CN108298582A - One kind is by VO2The preparation method of hollow ball and film that nanoscale twins surround - Google Patents

One kind is by VO2The preparation method of hollow ball and film that nanoscale twins surround Download PDF

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Publication number
CN108298582A
CN108298582A CN201810267447.3A CN201810267447A CN108298582A CN 108298582 A CN108298582 A CN 108298582A CN 201810267447 A CN201810267447 A CN 201810267447A CN 108298582 A CN108298582 A CN 108298582A
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hollow ball
nanoscale twins
film
solution
deionized water
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马飞
徐慧妍
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Xian Jiaotong University
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic

Abstract

The invention discloses one kind by VO2The preparation method of hollow ball and film that nanoscale twins surround.Vanadium presoma, ethylene glycol, reducing agent are added in a certain proportion of ethyl alcohol and water mixed liquid by the present invention, mixed liquor is transferred in reaction kettle again and carries out hydro-thermal reaction, after to product carry out centrifuge washing, drying obtain powder sample, it is heat-treated in an inert atmosphere, one kind can be obtained by VO2The hollow spherical powder of nanoscale twins composition.Utilize VO2The film that nanoscale twins hollow ball is prepared shows excellent optical property and sensitivity.First, VO2The uniform vertical distribution of nanoscale twins significantly improves the dispersibility of nanoscale twins and the porosity of film in hollow ball surface, is obviously improved film to visible light to transmissivity and modulation capability, reduces phase transformation sluggishness width.For VO2Application in intelligent glass field has important value.

Description

One kind is by VO2The preparation method of hollow ball and film that nanoscale twins surround
【Technical field】
The present invention relates to a kind of VO for intelligent glass pane2The preparation method of nanoscale twins hollow ball belongs to intellectual material Field is also closely related with the energy and field of environment protection.
【Background technology】
Vanadium dioxide (VO2) (68 DEG C) can occur from monoclinic phase (P2 crystal usually at relatively low temperatures1/ c, low temperature Phase) to tetragonal phase (P42/ mnm, high-temperature-phase) structure transformation, and with phase transformation (MIT) process from insulator to metallic state, Resistivity and optical characteristics mutate, in particular, its ir transmissivity is increased with temperature and drastically reduced, and this process is complete It is reversible.VO2The requirement of smart window is conformed exactly to the regulating and controlling effect of light afterwards before phase change.Functionally, intelligent window can perceive The environmental stimulis such as light, heat, electricity simultaneously make a response, the luminous intensity and indoor light and temperature for passing through glass with effective control.Work as ring Border temperature is less than phase transition temperature (Tc) when, VO2Insulator phase is shown as, there is high IR transmittance, temperature to gradually rise. When temperature is increased to TcWhen, VO2It is changed into metal phase, there is strong reflex, ir transmissivity rapidly to drop infrared light Low, passive feedback effect can keep indoor temperature horizontal.
Currently, energy crisis becomes the biggest problem of facing mankind, the energy is mainly used in building, industry and traffic.Its In, building energy consumption alreadys exceed industry and traffic, accounts for the 41% of total energy consumption, and air-conditioning and heating account for building energy consumption again 50%.If by VO2It applies in smart window, to substitute air-conditioning, it will mass energy is saved, therefore, for VO2Film is ground Studying carefully becomes very valuable and meaning.Currently, about VO2Smart window application still faces some problems, on the one hand, VO2Film can Light-exposed transmissivity is relatively low, and is a kind of shifting relationship with the light modulation ability of film, such as：It is thick by reducing film Degree is come when increasing transmission of visible light, the light modulation ability of film drastically declines.Seriously restrict VO2Reality in smart window field It applies on border.Experiment and result of calculation show that low particle size can improve the optical property of film, and size minimum can reach at present To 20~30nm, but it is difficult the particle prepared less than 20nm, and little particle is easy to happen serious aggregation, in addition, small The sluggish width of grain is usually larger, i.e., sensitivity is low.For these problems, VO is prepared the invention discloses a kind of2Nanoscale twins The method of hollow ball structure, the experimental results showed that, VO2Nanoscale twins hollow ball not only balances transmission of visible light and light modulation Ability, and its sensitivity significantly increases.
