CN108126712A - A kind of VOOH/VS4Micron composite granule and preparation method and application - Google Patents
A kind of VOOH/VS4Micron composite granule and preparation method and application Download PDFInfo
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- CN108126712A CN108126712A CN201711406620.5A CN201711406620A CN108126712A CN 108126712 A CN108126712 A CN 108126712A CN 201711406620 A CN201711406620 A CN 201711406620A CN 108126712 A CN108126712 A CN 108126712A
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000008187 granular material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000013019 agitation Methods 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000003755 preservative agent Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 46
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000011049 filling Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 150000001875 compounds Chemical class 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013066 combination product Substances 0.000 description 2
- 229940127555 combination product Drugs 0.000 description 2
- 230000005611 electricity 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
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- ZFDNHUHPLXMMBR-UHFFFAOYSA-N sulfanylidenevanadium Chemical compound [V]=S ZFDNHUHPLXMMBR-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- -1 vanadium oxygen radical ion Chemical class 0.000 description 1
Classifications
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of VOOH/VS4Micron composite granule and preparation method and application takes sodium metavanadate and thioacetamide to be added to simultaneously in deionized water and obtains solution A；Then ammonia spirit is added dropwise into solution A and obtains solution B；Hydro-thermal reaction is sealed after solution B is poured into reaction liner；Then the product for reacting postcooling is taken out, is collected after water and alcohol alternately clean；By drying to obtain VOOH/VS after the product freezing after cleaning4Micron composite granule.The VOOH/VS as made of method made above4The near-spherical structure composition that micron composite granule is about 10 μm by uniform diameter, part near-spherical structure are assembled, and the inside of micron ball is by a diameter of 0.5~1.0 μm, the micron VS that length is 1.0~2.0 μm4From accumulating, outside is made of stub at random the VOOH long sticks of a diameter of 50~200nm mono-crystalline structures.VOOH/VS4Micron composite granule is in the application of lithium/sodium-ion battery and optical electrical catalytic field.During using for sodium/lithium ion battery negative material and optical electrical catalyst, excellent chemical property and catalytic performance are shown.
Description
Technical field
The present invention relates to a kind of vanadium sub-group compound composite granules and preparation method thereof, and in particular to a kind of VOOH/VS4Micron
Composite granule and preparation method thereof and purposes.
Background technology
With big chain spacingThe one-dimensional chain of weak interchain interaction, high S contents and low development cost is green
Sulphur navajoite VS4[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.] it is considered in energy storage
There is wider development prospect, and they are in photocatalysis, ultracapacitor, sodium/lithium-ion electric with optical electrical catalytic field
It is applied in the fields such as pond.At present, about VS4Report be concentrated mainly on pure phase and the hydrothermal synthesis with carbon material compound phase
On, and their synthesis usually requires to introduce template, template includes graphene, carbon nanotube, conducting polymer (poly- thiophene
Fen, polypyrrole and polyaniline) and tetracid dianhydride etc., building-up process it is complex it is cumbersome [RoutCS, KimB-H, XuX,
Yang J,Jeong HY,OdkhuuD,etal.Synthesis andcharacterizationof patronite formof
vanadiumsulfide on graphitic layer.J AmChemSoc.2013；135:8720-5.].VOOH is only due to it
The special valence state changeable containing oxygen characteristic and V is considered having larger development potentiality in energy storage and optical electrical catalytic field,
And it is applied [Shao J, Ding Y, Li X, WanZ, WuC, Yang J, et in lithium/sodium electricity and electro-catalysis field
al.Low crystallinity VOOHhollow microspheres as anoutstanding high-rate
andlong-life cathode for sodiumionbatteries.J Mater ChemA.2013；1:12404-8.].So
And hydro-thermal method synthesis hollow structure is concentrated mainly on about the synthesis of VOOH at present, and need to usually introduce water in the synthesis process
Hydrazine is closed as reducing agent, building-up process is typically more complicated.Therefore, by using a kind of simple technology by both substances into
Row is compound, prepares the compound phase with special construction, so as to which the advantage of the two is overlapped performance, for promoting its electricity simultaneously
Chemistry and optical electrical catalytic performance will have very important significance.However, there is no VOOH/VS at present4Composite material prepares skill
The relevant report of art.
