fuel cell, method of preparing same, and fuel cell system including same |
| CN103426649A (en) * | 2013-08-21 | 2013-12-04 | 吉林大学 | Preparation method for different carbon fibers / cobalt hydroxide electrode and solid-liquid composite electrode system |
| CN105355875A (en) * | 2015-11-05 | 2016-02-24 | 盐城工学院 | Tungsten oxide nanowire wound composite material, preparation method and application |
| CN106449166A (en) * | 2016-11-08 | 2017-02-22 | 东华大学 | Preparation method of super capacitor based on single-wall carbon nanotube/tungsten oxide nanowire composite film electrodes |
| CN107523988A (en) * | 2017-07-21 | 2017-12-29 | 西北大学 | A kind of W18O49Coat carbon fibre composite and preparation method thereof |
| CN109706476A (en) * | 2019-02-28 | 2019-05-03 | 陕西科技大学 | A kind of carbon cloth surfaces growth in situ W18O49The preparation method of self-supporting electrode material |
| CN113943018A (en) * | 2021-10-25 | 2022-01-18 | 昆明理工大学 | Sea urchin-shaped W growing on foamed nickel in situ18O49Method for preparing micron array |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116505002A (en) * | 2023-06-29 | 2023-07-28 | 杭州德海艾科能源科技有限公司 | Graphite felt electrode for all-vanadium redox flow battery, and activation method and application thereof |
| CN116505002B (en) * | 2023-06-29 | 2023-09-29 | 杭州德海艾科能源科技有限公司 | Graphite felt electrode for all-vanadium redox flow battery, and activation method and application thereof |
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