【Invention content】
It is an object of the invention to overcome the above-mentioned prior art, one kind is provided by VO2The sky that nanoscale twins surround The preparation method of bulbus cordis and film.Present invention combination hydro-thermal reaction and heat treatment process, obtain by VO2The sky of nanoscale twins composition Using spin coating method thin-film material is made in hollow spherical powder by bulbus cordis structure.
In order to achieve the above objectives, the present invention is achieved by the following scheme：
One kind is by VO2The hollow ball preparation method that nanoscale twins surround, includes the following steps：
1) mixed solution for configuring ethyl alcohol and deionized water, vanadium precursor is dissolved into mixed solution, cell pulverization is used Instrument handles mixed solution, obtains mixed solution A；
2) ethylene glycol is added in the mixed solution A that step 1) obtains, reducing agent is uniformly added in magnetic agitation solution afterwards, after It is transferred in autoclave after continuous stirring and carries out hydro-thermal reaction, obtained reaction solution, the supernatant in reaction solution is poured out, is obtained Reaction product；
3) reaction product for obtaining step 2) uses deionized water and absolute ethyl alcohol eccentric cleaning respectively, is then dried in vacuum It is dried in case, obtains powdered product；
4) powdered product that step 3) obtains is heat-treated under an inert atmosphere, powder B is made, to be a kind of by VO2 The hollow ball that nanoscale twins surround.
Further improvement of the present invention is：
The volume ratio of ethyl alcohol and deionized water is (1~6) in step 1)：1, vanadium precursor in the solution a concentration of 0.025~0.1mol/L makes vanadium precursor fully dissolve, obtains mixed solution A with cell pulverization instrument processing mixed solution；Before vanadium Body selects the vanadic salts for including+5 valence vanadium, including：Ammonium metavanadate (NH4VO3), sodium metavanadate (NaVO3), sodium pyrovanadate (Na4V2O7)。
The volume of ethylene glycol is the 2.5~14.5% of mixed solution A volume in step 2), the concentration of reducing agent in the solution For 0.064~0.128mol/L；The liner of autoclave is polytetrafluoroethylene (PTFE), the compactedness of autoclave is 50~ 80%, the temperature of hydro-thermal reaction is 180~220 DEG C, and the reaction time is 20~28h；
Reducing agent selects the acid of reproducibility, including：Formic acid (H2CO2), oxalic acid (H2C2O4), lactic acid (C3H6O3), malic acid (C4H6O5)。
Reaction solution uses deionized water and each eccentric cleaning of absolute ethyl alcohol 3 times respectively in step 3), wherein cleaning each time, instead It is 1 to answer the volume ratio of product and deionized water：The volume ratio of (10~15), reaction product and absolute ethyl alcohol is 1：(5~10)； When being dried in vacuum drying oven, drying temperature is 50~100 DEG C, and drying time is 7~12h.
Step 4) heat treatment temperature is 300~450 DEG C, and the time is 1~3h.
One kind is by VO2The hollow ball that nanoscale twins surround, a diameter of 400~2000nm of hollow ball, hollow ball appearance Face is attached with nanoscale twins, and nanoscale twins length is 50~100nm, and width is 30~60nm, and thickness is 5~7nm.
A kind of VO2The preparation method of film, which is characterized in that include the following steps：
(1) powder B is distributed in deionized water, dispersant and polyurethane is added, carries out magnetic agitation under room temperature, obtains Compound C；
(2) compound C is spun to quartz glass or polyethylene terephthalate surface and drying, obtains target thin Film.
It is 1 that dispersant and the volume ratio of polyurethane, which is added, in step (1)：(10~20), 3~5h of magnetic agitation under room temperature.
Drying temperature is 80~100 DEG C in step (2), 1~2min of drying time.
A kind of VO2Film, the VO2Film is one kind by VO2The film prepared by hollow ball that nanoscale twins surround, The middle a diameter of 400~2000nm of hollow ball, hollow outer surface of ball are attached with nanoscale twins, and nanoscale twins length is 50~100nm, Width is 30~60nm, and thickness is 5~7nm.