Invention content
The purpose of the present invention is to provide a kind of reaction process is simple, temperature is low, easily-controllable and do not need to large scale equipment and severe
Carve the VOOH/VS of reaction condition4Micron composite granule and preparation method thereof and purposes.
In order to achieve the above objectives, the preparation method that the present invention uses includes the following steps：
Step 1：Take 2.0~2.5g sodium metavanadates and 3.4~3.8g thioacetamides be added to simultaneously 55~65ml go from
In sub- water, magnetic agitation or ultrasonic disperse obtain half clear solution A；
Step 2：Then the ammonia spirit of 0.7~0.9mol/L is added dropwise dropwise into solution A, until solution ph reaches
10.6~10.8, obtain solution B；
Step 3：It is sealed after solution B is poured into reaction liner, liner is placed on homogeneous reaction instrument loaded on fixation in outer kettle
In, 175~185 DEG C of progress hydro-thermal reactions are heated to by room temperature under rotation status；
Step 4：After hydro-thermal reaction, reaction kettle is naturally cooled into room temperature, then takes the product for reacting postcooling
Go out, collected after water and alcohol alternately clean；
Step 5：Product after cleaning is placed in the cold well of freeze drier, under the conditions of -30~-20 DEG C freeze 2~
5 hour, then the product after freezing is placed in pallet, covers seal closure, be evacuated down to 20~30Pa, dry 18~for 24 hours after
Product is collected to get to VOOH/VS4Micron composite granule.
Step 1) the magnetic agitation 55~65min of magnetic agitation under the speed conditions of 500~800r/min.
The rate of addition of step 2) the control ammonia spirit is 0.13~0.16ml/min, and it is molten to drip a drop ammonium hydroxide
Liquid after stirring is until solution ph stablizes, then instills next drop ammonia spirit, until reacting liquid pH value be adjusted to 10.6~
10.8。
The packing ratio that the step 3) solution B pours into reaction liner is 55~65%.
The step 3) under the speed conditions of 5~15r/min by room temperature be heated to 175~185 DEG C of hydro-thermal reactions 23~
25h。
Alternately cleaning using suction filtration or centrifuges 3-6 times for the step 4) water and alcohol.
The step 4) is collected to be carried out using suction filtration or centrifugation.
Step 5) the product is sealed before being put into pallet and being dried with the preservative film for pricking hole.
The VOOH/VS as made of method made above4The near-spherical that micron composite granule is about 10 μm by uniform diameter
Structure composition, part near-spherical structure are assembled, and the inside of micron ball is by a diameter of 0.5~1.0 μm, length 1.0
~2.0 μm of micron VS4For stub from accumulating, outside is random by the VOOH long sticks of a diameter of 50~200nm mono-crystalline structures
Composition.
VOOH/VS4Micron composite granule is in the application of lithium/sodium-ion battery and optical electrical catalytic field.Using for sodium/lithium
When ion battery cathode material and optical electrical catalyst, excellent chemical property and catalytic performance are shown.
The present invention is using hydro-thermal method, is respectively vanadium source and sulphur source with sodium metavanadate and thioacetamide using water as solvent,
By parameters such as their concentration of Collaborative Control and proportioning, reaction temperature, reaction time, especially stringent control pH value in reaction,
When three parameters of ammonia concn are filled, realize the three-dimensional self assembly VS of one step hydro thermal method generation4Micron ball, and in micron ball table
It looks unfamiliar the controllable preparation of long VOOH long sticks composite construction.This method reaction process is simple, temperature is low, easily-controllable and do not need to large size and set
Standby and harsh reaction condition can realize the structure that two kinds of substances combine in a specific way simultaneously in a reaction process.
When applying above-mentioned product for sodium/lithium ion battery negative material and optical electrical catalyst, it can show excellent electrification
Learn performance and catalytic performance.
