CN108126712B - VOOH/VS4Micron composite powder and its prepn and application - Google Patents
VOOH/VS4Micron composite powder and its prepn and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000000843 powder Substances 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 238000011049 filling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003755 preservative agent Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 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 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 51
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000001627 detrimental effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- -1 vanadyl ions Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/33—
-
- B01J35/39—
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—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
-
- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
VOOH/VS4A micron composite powder and a preparation method and application thereof are provided, wherein sodium metavanadate and thioacetamide are simultaneously added into deionized water to obtain a solution A; then, dropwise adding an ammonia water solution into the solution A to obtain a solution B; pouring the solution B into the reaction lining, and then sealing the hydrothermal reaction; then taking out the cooled product after reaction, and collecting the product after alternately cleaning by water and alcohol; freezing and drying the cleaned product to obtain VOOH/VS4Micron composite powder. VOOH/VS prepared by the above preparation method4The micron composite powder consists of a uniform spherical-like structure with the diameter of about 10 mu m, part of the spherical-like structure is gathered, and the inside of the micron sphere is provided with micron VS with the diameter of 0.5-1.0 mu m and the length of 1.0-2.0 mu m4The short rods are formed by self-stacking, and the outer part of the short rods is formed by randomly forming VOOH long rods with a single crystal structure with the diameter of 50-200 nm. VOOH/VS4The micron composite powder is applied in the fields of lithium/sodium ion batteries and photo/electro-catalysis. When the material is applied to a sodium/lithium ion battery cathode material and a photo/electro-catalyst, the material shows excellent electrochemical performance and catalytic performance.
Description
Technical Field
The invention relates to vanadium compound composite powder and a preparation method thereof, in particular to VOOH/VS4Micron composite powder and its preparation process and use.
Background
With large chain pitch
One-dimensional chain-like LVS with weak inter-chain interaction, high S content and low development cost4[Xu X,Jeong S,Rout CS,Oh P,Ko M,KimH,et al.Lithiumreaction mechanismandhigh rate capability of VS4-graphene nanocomposite as an anode material for lithiumbatteries.J Mater ChemA.2014；2:10847-53.]Are considered to have wider development prospects in the fields of energy storage and photo/electro-catalysis, and have been applied to the fields of photocatalysis, supercapacitors, sodium/lithium ion batteries and the like. At present, with respect to VS4The reports mainly focus on hydrothermal synthesis of pure phases and carbon material composite phases, and the synthesis of the pure phases and the carbon material composite phases usually needs to introduce a template agent, wherein the template agent comprises graphene, carbon nano tubes, conductive polymers (polythiophene, polypyrrole and polyaniline), perylenetetracarboxylic dianhydride and the like, and the synthesis process is complex and tedious [ RoutCS, KimB-H, XuX, Yang J, Jeong HY, OdkhuuD, et. 135:8720-5.]. VOOH is considered to have a great potential for development in the fields of energy storage and photo/electrocatalysis due to its unique oxygen-containing property and variable valence of V, and has been applied in the fields of lithium/sodium electricity and electrocatalysis [ Shao J, Ding Y, Li X, WanZ, WuC, Yang J, et al, low crystalline voohalow microspheres as an output connecting high-rate and simple residence for materials. 1:12404-8.]. However, the synthesis of VOOH is mainly focused on the synthesis of hollow structures by hydrothermal method, andhydrazine hydrate is generally required to be introduced as a reducing agent in the synthesis process, and the synthesis process is generally complex. Therefore, the two substances are compounded by adopting a simple technology to prepare the composite phase with a special structure, so that the advantages of the two substances are exerted in a superposed manner, and the method has very important significance for simultaneously improving the electrochemical and photo/electro-catalytic performances of the composite phase. However, at present, there is no VOOH/VS4The related report of the composite material preparation technology.
Disclosure of Invention
The invention aims to provide VOOH/VS which has simple reaction process, low temperature, easy control and no need of large-scale equipment and harsh reaction conditions4Micron composite powder and its preparation process and use.
In order to achieve the purpose, the preparation method adopted by the invention comprises the following steps:
the method comprises the following steps: simultaneously adding 2.0-2.5 g of sodium metavanadate and 3.4-3.8 g of thioacetamide into 55-65 ml of deionized water, and performing magnetic stirring or ultrasonic dispersion to obtain a semi-clear solution A;
step two: then dropwise adding 0.7-0.9 mol/L ammonia water solution into the solution A until the pH value of the solution reaches 10.6-10.8 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 175-185 ℃ in a rotating state to perform hydrothermal reaction;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out a cooled product after the reaction, and collecting the product after alternately cleaning by water and alcohol;
step five: placing the cleaned product in a cold well of a freeze dryer, freezing for 2-5 hours at-30 to-20 ℃, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 20-30 Pa, drying for 18-24 hours, and collecting the product to obtain VOOH/VS4Micron composite powder.
