CN114558616A - Preparation method and application of natural fiber composite material wrapped by zinc stannate - Google Patents
Preparation method and application of natural fiber composite material wrapped by zinc stannate Download PDFInfo
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- CN114558616A CN114558616A CN202210197409.1A CN202210197409A CN114558616A CN 114558616 A CN114558616 A CN 114558616A CN 202210197409 A CN202210197409 A CN 202210197409A CN 114558616 A CN114558616 A CN 114558616A
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- composite material
- fiber composite
- zinc
- natural fiber
- zinc stannate
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- 239000000835 fiber Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 239000004917 carbon fiber Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 31
- 238000003756 stirring Methods 0.000 description 31
- 229910052725 zinc Inorganic materials 0.000 description 31
- 239000000463 material Substances 0.000 description 18
- 239000011941 photocatalyst Substances 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007717 ZnSnO Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- H—ELECTRICITY
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of preparation of composite materials, in particular to a preparation method and application of a natural fiber composite material wrapped by zinc stannate. The invention utilizes the unique hierarchical porous reticular structure, high specific surface area and excellent flexibility of the natural fiber, can effectively prevent the agglomeration of zinc stannate, and fully exerts the catalytic performance of the zinc stannate; meanwhile, the prepared composite material has a macroscopic fiber structure, so that the zinc stannate can be recycled more conveniently, and the preparation method has important significance in further development of photocatalysis and energy recycling.
Description
Technical Field
The invention relates to the field of preparation of composite materials, in particular to a preparation method and application of a natural fiber composite material wrapped by zinc stannate.
Background
Zinc metastannate (ZnSnO)3) The flame-retardant silicon-based composite material is an important semiconductor material, has the characteristics of high safety, no toxicity, good thermal stability, high flame-retardant efficiency, easiness in use and the like, and has important application in the fields of gas sensitivity, catalysis, flame retardance, lithium batteries and the like.
On one hand, zinc metastannate is an excellent photocatalyst material, has strong oxidation-reduction capability, can generate photoproduction electrons and holes under the illumination condition to improve the quantum efficiency, thereby expanding the wavelength range of exciting light and further fully utilizing solar energy to improve the stability of the photocatalyst. Therefore, the use of zinc metastannate as photocatalyst for optimizing environment is attracting more and more attention, and researchers have been intensively studying the use of zinc metastannate as photocatalyst. The existing nano zinc metastannate has excellent photocatalytic activity, but has high surface energy, so that the nano zinc metastannate is easy to agglomerate in a cycle test and has low recovery rate. Therefore, the zinc metastannate with excellent catalytic performance is obtained, the problem that the powder material is difficult to recover after being used is solved, and the method has important theoretical and practical significance for further development of photocatalysis and energy recycling.
On the other hand, zinc metastannate has a high theoretical specific capacity (1317 mAh. g)-1) The method has great potential in the aspect of being used as a cathode material of a lithium ion battery. However, current research work on zinc metastannate as a negative electrode material of lithium ion batteries is quite limited, mainly because the zinc metastannate is severely crushed and agglomerated during the circulation process, which results in rapid capacity decay and circulationThe stability becomes poor. And as a semiconductor material, the lower electronic conductivity of zinc metastannate can cause the battery to generate larger polarization, thereby reducing the practical performance of the material and further hindering the development and application of the material in the lithium ion battery. How to regulate and control the organization structure of the electrode material and obtain the lithium ion battery with high specific capacity, good cycle performance and excellent rate performance is a key and difficult point of current research.
Disclosure of Invention
The purpose of the application is to overcome the defects in the prior art, and provide a preparation method of a natural fiber composite material wrapped by zinc stannate.
The invention provides a preparation method of a natural fiber composite material wrapped by zinc stannate, which takes zinc salt and tin salt as precursors, urea as a mineralizer and natural fiber as a template to prepare the natural fiber composite material wrapped by the zinc stannate through hydrothermal reaction.
Compared with the prior art, the preparation method of the natural fiber composite material wrapped by zinc stannate provided by the invention has the following advantages:
the invention utilizes the unique hierarchical porous reticular structure, high specific surface area and excellent flexibility of the natural fiber, can effectively prevent the agglomeration of zinc stannate, and fully exerts the catalytic performance of the zinc stannate; meanwhile, the prepared composite material has a macroscopic fiber structure, so that the zinc stannate can be recycled more conveniently, and the preparation method has important significance in further development of photocatalysis and energy recycling.
Preferably, the natural fiber is filter paper or absorbent cotton.
Preferably, the natural fibers are quantitative filter papers.