Specifically have the beneficial effect that：
(1) present invention using a step hydro-thermal reaction due to directly synthesizing final product, thus has low synthesis temperature
Degree, simple synthesis path do not need to large scale equipment and harsh reaction condition；
(2) vanadium source used in the present invention is sodium metavanadate, sulphur source is thioacetamide, both raw materials are common materials,
It is cheap and easy to get, at low cost, yield is high, reaction is easily-controllable, without post-processing, environmentally friendly, can be suitble to mass produce；
(3) the product chemistry composition of the invention prepared is uniform, purity is high, pattern is uniform, is born as lithium/sodium-ion battery
Excellent performance can be shown when pole material and optical electrical catalyst；
(4) present invention passes through stringent Collaborative Control vanadium source, the concentration of sulphur source and proportioning, reaction temperature, reaction time, reaction
PH value fills the when parameters such as ammonia concn, the control of vanadium sulphur existence in reaction is realized, so as to make reaction initial period
Mainly generate VS4, stage middle and later periods mainly generates VOOH, finally realizes high-purity and uniform VOOH/VS4The system of composite material
It is standby；
(5) present invention does not introduce any template or surfactant during the three-dimensional self-assembled structures of synthesis,
Entire self assembling process is the self-template effect control by reaction raw materials, thus entirely react it is simple, easily-controllable, efficient and it is low into
This；
(6) present invention in pH value for VOOH/VS4The synthesis of micron composite granule plays crucial effect, and pH represents molten
H in liquid+/OH-Number, different pH value will influence solution in the existence in sulphur source and vanadium source, and then influence water-heat process in
VS4With the generation of VOOH, while the combined state both influenced.Excessively high pH value is unfavorable for S2 2-The formation of ion, it is then unfavorable
In VS4Synthesis.Meanwhile excessively high pH is easy to make thioacetamide hydrolysis generation S2-, then generation is reacted with vanadium oxygen radical ion
VS2.Too low pH value can not provide sufficient OH-, and then VOOH can not be generated.Therefore, regulation and control reaction solution pH is for VOOH/
VS4The realization of composite construction has the function of key.
(7) present invention in reaction-filling ratio for pure phase VOOH/VS4The synthesis of micron composite granule plays crucial work
With.Reaction-filling influences reaction pressure, and then influence the Nomenclature Composition and Structure of Complexes of generation product than main.Too low reaction-filling ratio is not
Conducive to make in reaction in thioacetamide-divalent sulphur is converted into -1 valency, and then that generate is VS2.Meanwhile low reaction-filling
Than the abundant generation for being unfavorable for reaction, then have part thioacetamide and be converted to sulphur simple substance dephasign.Excessively high packing ratio meeting
Accelerate the nucleation rate of VOOH, and then VOOH can be made to tend to generation graininess.Therefore, regulation and control reaction-filling ratio for
VOOH/VS4The realization of composite construction also has the function of key.
(8) concentration of solution ph ammonium hydroxide is adjusted in the present invention for pure phase VOOH/VS4Micron composite granule equally has
There is important role.Excessively high ammonia concn, topical solutions pH value is excessively high during making pH adjustings, a large amount of miscellaneous so as to generate
Phase.
(9) combination product prepared by the present invention has unique composite construction, wherein VS4Stub accumulates the micron formed certainly
Spherical self-assembled structures have unique physics confinement effect, and this confinement effect can effectively inhibit charge and discharge process VS4's
Volume expansion/contraction, so as to promote the cycle performance of material.In addition, VS4Mono- sides of nano bar-shape VOOH of micron ball surface
Face can further suppress VS4Volume expansion, the fake capacitance characteristic of another aspect VOOH can dramatically speed up the transmission of charge
Speed, and then the electrochemical reaction power of composite material can be promoted, the final high rate performance for promoting material.Meanwhile VOOH
The unique mono-crystalline structures of nanometer rods can show preferable structural stability in charge and discharge process, can also show good
Charge-transporting.
