CN116386928B - Sodium alginate/titanium dioxide composite porous electrode material and preparation method thereof - Google Patents
Sodium alginate/titanium dioxide composite porous electrode material and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 115
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 52
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 52
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 52
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000007772 electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 51
- 239000002135 nanosheet Substances 0.000 claims abstract description 37
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007783 nanoporous material Substances 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- -1 fluorine ions Chemical class 0.000 claims description 4
- 239000011858 nanopowder Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000012776 electronic material Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 239000011343 solid material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 150000004676 glycans Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- 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
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- 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
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- 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
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- 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
Abstract
The invention belongs to the technical field of semiconductor electronic materials, and particularly relates to a sodium alginate/titanium dioxide composite porous electrode material and a preparation method thereof. Graphene, sodium alginate and TiO in the composite porous electrode material 2 Mass ratio of nanosheets 4: 10-19: 36-76; the preparation method is that a flaky anatase phase titanium dioxide nano-sheet structure is prepared, and graphene and sodium alginate are used as two-dimensional TiO 2 The nano-sheet connected 'skeleton', the graphene is used as a supporting 'skeleton' to form a sheet-layered porous structure, so that the electrical conductivity between sheets can be improved, and the TiO is improved 2 The electron transmission performance of the nano-sheet, the addition of sodium alginate can improve the 'skeleton' strength, ensure that the porous structure of the nano-sheet is maintained when the electrode material is prepared, and finally the nano-sheet is annealed in argon, so that the concentration of oxygen vacancies of titanium dioxide can be improved on the basis of the porous structure of the material, and the conductivity and electrochemical activity of the nano-sheet are improved.
Description
Technical Field
The invention belongs to the technical field of semiconductor electronic materials, and particularly relates to a sodium alginate/titanium dioxide composite porous electrode material and a preparation method thereof.
Background
Titanium dioxide (TiO) 2 ) Is a comprehensive performanceExcellent semiconductor, and has the advantages of good stability, no toxicity, abundant reserves and the like, has wide application prospect in the fields of photocatalysis, environmental management, energy storage, conversion and the like, and even realizes commercialization in a plurality of fields. Titanium dioxide has the advantages of proper working voltage, low cost and good stability when being used as the anode material of the ion battery, but is used as semiconductor TiO 2 The inherent poor conductivity and low specific surface area result in unsatisfactory specific capacity and rate capability.
Heat treatment of nano TiO in hydrogen atmosphere 2 Obtaining black TiO 2 Has been reported for black TiO with high density of oxygen vacancies 2 It is a research hot spot due to its good conductivity and reactivity. In addition, graphene has a plurality of unique physicochemical properties, and the charge migration speed of the graphene can reach 15000 cm 2 Vs, and a specific surface area of up to 2600 m 2 And/g. The performances enable the graphene to have wide application prospects in various fields such as polymer composite materials, transparent conductive films, super capacitors, battery cathode materials and the like. Modification of TiO by means of graphene 2 Semiconductor materials have proven to significantly improve charge transport efficiency.
TiO 2 The nano sheet has higher activity compared with the traditional TiO due to the special two-dimensional structure, the exposure of the high-activity crystal face and the higher activity of a large number of unsaturated surface atoms 2 The nanomaterial has great application advantages compared with the nanomaterial. Nanometer TiO 2 In practical application, the performance is limited due to agglomeration and other problems. Therefore, it is necessary to use TiO 2 One or more materials are added between the nano sheets to be used as a connecting 'skeleton', and TiO is used as the material 2 The nano sheet is used for constructing a porous solid material with large specific surface area and good conductivity, and is hopeful to improve TiO 2 Is used for the electrochemical application.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sodium alginate/titanium dioxide composite porous electrode material and a preparation method thereof, wherein graphene and sodium alginate are used as two-dimensional TiO (titanium dioxide) by preparing anatase-phase titanium dioxide nanosheet structures with high exposure surfaces 2 Nano-sheet connected 'skeleton' and its making processThe titanium dioxide composite porous electrode material of sodium alginate and graphene is prepared to increase the specific surface area of the material and improve the conductivity and electrochemical activity of the material. The technical scheme adopted is as follows:
a sodium alginate/titanium dioxide composite porous electrode material is prepared by preparing a flaky anatase phase titanium dioxide nanosheet structure, and taking graphene and sodium alginate as two-dimensional TiO 2 Nanometer sheet connected 'skeleton', and preparing sodium alginate and graphene composite porous titanium dioxide electrode material to increase specific surface area of the material and improve TiO (titanium dioxide) 2 Electron transport properties of the nanoplatelets; wherein, graphene, sodium alginate and TiO 2 Mass ratio of nanosheets 4: 10-19: 36-76.