Compared with prior art, the invention has the advantages that：
Present invention combination hydro-thermal reaction and heat treatment process, obtain by VO2The hollow ball structure of nanoscale twins composition, uses Thin-film material is made in hollow spherical powder by spin coating method.Cell pulverization instrument is selected to keep vanadium precursor abundant in preparation process of the present invention Dissolving, using ethylene glycol as a part for solvent, and limits the dosage of ethylene glycol, nanoscale twins is made to be gathered into spherical knot Structure；Suitable reduction dosage is added, obtains the hollow ball structure surrounded by nanoscale twins；VO is obtained after heat treatment2Monoclinic phase.It receives The rice uniform vertical distribution of lamella not only increases the dispersibility of nanoscale twins, and significantly increase hole in hollow ball surface Gap rate.
By film produced by the present invention, VO2Nanoscale twins hollow ball not only balances transmission of visible light and light modulation energy Power, and its sensitivity significantly increases, and is suitable for the application in smart window field.It is counted according to the optical property of different-thickness film It was found that with the reduction (being reduced to 2.6 μm by 7.8 μm) of film thickness, it is seen that light transmission significantly increases, and is increased to by 50% 87.2%, and remain higher light modulation ability (film thickness be 2.6 μm when, light adjustment capability be 5.2%), it is seen that this Invention film obtained plays the role of balancing transmission of visible light and light modulation ability.
【Description of the drawings】
Fig. 1 (a) is the hollow ball SEM photograph before present invention heat treatment；
Fig. 1 (b) is the hollow ball TEM photos before present invention heat treatment；
Fig. 1 (c) is the XRD spectrum after present invention heat treatment；
Fig. 1 (d) is the SEM photograph after present invention heat treatment；
Fig. 2 (a) is different-thickness film of the present invention in 20 DEG C and 90 DEG C of light transmission；
Fig. 2 (b) is the optical property statistical chart of different-thickness film of the present invention；
Fig. 3 is the DSC curve after present invention heat treatment.
【Specific implementation mode】
The invention discloses one kind by VO2The preparation method of hollow ball and film that nanoscale twins surround.In order to become apparent from Illustrate the present invention, with reference to embodiment, the present invention will be further described.
It is described that technical scheme is as follows：
Step 1：In conjunction with hydro-thermal method and it is thermally treated resulting in by VO2The hollow ball structure that nanoscale twins surround；
1) volume ratio of the mixed solution of configuration ethyl alcohol and deionized water, ethyl alcohol and deionized water is (1~6)：1；Mixed It closes and vanadium precursor is added in solution, its a concentration of 0.025~0.1mol/L after the dissolving of vanadium precursor,；It is handled with cell pulverization instrument Mixed solution makes vanadium presoma fully be dissolved into mixed solution, obtains mixed solution A；
2) ethylene glycol is added in mixed solution A, the volume of ethylene glycol accounts for the volume 2.5~14.5% of mixed solution A, magnetic Reducing agent is uniformly added in power agitating solution afterwards, and a concentration of 0.064~0.128mol/L of reducing agent in the solution continues magnetic force and stirs It mixes after reacting fully, it is anti-that the reaction solution after stirring is transferred to progress hydro-thermal in the autoclave that liner is polytetrafluoroethylene (PTFE) It answers, the compactedness of autoclave is 50~80%, and the temperature of hydro-thermal reaction is 180~220 DEG C, and the reaction time is 20~28h, Natural cooling obtains the reaction solution of upper lower leaf, and the supernatant in reaction solution is poured out, reaction product is obtained.
Wherein, vanadium presoma selects the vanadic salts for including+5 valence vanadium, specially：Ammonium metavanadate (NH4VO3), sodium metavanadate (NaVO3), sodium pyrovanadate (Na4V2O7) etc.；Reducing agent is the acid for selecting reproducibility, such as formic acid (H2CO2), oxalic acid (H2C2O4), breast Acid (C3H6O3), malic acid (C4H6O5) etc..