(11) nanoscale of the combination product surface VOOH prepared by the present invention, can not only generate larger specific surface
Product, but also more surface-active sites can be provided, and then chemical property and catalytic performance can be promoted.In addition, this
Kind super-small can not only shorten charge transfer path, but also can provide more active sites for the storage of charge
Point, so as to promote the specific capacity of material and high rate performance.Meanwhile the VOOH surfaces of this super-small can expose more
Oxygen provides sufficient guarantee for production oxygen performance.
Description of the drawings
Fig. 1 is the X-ray diffractogram that the embodiment of the present invention 1 prepares product.
Fig. 2 is the low power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 3 is the high power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 4 is the high power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 5 is the super-high power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 6 is the high-resolution-ration transmission electric-lens figure that the embodiment of the present invention 1 prepares surface VOOH.
Fig. 7 is the scanning electron microscope (SEM) photograph that pH is adjusted to after 11.0 to (other conditions are identical with embodiment 1) products therefrom.
Fig. 8 is the scanning electron microscope (SEM) photograph that pH is adjusted to after 10.0 to (other conditions are identical with embodiment 1) products therefrom.
Fig. 9 be by the reaction-filling ratio in the embodiment of the present invention 1 be 50% after (other conditions are identical with embodiment 1)
The scanning electron microscope (SEM) photograph of products therefrom.
Figure 10 is (other conditions are complete with embodiment 1 after the reaction-filling ratio in the embodiment of the present invention 1 is adjusted to 70%
It is identical) scanning electron microscope (SEM) photograph of products therefrom.
Figure 11 is that the concentration of ammonium hydroxide is adjusted to (other conditions are identical with embodiment 1) products therefrom after 1.5mol/L
Scanning electron microscope (SEM) photograph.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1：
Step 1：2.4g sodium metavanadates and 3.6g thioacetamides is taken to be added to simultaneously in 60ml deionized waters, in 600r/
Magnetic agitation 60min obtains half clear solution A under the speed conditions of min；
Step 2：Then the ammonia spirit of 0.7mol/L is added dropwise dropwise into solution A, controls the rate of addition of ammonia spirit
For 0.15ml/min, a drop ammonia spirit is dripped, stirring is after solution ph is stablized, then instills next drop ammonia spirit,
Until solution ph reaches 10.6, solution B is obtained；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 60% packing ratio
It is placed in homogeneous reaction instrument, 180 DEG C of hydro-thermal reactions is heated to for 24 hours by room temperature under the speed conditions of 10r/min；
Step 4：After hydro-thermal reaction, reaction kettle is naturally cooled into room temperature, then takes the product for reacting postcooling
Go out, alternately filtered 3 times through water and alcohol and use collected by suction；
Step 5：Product after cleaning is placed in the cold well of freeze drier, freezes 2 hours under the conditions of -25 DEG C, so
The product after freezing is placed in pallet afterwards, seal closure is covered after being sealed with the preservative film for pricking hole, is evacuated down to 20Pa, is done
Product is collected after dry 18h to get to VOOH/VS4Micron composite granule.
It can be clearly seen that more elongated smooth diffraction maximum from Fig. 1, illustrate that the product has good crystallinity.
Meanwhile found by being compared with standard card, diffraction maximum can be divided into two kinds, and one kind corresponds to VS4, it is a kind of to correspond to VOOH,
Mean that by the product that the preparation method that this patent provides synthesizes be VS4With the compound of VOOH.
From figure 2 it can be seen that products therefrom is by uniform near-spherical structure composition, it is uniform with higher pattern
Property, part-spherical is assembled.
From figure 3, it can be seen that the diameter of the micron ball of products therefrom is about 10 μm, and outside is all by VOOH nanometer rods
Assemble at random.
Figure 4, it is seen that the inside of products therefrom be by a diameter of 0.5~1.0 μm, length be 1.0~2.0 μm
Micron VS4Stub is accumulated certainly.
From figure 5 it can be seen that in products therefrom VOOH long sticks a diameter of 50~200nm.