And (2) magnetically stirring the mixture in the step 1) for 55-65 min at a rotating speed of 500-800 r/min.
And 2) controlling the dropping speed of the ammonia water solution to be 0.13-0.16 ml/min, dropping a drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropping the next drop of ammonia water solution until the pH value of the reaction solution is adjusted to be 10.6-10.8.
The filling ratio of the solution B poured into the reaction lining in the step 3) is 55-65%.
And in the step 3), heating the mixture from room temperature to 175-185 ℃ at the rotating speed of 5-15 r/min, and carrying out hydrothermal reaction for 23-25 h.
And in the step 4), water and alcohol are alternately cleaned by suction filtration or centrifugation for 3-6 times.
And 4) performing suction filtration or centrifugation on the collection in the step 4).
And (3) sealing the product obtained in the step 5) by using a perforated preservative film before the product is placed into a tray for drying.
VOOH/VS prepared by the above preparation method4The micron composite powder consists of a uniform spherical-like structure with the diameter of about 10 mu m, part of the spherical-like structure is gathered, and the inside of the micron sphere is provided with micron VS with the diameter of 0.5-1.0 mu m and the length of 1.0-2.0 mu m4The short rods are formed by self-stacking, and the outer part of the short rods is formed by randomly forming VOOH long rods with a single crystal structure with the diameter of 50-200 nm.
VOOH/VS4The micron composite powder is applied in the fields of lithium/sodium ion batteries and photo/electro-catalysis. When the material is applied to a sodium/lithium ion battery cathode material and a photo/electro-catalyst, the material shows excellent electrochemical performance and catalytic performance.
The method adopts a hydrothermal method, takes water as a solvent, takes sodium metavanadate and thioacetamide as a vanadium source and a sulfur source respectively, and realizes the generation of the three-dimensional self-assembled VS by the one-step hydrothermal method by cooperatively controlling the concentration, the proportion, the reaction temperature, the reaction time and other parameters, particularly strictly controlling three parameters of the reaction pH value, the filling ratio and the ammonia water concentration4And (3) growing a VOOH long rod composite structure on the surface of the microsphere in a controllable manner. The method has the advantages of simple reaction process, low temperature, easy control, no need of large-scale equipment and harsh reaction conditions, and can simultaneously realize the structure that two substances are combined in a specific way in one reaction process. When the above product is used as sodiumThe lithium ion battery cathode material and the photo/electro-catalyst can show excellent electrochemical performance and catalytic performance.
The method has the following specific beneficial effects:
(1) the invention adopts one-step hydrothermal reaction to directly synthesize the final product, thereby having low synthesis temperature, simple synthesis path and no need of large-scale equipment and harsh reaction conditions;
(2) the vanadium source used in the method is sodium metavanadate, the sulfur source is thioacetamide, the two raw materials are common materials, and the method has the advantages of low price, easy obtainment, low cost, high yield, easy control of reaction, no need of post-treatment, environmental friendliness and suitability for large-scale production;
(3) the product prepared by the method has the advantages of uniform chemical composition, high purity and uniform appearance, and can show excellent performance when being used as a lithium/sodium ion battery cathode material and a photo/electro catalyst;
(4) the invention realizes the control of the existing state of vanadium and sulfur in the reaction by strictly and cooperatively controlling the concentration and the proportion of the vanadium source and the sulfur source, the reaction temperature, the reaction time, the reaction pH value, the filling ratio, the ammonia water concentration and other parameters, thereby leading the initial stage of the reaction to mainly generate VS4In the middle and later stage, VOOH is mainly generated, and finally high-purity and uniform VOOH/VS is realized4Preparing a composite material;
(5) in the process of synthesizing the three-dimensional self-assembly structure, no template agent or surfactant is introduced, and the whole self-assembly process is controlled by the self-template action of reaction raw materials, so that the whole reaction is simple, easy to control, high-efficiency and low in cost;
(6) the pH value of the invention is relative to VOOH/VS4The synthesis of micron composite powder plays a key role, and the pH represents H in solution+/OH-The different pH values of the water will influence the existence state of the sulfur source and the vanadium source in the solution, and further influence VS in the hydrothermal process4And VOOH, while affecting the complex state of the two. Too high a pH value is detrimental to S2 2-Formation of ions, in turn adverse to VS4And (4) synthesizing. At the same time, too high a pH tends to hydrolyze thioacetamide to S2-Followed by reaction with vanadyl ions to form VS2. Too low a pH does not provide sufficient OH-Further, VOOH cannot be produced. Thus, the pH of the reaction solution was adjusted to VOOH/VS4The realization of composite structures has a critical role.