3) use deionized water and each eccentric cleaning of absolute ethyl alcohol 3 times, cleaning order each without limitation respectively reaction product When secondary cleaning, the volume ratio of reaction solution and deionized water is 1：The volume ratio of (10~15), reaction solution and absolute ethyl alcohol is 1：(5 ~10)；Then it is dried in vacuum drying oven, drying temperature is 50~100 DEG C, and drying time is 7~12h, finally obtains powder Product.
4) powdered product is heat-treated under an inert atmosphere, heat treatment temperature be 300~450 DEG C, the time be 1~ 3h obtains target product：One kind is by VO2Nanoscale twins surround hollow ball structure powder, nanoscale twins length be 50~ 100nm, width are 30~60nm, and thickness is 5~7nm, and the size of hollow ball structure is 400~2000nm.
Step 2：Film is made in the hollow spherical powder obtained using spin-coating method；
5) the hollow ball structure powder that step 1 obtains is distributed in deionized water, and dispersant and polyurethane is added, Room temperature 3~5h of magnetic agitation obtains compound C, and the wherein volume ratio of dispersant and polyurethane is 1：(10~20)；
6) compound C is spun to quartz glass or the surface polyethylene terephthalate (PET), at 80~100 DEG C 1~2min of lower drying, can be obtained aimed thin film.
In the present invention, ethyl alcohol promotes nanoscale twins and is formed；Ethylene glycol makes nanoscale twins be gathered into the spherical of short texture Structure；Dissolving inside the acid induction ball of reproducibility, is allowed to form hollow ball structure, react the gas of generation from hollow ball inside to It is overflowed outside ball, promotes nanoscale twins vertical distribution in hollow ball surface.This structure not only increases the dispersibility of nanoscale twins, and And improve the porosity of hollow ball surface.
Fig. 1 (a) is the SEM photograph of the hollow ball obtained before being heat-treated, and Fig. 1 (b) is corresponding TEM photos.As can be seen that Nanoscale twins are uniformly embedded in hollow ball surface, not only increase the dispersibility of nanoscale twins, and piece interlayer porosity is big.Figure 1 (c) is the XRD spectrum after 450 DEG C are heat-treated 2 hours.As can be seen that all peaks both correspond to monoclinic phase VO2(JCPDS Card No.43-1051), illustrate high by nanoscale twins purity made from this method.Fig. 1 (d) is small through 450 DEG C of heat treatments 2 When after SEM photograph, it can be seen that sample surface morphology does not change after heat treatment.
Fig. 2 (a) be light transmission of the different-thickness film in 20 DEG C and 90 DEG C, test wavelength ranging from 250~ 2500nm, Fig. 2 (b) are the optical property statistical result of different-thickness film.Transmission of visible light (T-vis) is 700nm wavelength The transmissivity at place；Near infrared light modulation capability (Δ T in Fig. 2 (b)2500nm) be defined as 20 DEG C and 90 DEG C it is saturating at 2500nm wavelength Penetrate rate difference；T-visLAnd T-visHTransmission of visible light at respectively 20 and 90 DEG C；ΔTsolFor sunlight modulation capability, lead to Following formula is crossed to be calculated：
Wherein λ is wavelength,For solar radiation spectrum, T (λ, 20 DEG C), T (λ, 90 DEG C) is respectively 250-2500nm wave bands Light transmission at 20 and 90 DEG C.As can be seen that when film thickness is reduced to 2.6 μm by 7.8 μm, it is seen that light transmission (T- Vis it) is increased to 87.2% by 50%, and remains higher light modulation ability (Δ T when film thickness is 2.6 μmsolFor 5.2%), it is seen that the film prepared through the invention balances transmission of visible light and light modulation ability.
Fig. 3 is the later DSC curve of heat treatment, it can be seen that VO2The sluggish width of nanoscale twins hollow ball is 9.3 DEG C, Much smaller than nano particle sluggish width (>20 DEG C), significantly improve VO2Phase transformation sensitivity.