As can be seen from Figure 6 the lattice fringe of regular arrangement, it is mono-crystalline structures to illustrate VOOH nanometer rods.
It can be seen from figure 7 that the main phase of products therefrom is by VS2The micron ball of nanometer sheet self assembly.Therefore, increase pH
Value can lead to VS4It is changed into VS2。
As can be seen from Figure 8, products therefrom is by VS4The micron ball that stick is entwined, there is no the formation of VOOH.Cause
This, reduces the formation that pH value is unfavorable for VOOH.
It can be seen in figure 9 that product is by nano-sheet VS2It is formed with blocky S simple substance two parts.Therefore, reaction is reduced
Packing ratio is unfavorable for VS4Synthesis.
It can be seen from fig. 10 that products therefrom VS4The scale increase of stick, VOOH monocrystal rods become by nano particle group
It fills.Therefore, increase reaction-filling ratio is unfavorable for VOOH/VS of the present invention4The formation of composite construction.
It can be seen from fig. 11 that occur a large amount of block sulphur simple substances in product.Therefore, excessively high ammonia concn is unfavorable for
Pure phase VOOH/VS4The synthesis of micro-composites.
Embodiment 2：
Step 1：2.0g sodium metavanadates and 3.5g thioacetamides is taken to be added to simultaneously in 55ml deionized waters, in 500r/
Magnetic agitation 65min obtains half clear solution A under the speed conditions of min；
Step 2：Then the ammonia spirit of 0.9mol/L is added dropwise dropwise into solution A, controls the rate of addition of ammonia spirit
For 0.13ml/min, a drop ammonia spirit is dripped, stirring is after solution ph is stablized, then instills next drop ammonia spirit,
Until solution ph reaches 10.7, solution B is obtained；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 55% packing ratio
It is placed in homogeneous reaction instrument, 175 DEG C of hydro-thermal reaction 25h is heated to by room temperature under the speed conditions of 5r/min；
Step 4：After hydro-thermal reaction, reaction kettle is naturally cooled into room temperature, then takes the product for reacting postcooling
Go out, be collected by centrifugation through 6 uses of water and alcohol alternating centrifugal；
Step 5：Product after cleaning is placed in the cold well of freeze drier, freezes 3 hours under the conditions of -28 DEG C, so
The product after freezing is placed in pallet afterwards, seal closure is covered after being sealed with the preservative film for pricking hole, is evacuated down to 30Pa, is done
Product is collected after dry 22h to get to VOOH/VS4Micron composite granule.
Embodiment 3：
Step 1：2.2g sodium metavanadates and 3.8g thioacetamides is taken to be added to simultaneously in 65ml deionized waters, in 800r/
Magnetic agitation 55min obtains half clear solution A under the speed conditions of min；
Step 2：Then the ammonia spirit of 0.8mol/L is added dropwise dropwise into solution A, controls the rate of addition of ammonia spirit
For 0.16ml/min, a drop ammonia spirit is dripped, stirring is after solution ph is stablized, then instills next drop ammonia spirit,
Until solution ph reaches 10.7, solution B is obtained；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 65% packing ratio
It is placed in homogeneous reaction instrument, 185 DEG C of hydro-thermal reaction 23h is heated to by room temperature under the speed conditions of 8r/min；
Step 4：After hydro-thermal reaction, reaction kettle is naturally cooled into room temperature, then takes the product for reacting postcooling
Go out, alternately filtering 4 uses through water and alcohol is collected by centrifugation；
Step 5：Product after cleaning is placed in the cold well of freeze drier, freezes 5 hours under the conditions of -30 DEG C, so
The product after freezing is placed in pallet afterwards, seal closure is covered after being sealed with the preservative film for pricking hole, is evacuated down to 23Pa, is done
Product is collected after dry 20h to get to VOOH/VS4Micron composite granule.