(7) Reaction filling ratio of the invention to pure phase VOOH/VS4The synthesis of the micron composite powder plays a key role. The reaction fill ratio primarily affects the reaction pressure and, in turn, the composition and structure of the product formed. Too low a fill ratio is detrimental to the conversion of-2. sup. valent sulfur to-1. sup. valent sulfur in thioacetamide in the reaction, and VS is formed2. At the same time, the low reaction fill ratio is not conducive to the reaction taking place adequately, with the consequent conversion of some thioacetamide to the elemental sulfur impurity phase. Too high a fill ratio will increase the nucleation rate of VOOH, which in turn will make VOOH more prone to particle formation. Thus, the reaction fill ratio was adjusted for VOOH/VS4The realization of composite structures also has a critical role.
(8) In the invention, the concentration of ammonia water for adjusting the pH value of the solution is relative to pure phase VOOH/VS4The micron composite powder also has important function. Too high ammonia concentration can cause too high a local solution pH during pH adjustment, resulting in a large amount of heterogeneous phase.
(9) The composite product prepared by the invention has a unique composite structure, wherein VS4The micron spherical self-assembly structure formed by self-stacking of the short rods has unique physical confinement effect, and the confinement effect can effectively inhibit VS in the charge-discharge process4Can expand/contract, thereby improving the cycle performance of the material. Furthermore, VS4The nano rod-shaped VOOH on the surface of the microsphere can further inhibit VS4The volume expansion of the composite material is reduced, and the pseudo-capacitance characteristic of VOOH can remarkably accelerate the transmission speed of charges, so that the electrochemical reaction power of the composite material can be improved, and the multiplying power performance of the composite material is finally improved. Meanwhile, the unique single crystal structure of the VOOH nanorod can show better structural stability in the charging and discharging processes and also can show good charge transmission performance.
(11) The nano-scale of VOOH on the surface of the composite product prepared by the method not only can generate larger specific surface area, but also can provide more surface active sites, thereby improving the electrochemical performance and the catalytic performance. In addition, the super-small size can not only shorten a charge transmission path, but also provide more active sites for charge storage, so that the specific capacity and rate capability of the material can be improved. At the same time, the ability of such ultra-small VOOH surfaces to expose more oxygen provides sufficient assurance of oxygen generating performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1 of this invention.
FIG. 2 is a scanning electron micrograph of a product prepared according to example 1 of the present invention.
FIG. 3 is a high power scanning electron micrograph of the product prepared in example 1 of the present invention.
FIG. 4 is a high power scanning electron micrograph of the product prepared in example 1 of the present invention.
FIG. 5 is a super high power scanning electron micrograph of the product prepared in example 1 of the present invention.
FIG. 6 is a high-resolution transmission electron micrograph of VOOH on the surface of the product prepared in example 1 of the present invention.
FIG. 7 is a scanning electron micrograph of a product obtained after pH adjustment to 11.0 (otherwise exactly the same conditions as in example 1).
FIG. 8 is a scanning electron micrograph of a product obtained after pH adjustment to 10.0 (otherwise exactly the same conditions as in example 1).
FIG. 9 is a scanning electron micrograph of a product obtained after setting the reaction filling ratio in example 1 of the present invention to 50% (otherwise, exactly the same conditions as in example 1).
FIG. 10 is a scanning electron micrograph of a product obtained by adjusting the reaction filling ratio to 70% in example 1 of the present invention (otherwise, exactly the same conditions as in example 1).
FIG. 11 is a scanning electron micrograph of a product obtained after adjusting the concentration of aqueous ammonia to 1.5mol/L (other conditions were exactly the same as in example 1).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
the method comprises the following steps: 2.4g of sodium metavanadate and 3.6g of thioacetamide are simultaneously added into 60ml of deionized water, and the mixture is magnetically stirred for 60min under the condition of the rotating speed of 600r/min to obtain a semi-clear solution A;
step two: dropwise adding 0.7mol/L ammonia water solution into the solution A, controlling the dropping speed of the ammonia water solution to be 0.15ml/min, dropwise adding one drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of ammonia water solution until the pH value of the solution reaches 10.6 to obtain a solution B;
step three: pouring the solution B into a reaction lining according to the filling ratio of 60%, sealing, placing the lining in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 180 ℃ under the condition of the rotation speed of 10r/min for hydrothermal reaction for 24 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out a cooled product after the reaction, and performing suction filtration and collection on the product for 3 times by alternately performing suction filtration on water and alcohol;
step five: placing the cleaned product in a cold well of a freeze dryer, freezing for 2 hours at-25 ℃, then placing the frozen product in a tray, sealing by using a perforated preservative film, covering a sealing cover, vacuumizing to 20Pa, drying for 18 hours, and collecting the product to obtain VOOH/VS4Micron composite powder.