Embodiment 1：
1) configuration volume ratio is 4:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.05mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 3% of mixed solution A, adds Enter oxalic acid (H2C2O4), a concentration of 0.1mol/L of oxalic acid in the solution continues to stir that be transferred to liner after reaction fully be poly- Carry out hydro-thermal reaction in the autoclave of tetrafluoroethene, compactedness 70%, at 200 DEG C hydro-thermal reaction for 24 hours, natural cooling, Reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1：10, the volume ratio of reaction solution and absolute ethyl alcohol is 1：8；Reaction solution after cleaning is dried 10h at 70 DEG C and is obtained Powdery product；
4) powdery product is heat-treated 2h for 450 DEG C under an argon atmosphere, obtained by VO2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:10 volume ratio is added Into deionized water, room temperature magnetic agitation 4h obtains compound；
6) compound is spun in glass substrate, dry 2min at 100 DEG C, you can film is made.
It is obtained by VO through this embodiment2The hollow ball structure powder that nanoscale twins surround, nanoscale twins length are 50 ~100nm, width are 30~60nm, and thickness is 5~7nm, and the size of hollow ball structure is 400~2000nm.
Embodiment 2：
1) configuration volume ratio is 3:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.025mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is made fully to be dissolved into mixing In solution, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 5% of mixed solution A, adds Enter oxalic acid (H2C2O4), a concentration of 0.064mol/L of oxalic acid in the solution continues to stir being transferred to liner after reaction fully and be Carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 60%, hydro-thermal reaction 26h, naturally cold at 190 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1：12, the volume ratio of reaction solution and absolute ethyl alcohol is 1：5；Reaction solution after cleaning dries 8h at 50 DEG C and obtains powder Last shape product；
4) powdery product is heat-treated 1h for 300 DEG C under an argon atmosphere, obtained by VO2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:15 volume ratio is added Into deionized water, room temperature magnetic agitation 5h obtains compound；
6) compound is spun in glass substrate, dry 1min at 90 DEG C, you can film is made.
Embodiment 3：
1) configuration volume ratio is 2:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.03mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 10% of mixed solution A, adds Enter formic acid (H2CO2), a concentration of 0.07mol/L of formic acid in the solution continues to stir that be transferred to liner after reaction fully be poly- Carry out hydro-thermal reaction in the autoclave of tetrafluoroethene, compactedness 50%, hydro-thermal reaction 22h at 185 DEG C, natural cooling, Reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:15, the volume ratio of reaction solution and absolute ethyl alcohol is 1:10；Reaction solution after cleaning is dried 9h at 80 DEG C and is obtained Powdery product；
4) powdery product is heat-treated 2h for 320 DEG C under an argon atmosphere, obtained by VO2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:10 volume ratio is added Into deionized water, room temperature magnetic agitation 3h obtains compound；
6) compound is spun in glass substrate, 80 DEG C of dry 2min, you can film is made.
Embodiment 4：
1) configuration volume ratio is 1:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.04mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 2.5% of mixed solution A, Oxalic acid (H is added2C2O4), a concentration of 0.08mol/L of oxalic acid in the solution continues to stir being transferred to liner after reaction fully To carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 80%, hydro-thermal reaction 20h, naturally cold at 182 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to absolute ethyl alcohol and deionized water respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:11, the volume ratio of reaction solution and absolute ethyl alcohol is 1:7；Reaction solution after cleaning dries 7h at 60 DEG C and obtains powder Last shape product；
4) by powdery product, 360 DEG C of heat treatment 2h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:20 volume ratio is added Into deionized water, room temperature magnetic agitation 4h obtains compound；
6) compound is spun in glass substrate, 85 DEG C of dry 2min, you can film is made.
Embodiment 5：
1) configuration volume ratio is 5:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.045mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is made fully to be dissolved into mixing In solution, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 7% of mixed solution A, adds Enter oxalic acid (H2C2O4), a concentration of 0.095mol/L of oxalic acid in the solution continues to stir being transferred to liner after reaction fully and be Carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 55%, hydro-thermal reaction 21h, naturally cold at 188 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:13, the volume ratio of reaction solution and absolute ethyl alcohol is 1:6；Reaction solution after cleaning is dried 12h at 55 DEG C and is obtained Powdery product；
4) by powdery product, 400 DEG C of heat treatment 3h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:15 volume ratios are added to In deionized water, room temperature magnetic agitation 5h obtains compound；
6) compound is spun in glass substrate, 95 DEG C of dry 2min, you can film is made.
