CN106046863A - Preparation method for multifunctional TiO2 nano-paint - Google Patents
Preparation method for multifunctional TiO2 nano-paint Download PDFInfo
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- CN106046863A CN106046863A CN201610258617.2A CN201610258617A CN106046863A CN 106046863 A CN106046863 A CN 106046863A CN 201610258617 A CN201610258617 A CN 201610258617A CN 106046863 A CN106046863 A CN 106046863A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
Abstract
The invention provides a preparation method for a multifunctional TiO2 nano-paint. The preparation method comprises the following steps: preparation of a TiO2 solution with butyl titanate as a titanium source, isopropanol as a solvent and diethanolamine as a hydrolysis inhibitor; and dispersion and surface modification of the TiO2 nano-solution: carrying out TiO2 surface modification on the obtained TiO2 solution with sodium silicate as a dispersing agent and silane as a coupling agent so as to obtain the multifunctional TiO2 nano-paint. The multifunctional TiO2 nano-paint prepared in the invention can be directly sprayed on the surface of a substrate at normal temperature and has good bonding action on the substrate; surface cleanness of a photovoltaic assembly is maintained mainly in virtue of super hydrophilicity and self-cleaning performance of a formed coating; and the photoelectric conversion rate of the photovoltaic assembly is improved.
Description
Technical field
The present invention relates to a kind of multi-functional TiO2The preparation method of nano paint, is used for increasing photovoltaic particularly to one and sends out
Electric has super hydrophilic, the multi-functional TiO of self-cleaning function2The preparation method of nano paint.
Background technology
In the running of photovoltaic plant, the generated energy in power station is often affected by several factors, wherein assembly
The clean-up performance on surface can have a strong impact on the delivery efficiency of assembly, can reduce assembly generated energy as dust blocks, and local dust hides
Gear then can cause hot spot effect, may cause component failures time more serious, reduces service life, typically not over 20 years.For
Improve the generated energy in power station, assembly that power station battery component to be used photoelectric conversion rate is high, should also be avoided other factors
The component power loss brought.Therefore, in order to avoid the impact of assembly surface dust, during cleaning assembly has become power station O&M on schedule
A important process.But, for the large-sized photovoltaic power station of tens megawatts the most hundreds of megawatt, component count reaches
To tens thousand of the most hundreds thousand of pieces, at this moment, cleaning is the heaviest, and needs certain cost.Then, in order to reduce power station
O&M cost, improve the gene-ration revenue in power station, get more and more and arise at the historic moment for realizing the product of photovoltaic module automatically cleaning ability.
In prior art, generally by covering self-cleaning material on photovoltaic component glass surface, it is possible to make the dust can not be
Assembly surface deposits and sticks together, thus reaches the self-cleaning effect of assembly.
But, major part self-cleaning material on the market is confined to simple function, such as much at coating photovoltaic module glass
After glass, the light transmittance of assembly can be reduced, affect the generated energy of assembly；It is that have because formula uses the nanoparticles such as silicon dioxide,
Easily form crackle after aging, separate with matrix material.Therefore, it is possible to ensure not affect the light transmittance of assembly, promote sending out of assembly
The Multi-function self-cleaning product that electricity meets again 25 year service life of assembly is few.
One as disclosed in patent CN104745025A is with nano-TiO2Particle slurry is the nanocomposite coatings of raw material,
Make film layer hydrophobic by changing material surface nanotopography, but glass surface easily adheres to oiliness thing under this hydrophobic technology
Matter, and be difficult to be rinsed, cleaning effect is bad, and this area is generally acknowledged always, and hydrophobic group is very easy to and environmental activity,
Hydrophobic effect is gradually lost, it is impossible to ensure Long Service Life in half a year.
As titania/silica is prepared for nanocomposite solution, patent CN by patent CN103626404 A
It is compound that titania/silica, triethanolamine, Polyethylene Glycol, ethylene glycol and aluminium sesquioxide are formed by 103936292 A
Coating liquid, although can self-cleaning glass, improve light permeable rate, but all lack luminescence generated by light and upper conversion and the optics of lower conversion
Characteristic, does not improve light utilization efficiency thus does not make battery conversion efficiency increase.And there is no Superhydrophilic and decomposing organic matter
Ability.
Although patent CN103288358 discloses a kind of super-hydrophilic self-cleaning fog-proof anti-reflection coating and preparation has
The function of the anti-reflection of superhydrophilic self-cleaning, but it has been the absence of the ability of decomposing organic matter, and also this patent uses colloidal sol to coagulate
Glue method, not only needs to process through high temperatureization, in addition it is also necessary to 3 layers of coating also to be calcined and be immersed the steps such as washing dries up, and prepare
Film layer does not has reliability and the weatherability of 25 years as long as, does not has practical value for existing glass.