From fig. 1, it is clear that the diffraction peak is more elongated and smoother, indicating that the product has good crystallinity. Meanwhile, through comparison with a standard card, the diffraction peaks can be divided into two types, one type corresponds to VS4One corresponding to VOOH means that the product synthesized by the preparation method provided by this patent is VS4And VOOH.
As can be seen from FIG. 2, the resulting product is composed of uniform spheroidal structures with high morphological uniformity, with some spheroidal structures being aggregated.
As can be seen from FIG. 3, the diameter of the microspheres of the obtained product is about 10 μm, and the outside is all randomly assembled by VOOH nanorods.
As can be seen from FIG. 4, the interior of the resulting product is defined by a micron VS of 0.5 to 1.0 μm in diameter and 1.0 to 2.0 μm in length4The short rods are formed by self-stacking.
As can be seen from FIG. 5, the diameter of the VOOH long rod in the obtained product is 50-200 nm.
The regularly arranged lattice stripes can be seen in fig. 6, which shows that the VOOH nanorods have a single crystal structure.
As can be seen from FIG. 7, the major phase of the resulting product is represented by VS2Nanosheet self-assembled microspheres. Thus, increasing the pH results in VS4Transition to VS2。
As can be seen in FIG. 8, the resulting product is represented by VS4The rod-wound microspheres did not have VOOH formation. Therefore, reducing the pH is detrimental to VOOH formation.
As can be seen in FIG. 9, the product consists of nanosheets VS2And a blocky S simple substance. Therefore, lowering the reaction fill ratio is detrimental to VS4And (4) synthesizing.
As can be seen in FIG. 10, the resulting product VS4The rod size is increased and the VOOH single crystal rod becomes assembled from nanoparticles. Therefore, increasing the reaction fill ratio is not conducive to the VOOH/VS aspect of the invention4And (4) forming a composite structure.
As can be seen from fig. 11, a large amount of bulk elemental sulfur is present in the product. Therefore, too high ammonia concentration is detrimental to the pure phase VOOH/VS4And (4) synthesizing a micron composite material.
Example 2:
the method comprises the following steps: 2.0g of sodium metavanadate and 3.5g of thioacetamide are simultaneously added into 55ml of deionized water, and the mixture is magnetically stirred for 65min under the condition of the rotating speed of 500r/min to obtain a semi-clear solution A;
step two: dropwise adding 0.9mol/L ammonia water solution into the solution A, controlling the dropping speed of the ammonia water solution to be 0.13ml/min, dropwise adding one drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of ammonia water solution until the pH value of the solution reaches 10.7 to obtain a solution B;
step three: pouring the solution B into a reaction lining according to the filling ratio of 55%, sealing, placing the lining in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 175 ℃ under the condition of the rotating speed of 5r/min for hydrothermal reaction for 25 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, and performing alternate centrifugation on water and alcohol for 6 times and performing centrifugal collection;
step five: placing the cleaned product in a cold well of a freeze dryer, freezing for 3 hours at-28 ℃, then placing the frozen product in a tray, sealing by using a perforated preservative film, covering a sealing cover, vacuumizing to 30Pa, drying for 22 hours, and collecting the product to obtain VOOH/VS4Micron composite powder.
Example 3:
the method comprises the following steps: 2.2g of sodium metavanadate and 3.8g of thioacetamide are simultaneously added into 65ml of deionized water, and the mixture is magnetically stirred for 55min under the condition of the rotating speed of 800r/min to obtain a semi-clear solution A;
step two: dropwise adding 0.8mol/L ammonia water solution into the solution A, controlling the dropping speed of the ammonia water solution to be 0.16ml/min, dropwise adding one drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of ammonia water solution until the pH value of the solution reaches 10.7 to obtain a solution B;
step three: pouring the solution B into a reaction lining according to a filling ratio of 65%, sealing, placing the lining in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 185 ℃ under the condition of a rotating speed of 8r/min for hydrothermal reaction for 23 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, performing suction filtration on water and alcohol alternately for 4 times, and performing centrifugal collection;
step five: placing the cleaned product in a cold well of a freeze dryer, freezing for 5 hours at-30 ℃, then placing the frozen product in a tray, sealing by using a perforated preservative film, covering a sealing cover, vacuumizing to 23Pa, drying for 20 hours, and collecting the product to obtain VOOH/VS4Micron composite powder.