Embodiment 6：
1) configuration volume ratio is 6:1 ethyl alcohol and deionized water mixed solution, and sodium pyrovanadate is added, sodium pyrovanadate is molten A concentration of 0.055mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is made fully to be dissolved into mixing In solution, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 9% of mixed solution A, adds Enter oxalic acid (H2C2O4), a concentration of 0.128mol/L of oxalic acid in the solution continues to stir being transferred to liner after reaction fully and be Carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 65%, hydro-thermal reaction 25h, naturally cold at 192 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:12, the volume ratio of reaction solution and absolute ethyl alcohol is 1:8；Reaction solution after cleaning is dried 11h at 100 DEG C and is obtained Powdery product；
4) by powdery product, 380 DEG C of heat treatment 2h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:12 volume ratio is added Into deionized water, room temperature magnetic agitation 3h obtains compound；
6) compound is spun on PET substrate, 82 DEG C of dry 2min, you can film is made.
Embodiment 7：
1) configuration volume ratio is 5:1 ethyl alcohol and deionized water mixed solution, and sodium metavanadate (NaVO is added3), inclined vanadium A concentration of 0.06mol/L of sour sodium in the solution；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is made fully to dissolve Into mixed solution, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 8.5% of mixed solution A, Lactic acid (C is added3H6O3), a concentration of 0.09mol/L of lactic acid in the solution continues to stir being transferred to liner after reaction fully To carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 75%, hydro-thermal reaction 27h, naturally cold at 198 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:13, the volume ratio of reaction solution and absolute ethyl alcohol is 1:9；Reaction solution after cleaning dries 8h at 95 DEG C and obtains powder Last shape product；
4) by powdery product, 420 DEG C of heat treatment 2h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:11 volume ratio is added Into deionized water, room temperature magnetic agitation 3h obtains compound；
6) compound is spun on PET substrate, 88 DEG C of dry 2min, you can film is made.
Embodiment 8：
1) configuration volume ratio is 4:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.1mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 10% of mixed solution A, adds Enter oxalic acid (H2C2O4), a concentration of 0.105mol/L of oxalic acid in the solution continues to stir being transferred to liner after reaction fully and be Carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 53%, hydro-thermal reaction 23h, naturally cold at 195 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:10, the volume ratio of reaction solution and absolute ethyl alcohol is 1:10；Reaction solution after cleaning is dried 7h at 90 DEG C and is obtained Powdery product；
4) by powdery product, 430 DEG C of heat treatment 3h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:16 volume ratio is added Into deionized water, room temperature magnetic agitation 4h obtains compound；
6) compound is spun on PET substrate, 92 DEG C of dry 2min, you can film is made.
Embodiment 9：
1) configuration volume ratio is 3:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.09mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 11.5% of mixed solution A, Malic acid (C is added4H6O5), a concentration of 0.11mol/L of malic acid in the solution, after 2ml ethylene glycol is added, magnetic agitation is extremely Solution is uniform, and the malic acid (C of 0.005mol is added4H6O5), continue to stir that liner is transferred to after reaction fully is polytetrafluoroethyl-ne Carry out hydro-thermal reaction in the autoclave of alkene, compactedness 58%, hydro-thermal reaction 28h at 215 DEG C, natural cooling obtains anti- Liquid is answered, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:15, the volume ratio of reaction solution and absolute ethyl alcohol is 1:15；Reaction solution after cleaning is dried 12h at 85 DEG C and is obtained Powdery product；
4) by powdery product, 410 DEG C of heat treatment 1h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:17 volume ratio is added Into deionized water, room temperature magnetic agitation 5h obtains compound；
6) compound is spun on PET substrate, 98 DEG C of dry 2min, you can film is made.