Preferably, the natural fibers are pre-treated quantitative filter paper in a manner that: and scraping a certain amount of filter paper by using a blade, so that the filter paper fibers become loose, and obtaining the pretreated certain amount of filter paper fibers.
The quantitative filter paper has a special hierarchical micro-nano structure and a large specific surface area, can provide more active sites for photochemical reaction, further improves the photocatalytic performance of the material, and has looser fibers obtained by pretreatment and more excellent wrapping effect.
Preferably, the zinc salt is at least one of zinc chloride, zinc nitrate or zinc acetate, and the tin salt is tin tetrachloride.
Preferably, the preparation method of the natural fiber composite material wrapped by zinc stannate specifically comprises the following steps:
dispersing the natural fibers in water to obtain a natural fiber dispersion liquid, wherein the mass ratio of the natural fibers to the water is (0.05-0.2) to (20-40);
and step two, uniformly mixing the zinc salt, the tin salt and water to obtain a mixed solution, adding the natural fiber dispersion solution, reacting for 4-6 hours, adding the urea, and carrying out hydrothermal reaction to obtain the natural fiber composite material wrapped by the zinc stannate.
Preferably, in the first step, the specific operation of dispersing is: stirring for 0.5-2 h after ultrasonic treatment for 10-20 min, wherein the stirring speed is 500-1000 r/min.
Preferably, in the second step, the natural fiber dispersion liquid is added dropwise, and the dropwise adding time is 8-10 min.
Preferably, step two further comprises water washing and drying after the hydrothermal reaction.
The natural fiber composite material wrapped by zinc stannate is prepared by a simple one-step hydrothermal method, and the whole preparation process is simple, low in cost and easy for industrial production. The invention adopts natural fibers with wide sources and low price as raw materials, utilizes the unique hierarchical porous network structure and high specific surface area thereof, is more beneficial to carrying out photochemical reaction, obviously improves the photocatalytic performance of zinc metastannate, and simultaneously prepares the obtained composite material with a macroscopic fiber structure, can solve the problem that the catalytic material is difficult to recover in practical application, and improves the capability of degrading pollutants in wastewater by photocatalysis.
Preferably, the molar ratio of the zinc salt to the tin salt is 1:1, and the concentration of the zinc salt in the mixed solution is 0.1-0.25 mmol/L.
When the concentration is too low, the zinc stannate is not uniformly wrapped on the surface of the natural fiber; at too high a concentration, more bulky zinc stannate will appear.
Preferably, the addition amount of the urea is 0.3-2 g/L.
The above-mentioned preferred amount of addition is calculated as the sum of the volumes of the natural fiber dispersion liquid in the step one and the mixed solution in the step two.
Preferably, the temperature of the hydrothermal reaction is 100-150 ℃, and the time is 6-12 h.
The invention also provides a preparation method of the carbon fiber composite material wrapped by the zinc stannate, and the carbon fiber composite material wrapped by the zinc stannate is prepared by calcining the natural fiber composite material wrapped by the zinc stannate under the protection of inert gas or nitrogen.
The invention utilizes the support and buffer action of the carbon fiber material, maintains the high specific capacity characteristic of the zinc metastannate, simultaneously can increase the cycling stability, and can solve the serious volume effect generated when the zinc metastannate is cyclically subjected to lithium extraction.
Preferably, the conditions of the calcination are: the calcination temperature is 300-500 ℃, the heating rate is 1-5 ℃/min, and the calcination time is 4-8 h.
The invention also provides the application of the natural fiber composite material prepared by the preparation method of the natural fiber composite material wrapped by the zinc stannate in photocatalysis.
The photocatalyst prepared from the natural fiber composite material wrapped by the zinc stannate provided by the invention has excellent photocatalytic performance, and the degradation rate of rhodamine B can reach 98.8%.
The invention also provides application of the carbon fiber composite material prepared by the preparation method of the carbon fiber composite material wrapped by the zinc stannate in a lithium ion battery.
The lithium battery assembled by taking the carbon fiber composite material wrapped by the zinc stannate as the lithium ion battery cathode material has the advantages of large specific capacity, high cycling stability, long cycling life and the like, the charging and discharging specific capacity of the first circle is 848mAh/g and 1481mAh/g respectively, the coulombic efficiency reaches 57%, after 100 cycles, the discharging specific capacity still remains 613mAh/g, and the coulombic efficiency after stabilization is kept above 98%.