The preparation method of the sodium alginate/titanium dioxide composite porous electrode material comprises the following steps:
（1）TiO 2 preparation of nanosheets:
measuring a certain volume of analytically pure butyl titanate and hydrofluoric acid solution respectively, mixing, placing into an ultrasonic cleaner, ultrasonic dispersing, transferring into a hydrothermal reaction kettle, and placing the hydrothermal reaction kettle into an oven for reaction to prepare platy titanium dioxide nano powder, namely TiO 2 A nano-sheet.
Prepared TiO 2 The flaky anatase phase nano titanium dioxide with a high exposure surface has high activity.
(2) Preparation of a titanium dioxide composite porous electrode material with sodium alginate and graphene as 'frameworks':
dispersing single-layer or few-layer graphene in water to prepare a graphene aqueous solution, and marking the graphene aqueous solution as a solution A; dissolving sodium alginate in water to prepare sodium alginate aqueous solution, and marking the aqueous solution as solution B; solution A, solution B and TiO 2 Uniformly mixing the nano sheets, pre-freezing by using liquid nitrogen, freeze-drying, and finally annealing to obtain the black block-shaped nano porous material, thus obtaining the composite porous electrode material.
Preferably, in the step (1), the volume ratio of butyl titanate to hydrofluoric acid is 25:6, the concentration of hydrofluoric acid is 40%.
Preferably, in the step (1), the temperature of the oven is 190-220 ℃ and the reaction time is 20-30 h.
Preferably, in the step (1), after the reaction is completed, the following steps are further required to obtain the platy titanium dioxide nano powder:
and (3) after the reaction kettle is naturally and completely cooled, removing supernatant in the reaction kettle, centrifugally separating lower-layer sediment for 3-5 times by using absolute ethyl alcohol and deionized water respectively, removing fluorine ions on the surface of the obtained powder, and finally, placing the centrifuged sediment in a 60 ℃ oven for drying.
Preferably, the fluoride ion on the powder surface is removed by washing with a sodium hydroxide solution having a concentration of 0.1mol/L, and then washing with distilled water by centrifugation to neutrality.
As a further preferred aspect, the mass ratio of graphene, sodium alginate and TiO2 nanosheets is 4:16:48.
preferably, in the step (2), the concentration of the graphene in the solution A is 2 mg/ml.
Preferably, in the step (2), the annealing treatment is performed in argon at 180-200 ℃ for 1.5-2 hours.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the flaky anatase phase nano titanium oxide with high exposure surface, adds graphene as a supporting 'skeleton' to form a lamellar porous structure, improves the electrical conductivity between sheets and improves TiO (titanium oxide) 2 Electron transport properties of the nanoplatelets; because few-layer graphene can not provide enough supporting force for the porous structure, sodium alginate can be used as a binder to improve the performance well, and the polysaccharide chain structure of the sodium alginate ensures TiO 2 The adsorption force of the nano-sheet, therefore, the nano-sheet is used as a 'skeleton' in the porous material, so that the 'skeleton' strength can be improved, and the porous structure of the nano-sheet is ensured to be maintained when the electrode material is prepared.
In the preparation method, finally, annealing treatment is carried out in argon, so that the concentration of oxygen vacancies of titanium dioxide is improved on the basis of guaranteeing the porous structure of the material, and the conductivity and electrochemical activity of the material are improved.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of the cross-sectional morphology of a composite porous electrode material obtained in examples 1, 2, 3 and comparative example 1 of the present invention.
FIG. 2 is a graph showing the voltammogram of the composite porous electrode material obtained in examples 1, 2, 3 and comparative example 2 of the present invention.
Detailed Description
The drawings are for illustrative purposes only; for the purpose of better illustrating the embodiments, certain elements of the drawings may be omitted, enlarged or reduced and do not represent the size of the actual product; some well-known structures in the drawings and descriptions thereof may be omitted to those skilled in the art.
The technical solutions in the embodiments of the present specification will be clearly and completely described below with reference to the drawings in the embodiments of the present specification.
Example 1, a sodium alginate/titanium dioxide composite porous electrode material, the preparation method is as follows.