Embodiment 10：
1) configuration volume ratio is 2:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.8mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 13% of mixed solution A, adds Enter oxalic acid (H2C2O4), a concentration of 0.115mol/L of oxalic acid in the solution continues to stir being transferred to liner after reaction fully and be Carry out hydro-thermal reaction in the autoclave of polytetrafluoroethylene (PTFE), compactedness 64%, hydro-thermal reaction 22h, naturally cold at 210 DEG C But, reaction solution is obtained, the supernatant in reaction solution is poured out, obtains reactant；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:14, the volume ratio of reaction solution and absolute ethyl alcohol is 1:8；Reaction solution after cleaning dries 9h at 55 DEG C and obtains powder Last shape product；
4) by powdery product, 390 DEG C of heat treatment 1h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:18 volume ratio is added Into deionized water, room temperature magnetic agitation 5h obtains compound；
6) compound is spun on PET substrate, 93 DEG C of dry 2min, you can film is made.
Embodiment 11：
1) configuration volume ratio is 1:1 ethyl alcohol and deionized water mixed solution, and ammonium metavanadate is added, ammonium metavanadate is molten A concentration of 0.07mol/L in liquid；With cell pulverization instrument pulverization process mixed solution, vanadium precursor is set fully to be dissolved into mixing molten In liquid, solution A is obtained；
2) magnetic agitation is uniform to solution after ethylene glycol being added, and the volume of ethylene glycol accounts for the volume 14.5% of mixed solution A, Oxalic acid (H is added2C2O4), a concentration of 0.12mol/L of oxalic acid in the solution, after 5ml ethylene glycol is added, magnetic agitation to solution Uniformly, the oxalic acid (H of 0.012mol is added2C2O4), continue to stir the height for being transferred to that liner is polytetrafluoroethylene (PTFE) after reaction fully Hydro-thermal reaction is carried out in pressure reaction kettle, and compactedness 78%, hydro-thermal reaction 25h at 180 DEG C, natural cooling obtains reaction solution, will Supernatant in reaction solution is poured out, and reactant is obtained；
3) reactant is used to deionized water and absolute ethyl alcohol respectively, and respectively cleaning is three times, wherein reaction solution and deionized water Volume ratio is 1:10, the volume ratio of reaction solution and absolute ethyl alcohol is 1:7；Reaction solution after cleaning is dried 10h at 65 DEG C and is obtained Powdery product；
4) by powdery product, 310 DEG C of heat treatment 2h are obtained by VO under an argon atmosphere2The hollow ball that nanoscale twins surround Structure powder；
5) hollow ball structure powder is distributed in deionized water, by dispersant and polyurethane with 1:19 volume ratio is added Into deionized water, room temperature magnetic agitation 4h obtains compound；
6) compound is spun on PET substrate, 100 DEG C of dry 2min, you can film is made.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.

Claims (10)

1. one kind is by VO2The hollow ball preparation method that nanoscale twins surround, which is characterized in that include the following steps：
1) mixed solution for configuring ethyl alcohol and deionized water, vanadium precursor is dissolved into mixed solution, at cell pulverization instrument Mixed solution is managed, mixed solution A is obtained；
2) ethylene glycol is added in the mixed solution A that step 1) obtains, reducing agent is uniformly added in magnetic agitation solution afterwards, continues to stir It is transferred to after mixing in autoclave and carries out hydro-thermal reaction, obtain reaction solution, the supernatant in reaction solution is poured out, is reacted Product；
3) reaction product for obtaining step 2) uses deionized water and absolute ethyl alcohol eccentric cleaning respectively, then in vacuum drying oven Drying, obtains powdered product；
4) powdered product that step 3) obtains is heat-treated under an inert atmosphere, powder B is made, to be a kind of by VO2Nanometer sheet The hollow ball that layer surrounds.