Example 4:
the method comprises the following steps: 2.5g of sodium metavanadate and 3.4g of thioacetamide are simultaneously added into 63ml of deionized water, and a semi-clear solution A is obtained through ultrasonic dispersion;
step two: dropwise adding 0.85mol/L ammonia water solution into the solution A, controlling the dropping speed of the ammonia water solution to be 0.14ml/min, dropwise adding one drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of ammonia water solution until the pH value of the solution reaches 10.8 to obtain a solution B;
step three: pouring the solution B into a reaction lining according to a filling ratio of 63%, sealing, placing the lining in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 183 ℃ under the condition of a rotating speed of 15r/min for hydrothermal reaction for 24 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out a cooled product after the reaction, alternately centrifuging for 5 times by using water and alcohol, and collecting by suction filtration;
step five: placing the cleaned product in a cold well of a freeze dryer, freezing for 4 hours at-20 ℃, then placing the frozen product in a tray, sealing by using a perforated preservative film, covering a sealing cover, vacuumizing to 28Pa, drying for 24 hours, and collecting the product to obtain VOOH/VS4Micron composite powder.
Claims (10)
1. VOOH/VS4The preparation method of the micron composite powder is characterized by comprising the following steps:
the method comprises the following steps: simultaneously adding 2.0-2.5 g of sodium metavanadate and 3.4-3.8 g of thioacetamide into 55-65 mL of deionized water, and performing magnetic stirring or ultrasonic dispersion to obtain a semi-clear solution A;
step two: then dropwise adding 0.7-0.9 mol/L ammonia water solution into the solution A until the pH value of the solution reaches 10.6-10.8 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 175-185 ℃ in a rotating state to perform hydrothermal reaction;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out a cooled product after the reaction, and collecting the product after alternately cleaning by water and alcohol;
step five: placing the cleaned product in a cold well of a freeze dryer, freezing for 2-5 hours at-30 to-20 ℃, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 20-30 Pa, drying for 18-24 hours, and collecting the product to obtain VOOH/VS4Micron composite powder.
2. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: the rotating speed of the magnetic stirring in the step one) is 500-800 r/min, and the time is 55-65 min.
3. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: and step two), controlling the dropping speed of the ammonia water solution to be 0.13-0.16 mL/min, dropping a drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropping the next drop of ammonia water solution until the pH value of the reaction solution is adjusted to be 10.6-10.8.
4. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: and in the third step), the filling ratio of the solution B poured into the reaction lining is 55-65%.
5. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: and step three), heating the mixture from room temperature to 175-185 ℃ at the rotating speed of 5-15 r/min, and carrying out hydrothermal reaction for 23-25 h.
6. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: and step four), alternately cleaning water and alcohol by adopting suction filtration or centrifugation for 3-6 times.
7. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: and step four) collection is carried out by suction filtration or centrifugation.
8. VOOH/VS as in claim 14The preparation method of the micron composite powder is characterized by comprising the following steps: and sealing the product obtained in the step five) by using a perforated preservative film before the product is placed into a tray for drying.
9. VOOH/VS prepared by the preparation method of claim 14The micron composite powder is characterized in that: VOOH/VS4The micron composite powder consists of a uniform spherical-like structure with the diameter of about 10 mu m, part of the spherical-like structure is gathered, and the inside of the micron sphere is provided with micron VS with the diameter of 0.5-1.0 mu m and the length of 1.0-2.0 mu m4The short rods are formed by self-stacking, and the outer part of the short rods is formed by randomly forming VOOH long rods with a single crystal structure with the diameter of 50-200 nm.
10. A VOOH/VS as claimed in claim 94The micron composite powder is applied in the fields of lithium/sodium ion batteries and photo/electro-catalysis.
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| CN108726571B (en) * | 2018-07-02 | 2021-04-23 | 陕西科技大学 | VS (virtual switch)4nanorod/VS2Nano sheet three-dimensional self-assembly hollow rod-shaped composite powder and preparation method thereof |
| CN109295475B (en) * | 2018-10-10 | 2020-01-21 | 陕西科技大学 | Preparation method of selenium-doped vanadium selenide composite material |
| CN110368955B (en) * | 2019-08-12 | 2022-06-07 | 陕西科技大学 | VS (virtual switch)2Preparation method of CdS composite photocatalyst |
| CN115092961B (en) * | 2022-07-14 | 2023-12-22 | 贵州大学 | Preparation method and application of hollow spherical shell structured vanadium oxyhydroxide |
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