Drawings
FIG. 1 is a scanning electron microscope image of the natural fiber composite material wrapped by zinc metastannate prepared in example 1 under different times;
FIG. 2 is an X-ray diffraction pattern of the zinc metastannate wrapped natural fiber composite prepared in example 1;
FIG. 3 is a scanning electron microscope image of the natural fiber composite wrapped with zinc metastannate prepared in example 2;
FIG. 4 is a scanning electron microscope image of the natural fiber composite wrapped with zinc metastannate prepared in example 3;
FIG. 5 is a scanning electron microscope image of the natural fiber composite wrapped with zinc metastannate prepared in example 4;
FIG. 6 is a scanning electron microscope image of a pure zinc metastannate material prepared in comparative example 1;
FIG. 7 is a scanning electron microscope image of a carbon fiber composite wrapped with zinc metastannate prepared in example 5;
FIG. 8 is an X-ray diffraction pattern of the zinc metastannate wrapped carbon fiber composite prepared in example 5;
FIG. 9 is a scanning electron microscope image of a pure zinc metastannate material prepared in comparative example 2;
FIG. 10 is a graph of photocatalysts 1 and 2 prepared in example 1 and comparative example 1 respectively degrading an organic simulated pollutant rhodamine B in a photocatalytic manner;
fig. 11 is a constant current charge-discharge cycle performance curve of batteries 1 and 2 respectively assembled as negative electrode materials of lithium ion batteries in example 5 and comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The pretreatment mode for quantitative filter paper fibers in the following examples is: and (3) taking commercially available quantitative filter paper, scraping the filter paper sheet by using a disinfected blade, and obtaining the pretreated quantitative filter paper fiber after the filter paper fiber is loosened.
Example 1:
the embodiment provides a preparation method of a natural fiber composite material, which comprises the following steps:
step one, adding 0.1g of pretreated quantitative filter paper fibers into 25mL of water, carrying out ultrasonic treatment for 15min, and stirring for 1h to obtain a quantitative filter paper fiber dispersion solution;
step two, adding a proper amount of SnCl into 25mL of water4·4H2O and Zn (CH)3CO2)2·2H2O, stirring and mixing evenly to enable SnCl4·4H2O and Zn (CH)3CO2)2·2H2And (3) dropwise adding the quantitative filter paper fiber dispersion liquid under the stirring condition, continuously stirring for 5 hours, adding 0.027g of urea, stirring for 15 minutes, transferring to a 100mL high-pressure reaction kettle, carrying out hydrothermal reaction for 8 hours at 120 ℃, washing with water, and drying to obtain the natural fiber composite material wrapped by the zinc stannate, wherein the dropwise adding time is controlled to be 8 minutes, and the stirring speed of the first step and the second step is 1000 r/min. The scanning electron microscope images of the natural fiber composite material wrapped by the zinc stannate under different times are shown in figure 1, and the X-ray diffraction image is shown in figure 2.
Example 2:
the embodiment provides a preparation method of a natural fiber composite material, which comprises the following steps:
step one, adding 0.1g of pretreated quantitative filter paper fibers into 25mL of water, carrying out ultrasonic treatment for 15min, and stirring for 1h to obtain a quantitative filter paper fiber dispersion solution;
step two, adding a proper amount of SnCl into 25mL of water4·4H2O and Zn (CH)3CO2)2·2H2O, stirring and mixing evenly to enable SnCl4·4H2O and Zn (CH)3CO2)2·2H2And (3) dropwise adding the quantitative filter paper fiber dispersion liquid under the stirring condition, continuously stirring for 5 hours, adding 0.018g of urea, stirring for 15 minutes, transferring to a 100mL high-pressure reaction kettle, carrying out hydrothermal reaction for 8 hours at 120 ℃, washing with water, and drying to obtain the natural fiber composite material wrapped by the zinc stannate, wherein the dropwise adding time is controlled to be 10 minutes, and the stirring speed of the first step and the second step is 600 r/min. The scanning electron microscope image of the obtained natural fiber composite material wrapped by zinc stannate is shown in figure 3.
Example 3:
the embodiment provides a preparation method of a natural fiber composite material, which comprises the following steps:
step one, adding 0.1g of pretreated quantitative filter paper fibers into 25mL of water, carrying out ultrasonic treatment for 15min, and stirring for 1h to obtain a quantitative filter paper fiber dispersion solution;
step two, adding a proper amount of SnCl into 25mL of water4·4H2O and Zn (CH)3CO2)2·2H2O, stirring and mixing evenly to enable SnCl4·4H2O and Zn (CH)3CO2)2·2H2And (3) dropwise adding the quantitative filter paper fiber dispersion liquid under the stirring condition, continuously stirring for 5 hours, adding 0.036g of urea, stirring for 15 minutes, transferring to a 100mL high-pressure reaction kettle, carrying out hydrothermal reaction for 8 hours at 120 ℃, washing with water, and drying to obtain the natural fiber composite material wrapped by the zinc stannate, wherein the dropwise adding time is controlled to be 8 minutes, and the stirring speed of the first step and the second step is 800 r/min. The scanning electron microscope image of the obtained natural fiber composite material wrapped by zinc stannate is shown in fig. 4.