First step, high activity TiO 2 Preparation of nanosheets:
according to the volume portions, respectively measuring and analyzing pure butyl titanate 25 ml and hydrofluoric acid solution 6 ml with the concentration of 40%, mixing, placing in an ultrasonic cleaner, ultrasonic dispersing, transferring to a hydrothermal reaction kettle, placing in a baking oven with the temperature of 190 ℃ for reaction for 20-30 hours, taking out, and naturally cooling.
After the reaction kettle is completely cooled, opening, removing supernatant, and performing centrifugal separation on lower-layer sediment by using absolute ethyl alcohol and deionized water for three times respectively; and (3) washing with 0.1mol/L sodium hydroxide solution to remove fluoride ions on the surface of the powder, and then centrifuging with distilled water to neutrality.
And finally, placing the centrifuged precipitate in a baking oven at 60 ℃ for drying to obtain the flaky titanium oxide nano powder.
Secondly, preparing a sodium alginate/graphene/titanium dioxide composite porous block:
dispersing few layers of graphene in water to prepare a graphene aqueous solution A with the concentration of 2 mg/ml; dissolving sodium alginate in water to obtain 15 mg/ml sodium alginateAn aqueous solution B; tiO with high activity (100) surface prepared in the first step is selected as the solution A, the solution B and the solution B 2 Nano sheet of graphene, sodium alginate and TiO 2 The mass ratio of the nano-sheets is 4:10:36, pre-freezing with liquid nitrogen, freeze drying, and finally annealing at 200 ℃ in argon for 1.5. 1.5 h to obtain the black block nano composite porous electrode material.
Example 2, a sodium alginate/titanium dioxide composite porous electrode material, the preparation method is as follows.
In the second step, in the preparation of the sodium alginate/graphene/titanium dioxide composite porous electrode material, graphene, sodium alginate and TiO are used as the solution 2 The mass ratio of the nano-sheets is 4:16:48, pre-freezing with liquid nitrogen, freeze drying, and finally annealing at 200 ℃ in argon for 1.5. 1.5 h to obtain black block nano porous material.
Other points not described are the same as in example 1.
Example 3 a sodium alginate/titanium dioxide composite porous electrode material, the preparation method of which is as follows.
In the second step, in the preparation of the sodium alginate/graphene/titanium dioxide composite porous electrode material, graphene, sodium alginate and TiO are used as the solution 2 The mass ratio of the nano-sheets is 4:19:76, pre-freezing with liquid nitrogen, freeze-drying, and finally annealing at 200 ℃ in argon for 1.5. 1.5 h to obtain black block nano porous material.
Other points not described are the same as in example 1.
Comparative example 1 preparation of graphene/titania composite porous material, in the second step, the solution was prepared as graphene: tiO (titanium dioxide) 2 The mass ratio of the nano-sheets is 4:36, pre-freezing with liquid nitrogen, freeze drying, and finally annealing at 200 ℃ in argon for 1.5. 1.5 h to obtain black block nano porous material.
The remainder was the same as in example 1.
Comparative example 2 preparation of sodium alginate/titanium dioxide composite porous Material without graphene added in the second step, sodium alginate was used as the solution：TiO 2 The mass ratio of the nano-sheets is 1:4, after uniformly mixing, pre-freezing by liquid nitrogen, freeze-drying, and finally annealing at 200 ℃ in argon for 1.5 h to obtain the massive nano porous material.
The remainder was the same as in example 1.
As shown in FIG. 1, the porous materials obtained in examples 1, 2 and 3 have the morphology of solid sections, and the solid materials prepared by the method have a porous structure, and the structural skeleton mainly comprises flaky graphene and sodium alginate. With TiO 2 Increasing the amount of nanoplatelets, tiO 2 The adsorption capacity of the nano-sheets on the porous material 'skeleton' is increased and dense. Compared with comparative example 1, the addition of sodium alginate reduces the stacking density of 'skeleton' titanium dioxide, meanwhile, the strength of the composite porous electrode material is effectively improved, the titanium oxide of comparative example 1 has high surface aggregation density, and the obtained porous material is fragile and has poor strength by simply taking graphene sheets as 'skeleton' supporting structures, and the porous structure is probably lost when the porous material is extruded during application.