2. one kind according to claim 1 is by VO2The hollow ball preparation method that nanoscale twins surround, which is characterized in that step 1) volume ratio of ethyl alcohol and deionized water is (1~6) in：1, a concentration of 0.025~0.1mol/L of vanadium precursor in the solution, So that vanadium precursor is fully dissolved with cell pulverization instrument processing mixed solution, obtains mixed solution A；It includes+5 valences that vanadium precursor, which is selected, The vanadic salts of vanadium, including：Ammonium metavanadate (NH4VO3), sodium metavanadate (NaVO3), sodium pyrovanadate (Na4V2O7)。
3. one kind according to claim 1 is by VO2The hollow ball preparation method that nanoscale twins surround, which is characterized in that step 2) in the volume of ethylene glycol be mixed solution A volume 2.5~14.5%, reducing agent in the solution a concentration of 0.064~ 0.128mol/L；The liner of autoclave is polytetrafluoroethylene (PTFE), and the compactedness of autoclave is 50~80%, hydro-thermal reaction Temperature be 180~220 DEG C, the reaction time be 20~28h；
Reducing agent selects the acid of reproducibility, including：Formic acid (H2CO2), oxalic acid (H2C2O4), lactic acid (C3H6O3), malic acid (C4H6O5)。
4. one kind according to claim 1 is by VO2The hollow ball preparation method that nanoscale twins surround, which is characterized in that step 3) reaction solution uses deionized water and each eccentric cleaning of absolute ethyl alcohol 3 times respectively in, wherein clean each time, reaction product and go from The volume ratio of sub- water is 1：The volume ratio of (10~15), reaction product and absolute ethyl alcohol is 1：(5~10)；It is dried in vacuum drying oven When dry, drying temperature is 50~100 DEG C, and drying time is 7~12h.
5. one kind according to claim 1 is by VO2The hollow ball preparation method that nanoscale twins surround, which is characterized in that step 4) heat treatment temperature is 300~450 DEG C, and the time is 1~3h.
6. it is a kind of according to one kind made from claim 1-5 any one the methods by VO2The hollow ball that nanoscale twins surround, It is characterized in that, a diameter of 400~2000nm of hollow ball, hollow outer surface of ball are attached with nanoscale twins, nanoscale twins are long Degree is 50~100nm, and width is 30~60nm, and thickness is 5~7nm.
7. a kind of VO based on claim 1-5 any one the methods2The preparation method of film, which is characterized in that including with Lower step：
(1) powder B is distributed in deionized water, dispersant and polyurethane is added, carries out magnetic agitation under room temperature, obtains compound Object C；
(2) compound C is spun to quartz glass or polyethylene terephthalate surface and drying, obtains aimed thin film.
8. a kind of VO according to claim 72The preparation method of film, which is characterized in that step (1) be added dispersant and The volume ratio of polyurethane is 1：(10~20), 3~5h of magnetic agitation under room temperature.
9. a kind of VO according to claim 72The preparation method of film, which is characterized in that drying temperature is in step (2) 80~100 DEG C, 1~2min of drying time.
10. VO made from a kind of method according to claim 8 or claim 92Film, which is characterized in that the VO2Film is one kind By VO2The film prepared by hollow ball that nanoscale twins surround, the wherein a diameter of 400~2000nm of hollow ball, hollow ball appearance Face is attached with nanoscale twins, and nanoscale twins length is 50~100nm, and width is 30~60nm, and thickness is 5~7nm.
CN201810267447.3A 2018-03-28 2018-03-28 One kind is by VO2The preparation method of hollow ball and film that nanoscale twins surround Pending CN108298582A (en)

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CN109111243A (en) * 2018-09-20 2019-01-01 界首永恩机电科技有限公司 A kind of method that ceramics surface sprays complex copper powder
CN109133171A (en) * 2018-11-09 2019-01-04 吉林大学 A kind of spherical porous pattern VO of different-diameter size2And preparation method thereof
WO2022032745A1 (en) * 2020-08-10 2022-02-17 五邑大学 Vo2/mxene composite material, preparation method therefor and use thereof

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Publication number Priority date Publication date Assignee Title
CN109111243A (en) * 2018-09-20 2019-01-01 界首永恩机电科技有限公司 A kind of method that ceramics surface sprays complex copper powder
CN109111243B (en) * 2018-09-20 2020-12-11 界首永恩机电科技有限公司 Method for spraying composite copper powder on surface of ceramic artwork
CN109133171A (en) * 2018-11-09 2019-01-04 吉林大学 A kind of spherical porous pattern VO of different-diameter size2And preparation method thereof
WO2022032745A1 (en) * 2020-08-10 2022-02-17 五邑大学 Vo2/mxene composite material, preparation method therefor and use thereof

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