Example 4:
the embodiment provides a preparation method of a natural fiber composite material, which comprises the following steps:
step one, adding 0.1g of pretreated quantitative filter paper fibers into 25mL of water, carrying out ultrasonic treatment for 15min, and stirring for 1h to obtain a quantitative filter paper fiber dispersion solution;
step two, adding a proper amount of SnCl into 25mL of water4·4H2O and Zn (CH)3CO2)2·2H2O, stirring and mixing evenly to enable SnCl4·4H2O and Zn (CH)3CO2)2·2H2And (3) dropwise adding the quantitative filter paper fiber dispersion liquid under the stirring condition, continuously stirring for 5 hours, adding 0.045g of urea, stirring for 15 minutes, transferring to a 100mL high-pressure reaction kettle, carrying out hydrothermal reaction for 6 hours at 150 ℃, washing with water, and drying to obtain the natural fiber composite material wrapped by the zinc stannate, wherein the dropwise adding time is controlled to be 10 minutes, and the stirring speed of the first step and the second step is 600 r/min. The scanning electron microscope image of the obtained natural fiber composite material wrapped by zinc stannate is shown in fig. 5.
Example 5:
and calcining the natural fiber composite material wrapped by the zinc stannate obtained in the example 1 at 500 ℃ for 5 hours under the protection of nitrogen, wherein the heating rate is 2 ℃/min, so as to obtain the carbon fiber composite material wrapped by the zinc stannate. The scanning electron microscope image of the obtained zinc stannate-coated carbon fiber composite material is shown in fig. 7, and the X-ray diffraction image is shown in fig. 8.
Comparative example 1:
on the basis of the embodiment 1, a pure zinc metastannate material is prepared without adding quantitative filter paper fibers, and the specific steps are as follows: adding a proper amount of SnCl into 50mL of water4·4H2O and Zn (CH)3CO2)2·2H2O, stirring and mixing evenly to enable SnCl4·4H2O and Zn (CH)3CO2)2·2H2And adding 0.027g of urea into the mixture with the concentration of O of 0.15mmol/L, stirring the mixture for 15min, transferring the mixture into a 100mL high-pressure reaction kettle, performing hydrothermal reaction for 8h at 120 ℃, washing the product with water, and drying the product to obtain the pure zinc metastannate material, wherein the dripping time is controlled to be 8min, and the stirring speed is 1000 r/min. The scanning electron micrograph of the obtained pure zinc metastannate material is shown in FIG. 6.
Comparative example 2:
the nitrogen in example 5 was replaced by calcination in air at 500 ℃ for 5 hours, and the rest was the same as in example 5. And removing the natural fiber template through air calcination to prepare the pure zinc metastannate material. The scanning electron micrograph of the obtained pure zinc metastannate material is shown in FIG. 9.
Application example 1:
the natural fiber composite material wrapped with zinc stannate obtained in example 1 was prepared as a photocatalyst, which was denoted as photocatalyst 1, and the pure zinc metastannate material obtained in comparative example 1 was prepared as a photocatalyst, which was denoted as photocatalyst 2.
30mg of photocatalysts 1 and 2 are respectively weighed, rhodamine B is used as a target degradation product (the concentration is 5mg/L, the volume is 30mL), a 500W xenon lamp is used as a visible light source, an optical filter is used for filtering ultraviolet light smaller than 420nm, and after dark reaction for 30min, an XPA-7 type multi-test-tube stirring reactor is used for carrying out photocatalytic reaction. Sampling every 1h, measuring the absorbance of the simulated pollutant rhodamine B solution at the maximum absorption wavelength of 554nm by using an ultraviolet-visible spectrophotometer, and calculating the degradation rate of the simulated pollutant rhodamine B solution under visible light.
As can be seen from fig. 10, after 4 hours of illumination, the degradation rate of the photocatalyst 1 on rhodamine B is 98.8%, and the degradation rate of the photocatalyst 2 on rhodamine B is 93.8%, thereby indicating that the natural fiber composite material coated with zinc stannate prepared in example 1 has excellent photocatalytic performance.