Embodiment 4：
Step 1：2.5g sodium metavanadates and 3.4g thioacetamides is taken to be added to simultaneously in 63ml deionized waters, ultrasound point
It dissipates and obtains half clear solution A；
Step 2：Then the ammonia spirit of 0.85mol/L is added dropwise dropwise into solution A, controls the dropwise addition speed of ammonia spirit
It spends for 0.14ml/min, drips a drop ammonia spirit, after stirring is until solution ph stablizes, then to instill next drop ammonium hydroxide molten
Liquid until solution ph reaches 10.8, obtains solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 63% packing ratio
It is placed in homogeneous reaction instrument, 183 DEG C of hydro-thermal reactions is heated to for 24 hours by room temperature under the speed conditions of 15r/min；
Step 4：After hydro-thermal reaction, reaction kettle is naturally cooled into room temperature, then takes the product for reacting postcooling
Go out, collected by suction is used through water and alcohol alternating centrifugal 5 times；
Step 5：Product after cleaning is placed in the cold well of freeze drier, freezes 4 hours under the conditions of -20 DEG C, so
The product after freezing is placed in pallet afterwards, seal closure is covered after being sealed with the preservative film for pricking hole, is evacuated down to 28Pa, is done
Dry product of collecting afterwards for 24 hours is to get to VOOH/VS4Micron composite granule.
Claims (10)
1. a kind of VOOH/VS4The preparation method of micron composite granule, it is characterised in that：
Step 1：2.0~2.5g sodium metavanadates and 3.4~3.8g thioacetamides is taken to be added to 55~65ml deionized waters simultaneously
In, magnetic agitation or ultrasonic disperse obtain half clear solution A；
Step 2：Then the ammonia spirit of 0.7~0.9mol/L is added dropwise dropwise into solution A, until solution ph reaches 10.6
~10.8, obtain solution B；
Step 3：It is sealed after solution B is poured into reaction liner, liner is placed on loaded on fixation in outer kettle in homogeneous reaction instrument,
175~185 DEG C of progress hydro-thermal reactions are heated to by room temperature under rotation status；
Step 4：After hydro-thermal reaction, reaction kettle is naturally cooled into room temperature, then takes out the product for reacting postcooling,
It is collected after water and alcohol alternately clean；
Step 5：Product after cleaning is placed in the cold well of freeze drier, it is small that 2~5 are freezed under the conditions of -30~-20 DEG C
When, then the product after freezing is placed in pallet, covers seal closure, is evacuated down to 20~30Pa, drying 18~collect afterwards for 24 hours
Product is to get to VOOH/VS4Micron composite granule.
2. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 1)
The rotating speed of magnetic agitation is 500~800r/min, and the time is 55~65min.
3. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 2)
The rate of addition for controlling ammonia spirit is 0.13~0.16ml/min, drips a drop ammonia spirit, stirring is until solution ph
After stabilization, then next drop ammonia spirit is instilled, until reacting liquid pH value is adjusted to 10.6~10.8.
4. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 3)
The packing ratio that solution B pours into reaction liner is 55~65%.
5. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 3)
175~185 DEG C of 23~25h of hydro-thermal reaction are heated to by room temperature under the speed conditions of 5~15r/min.
6. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 4)
Alternately cleaning using suction filtration or centrifuges 3-6 times for water and alcohol.
7. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 4)
It collects and is carried out using suction filtration or centrifugation.
8. VOOH/VS according to claim 14The preparation method of micron composite granule, it is characterised in that：The step 5)
Product is sealed before being put into pallet and being dried with the preservative film for pricking hole.
9. a kind of VOOH/VS made of preparation method as described in claim 14Micron composite granule, it is characterised in that：VOOH/
VS4The near-spherical structure composition that micron composite granule is about 10 μm by uniform diameter, part near-spherical structure are assembled,
The inside of micron ball is by a diameter of 0.5~1.0 μm, the micron VS that length is 1.0~2.0 μm4Stub is accumulated certainly, external
It is made of at random the VOOH long sticks of a diameter of 50~200nm mono-crystalline structures.
10. a kind of VOOH/VS as claimed in claim 94Micron composite granule is in lithium/sodium-ion battery and optical electrical catalytic field
Application.
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