Meanwhile, the composite porous electrode materials obtained in examples 1, 2 and 3 were mixed and ground with carbon black, 1-methyl-2-pyrrolidone solution was added to sufficiently grind into uniform slurry, and the slurry was applied to a region of 1cm of foamed nickel to prepare a foamed nickel electrode sheet, which was allowed to stand as a working electrode in a 6mo1/L potassium hydroxide electrolyte for half an hour, and its cyclic voltammogram was analyzed in a three-electrode system, as shown in FIG. 2. The addition of graphene significantly increases the conductivity of the sample compared to the sample prepared in comparative example 2, especially example 2 shows a larger specific capacity, i.e. when graphene, sodium alginate, tiO 2 The mass ratio of the nano-sheets is 4:16: at 48, the specific capacitance of the final electrode material is better.
The titanium oxides mentioned in the present invention are titanium dioxide (TiO 2 ) The graphene used in the invention can be single-layer graphene or few-layer graphene, which are purchased directly, wherein the few-layer graphene is 3-5 layers, and the single-layer graphene has a good dispersing effect, but the cost is more expensive, so that the graphene used in the embodiment is few-layer graphene, and the expected effect can be achieved. Other places not describedAs in the prior art.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. A sodium alginate/titanium dioxide composite porous electrode material is characterized in that graphene and sodium alginate are used as two-dimensional TiO by preparing a flaky anatase phase titanium dioxide nanosheet structure 2 Preparing a titanium dioxide composite porous electrode material of sodium alginate and graphene by using a 'skeleton' connected with the nano-sheets; wherein, graphene, sodium alginate and TiO 2 Mass ratio of nanosheets 4: 10-19: 36-76.
2. The preparation method of the sodium alginate/titanium dioxide composite porous electrode material is characterized by comprising the following steps of:
（1）TiO 2 preparation of nanosheets:
measuring a certain volume of analytically pure butyl titanate and hydrofluoric acid solution respectively, mixing, placing into an ultrasonic cleaner, ultrasonic dispersing, transferring into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven for reaction, and preparing flaky anatase phase titanium dioxide nano powder, namely TiO 2 A nanosheet;
(2) Preparation of a titanium dioxide composite porous electrode material with sodium alginate and graphene as 'frameworks':
dispersing graphene in water to prepare a graphene aqueous solution, and marking the graphene aqueous solution as a solution A; dissolving sodium alginate in water to prepare sodium alginate aqueous solution, and marking the aqueous solution as solution B;
solution A, solution B and TiO 2 Uniformly mixing the nano sheets, pre-freezing by using liquid nitrogen, freeze-drying, and finally annealing to obtain the black block-shaped nano porous material, namely the composite porous electrode material.
3. The method for preparing the sodium alginate/titanium dioxide composite porous electrode material according to claim 2, wherein in the step (1), the volume ratio of butyl titanate to hydrofluoric acid is 25:6, the concentration of hydrofluoric acid is 40%.
4. The method for preparing the sodium alginate/titanium dioxide composite porous electrode material according to claim 2, wherein in the step (1), the temperature of an oven is 190-220 ℃ and the reaction time is 20-30 h.
5. The method for preparing the sodium alginate/titanium dioxide composite porous electrode material according to claim 2, wherein in the step (1), after the reaction is completed, the following steps are further required to obtain the flaky titanium dioxide nano powder:
and (3) after the reaction kettle is naturally and completely cooled, removing supernatant in the reaction kettle, centrifugally separating lower-layer sediment for 3-5 times by using absolute ethyl alcohol and deionized water respectively, removing fluorine ions on the surface of the obtained powder, and finally, placing the centrifuged sediment in a 60 ℃ oven for drying.
6. The preparation method of the sodium alginate/titanium dioxide composite porous electrode material according to claim 5, wherein the method for removing fluoride ions on the surface of the powder is to wash with sodium hydroxide solution with the concentration of 0.1mol/L, and then to centrifuge and wash with distilled water to neutrality.
7. The method for preparing the sodium alginate/titanium dioxide composite porous electrode material according to claim 2, wherein in the step (2), the mass ratio of graphene, sodium alginate and TiO2 nanosheets is 4:16:48.
8. the method for preparing a sodium alginate/titanium dioxide composite porous electrode material according to claim 2, wherein in the step (2), the concentration of the solution a graphene is 2 mg/ml.
9. The method for preparing the sodium alginate/titanium dioxide composite porous electrode material according to claim 2, wherein in the step (2), the annealing treatment is performed in argon at 180-200 ℃ for 1.5-2 hours.
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