Application example 2:
the carbon fiber composite material wrapped by the zinc stannate obtained in the example 5 is prepared into a lithium ion battery negative plate which is marked as lithium ion battery negative plate 1, and the pure zinc metastannate material obtained in the comparative example 2 is prepared into a lithium ion battery negative plate which is marked as lithium ion battery negative plate 2.
Respectively grinding the lithium ion battery negative plates 1 and 2 in agate mortars for 30min, then respectively weighing 40mg, mixing with conductive agent acetylene black and binder PVDF according to the mass ratio of 7: 2: 1, carrying out vacuum drying at 80 ℃ overnight, then preparing into paste slurry, carrying out ultrasonic treatment for 30min, adding magnetons, stirring overnight, then coating on foamed nickel, carrying out vacuum drying overnight, and tabletting.
And respectively assembling the lithium ion battery negative plates 1 and 2 and the positive plate-lithium plate in a glove box filled with argon to respectively obtain the CR2032 type button batteries 1 and 2. The electrolyte used was LiPF6 as solute, Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) as solvents in a volume ratio of 1:1, and the separator used was Celgard 2400.
And testing the assembled CR2032 type button batteries 1 and 2, and testing the charge-discharge cycle performance of the batteries under constant current and different multiplying powers by using a battery system, wherein the charge-discharge voltage range is 0.01-3.0V.
As shown in FIG. 11, the charge-discharge cycle performance of the battery 1 under a constant current of 100mA/g is respectively 848mAh/g and 1481mAh/g in the first-turn charge-discharge specific capacity, and the coulombic efficiency is about 57%. After 100 cycles, the discharge specific capacity is still 613mAh/g, and the coulomb efficiency after stabilization is kept above 98%. Comparing the constant current charge-discharge cycling performance of battery 2, it can be seen from fig. 11 that after 40 cycles, the specific capacity of battery 2 had decreased to 212 mAh/g. Therefore, the lithium battery assembled by the carbon fiber composite material wrapped by the zinc metastannate prepared in the example 5 has larger specific capacity and better cycling stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the natural fiber composite material wrapped by the zinc stannate is characterized in that the natural fiber composite material wrapped by the zinc stannate is prepared by taking zinc salt and tin salt as precursors, urea as a mineralizer and natural fibers as a template through hydrothermal reaction.
2. The method of preparing the natural fiber composite material wrapped with zinc stannate of claim 1, wherein the natural fiber is filter paper or absorbent cotton.
3. The method of preparing a zinc stannate-coated natural fiber composite of claim 2, wherein the natural fiber is quantitative filter paper.
4. The method for preparing the natural fiber composite material wrapped by the zinc stannate according to claim 1, wherein the zinc salt is at least one of zinc chloride, zinc nitrate or zinc acetate, and the tin salt is tin tetrachloride.
5. The method for preparing the natural fiber composite material wrapped by zinc stannate according to any one of claims 1 to 4, comprising the following steps:
dispersing the natural fibers in water to obtain a natural fiber dispersion liquid, wherein the mass ratio of the natural fibers to the water is (0.05-0.2) to (20-40);
and step two, uniformly mixing the zinc salt, the tin salt and water to obtain a mixed solution, adding the natural fiber dispersion solution, reacting for 4-6 hours, adding the urea, and carrying out hydrothermal reaction to obtain the natural fiber composite material wrapped by the zinc stannate.
6. The preparation method of the natural fiber composite material wrapped by the zinc stannate according to claim 5, wherein the molar ratio of the zinc salt to the tin salt is 1:1, and the concentration of the zinc salt in the mixed solution is 0.1-0.25 mmol/L; and/or
The addition amount of the urea is 0.3-2 g/L; and/or
The temperature of the hydrothermal reaction is 100-150 ℃, and the time is 6-12 h.
7. A preparation method of a zinc stannate-coated carbon fiber composite material is characterized in that the zinc stannate-coated carbon fiber composite material is prepared by calcining the natural fiber composite material coated with zinc stannate according to any one of claims 1 to 6 under the protection of inert gas or nitrogen.
8. The method of preparing a zinc stannate-coated carbon fiber composite of claim 7, wherein the calcining conditions are: the calcination temperature is 300-500 ℃, the heating rate is 1-5 ℃/min, and the calcination time is 4-8 h.
9. The use of a natural fiber composite material prepared by the method of any one of claims 1 to 6 for photocatalysis.
10. Use of the carbon fiber composite material prepared by the method for preparing a zinc stannate-coated carbon fiber composite material according to claim 7 or 8 in a lithium ion battery.
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