Although patent CN102898875A has hydrophilic effect, but does not increase the effect of light permeable rate and decomposing organic matter
Really, and manufacturing process is loaded down with trivial details.
For photovoltaic module self-cleaning glass, above method is required to bigger equipment investment, and is difficult to reach high printing opacity
Rate effect, can not be used for transforming built power station photovoltaic module.And use process operation complicated, need special spraying work
Skill, it is impossible to use light professional equipment direct spraying in assembly glass surface at normal temperatures.
Summary of the invention
The technical problem to be solved is to provide that a kind of having of photovoltaic generation be super hydrophilic, automatically cleaning for increasing
The multi-functional TiO of function2Nano paint preparation method, simple through the inventive method preparation process, the multi-functional TiO of preparation2Receive
Rice coating has preferable dispersibility, in substrate surface, can have the stronger cohesive force with base material by direct spraying at normal temperatures,
Main Superhydrophilic and the photocatalysis effect forming coating that utilize, the surface cleaning of holding photovoltaic module, moreover it is possible to strengthen photovoltaic group
The photoelectric conversion rate of part.
One aspect of the present invention is to provide a kind of multi-functional TiO2The preparation method of nano paint, including walking as follows
Rapid:
1)TiO2Prepared by solution: with butyl titanate for titanium source, and isopropanol is solvent, and diethanolamine is hydrolysis inhibitor system
Standby TiO2Solution, and
2)TiO2The dispersion of nanometer solution and surface modification: to step 1) the middle TiO obtained2Solution, does with sodium silicate and disperses
Agent, silane makees coupling agent, to TiO2Modifying surface, obtain the multi-functional TiO of the present invention2Nano paint.
Multi-functional TiO of the present invention2The preparation method of nano paint, using butyl titanate is titanium source, and isopropanol is
Solvent, diethanolamine is that hydrolysis inhibitor is to prepare TiO2Solution.Then using sodium silicate to do dispersant, monosilane makees coupling agent
At TiO2Surface produces adsorption, to TiO2Nano material carries out surface modification, hydroxyl layer cladding is got up, it is to avoid nanometer material
Interaction between material.The multi-functional TiO that the present invention can be prepared with simple spraying coating process at normal temperatures2Nano paint is at base
Film forming on material, TiO2Can be bonded completely with glass at short notice.
The multi-functional TiO prepared by preparation method of the present invention2Nano paint is a kind of activated water based sols,
Spray through the substrate surface at such as glass, can quickly form the film layer of inorganic nanostructures without heat treatment.By this
Bright multi-functional TiO2The glass plate of nano paint spraying photovoltaic module, TiO2Can be bonded completely with glass at short notice.
Preferably, above-mentioned multi-functional TiO2TiO in nano paint2For anatase type nano TiO2Particle.
Described film layer has Superhydrophilic and photocatalysis effect, the most effectively, increases the generated energy of photovoltaic module.
This film layer not only can increase the light transmittance of glass, improves the generating efficiency of assembly, moreover it is possible to make photovoltaic component glass table
Face has super hydrophilic ability and automatically cleaning ability, eliminates dust and the greasy filth impact on assembly, it will help promote photovoltaic
The generated energy of assembly.Under the joint effect of instantaneous and long-term additional issue mechanism, generated energy promotes amplitude 3-5%.Additionally, due to this
The TiO that preparation method described in invention is modified2Nanoparticle can fully absorb and utilize ultraviolet to carry out catalytic reaction, thus drops
Low photovoltaic module ultra-violet absorption amount, delays that assembly backboard EVA's is aging, extends assembly service life.
Preferably, the multi-functional TiO prepared by preparation method of the present invention2Nano paint is formed at substrate surface
A layer thickness is about the colourless transparent film of 150nm.
The multi-functional TiO prepared by preparation method of the present invention2After nano paint is sprayed at assembly glass surface,
Combine with nanoparticle mixture form and glass chemistry, it is possible to glass surface roughness is greatly reduced, reduce diffuse-reflectance effect
Impact on light transmittance.Preferably, it is coated with multi-functional TiO of the present invention2The assembly glass surface of nano paint coarse
Degree is 40-60nm.
The multi-functional TiO prepared by preparation method of the present invention2After nano paint is sprayed at assembly glass surface,
Can degradation of organic substances effectively within the unit interval.Preferably, it is coated with multi-functional TiO of the present invention2Nano paint
The average photodissociation index of assembly glass surface is 38.3nmol/L/min.
The multi-functional TiO prepared by preparation method of the present invention2Nano paint utilizes wherein modified TiO2Composition,
Make film layer after being applied to assembly glass surface, produce luminescence generated by light and upper conversion (UC gain), lower conversion (DC
Gain) luminescent effect, the energy of infrared band energy and ultraviolet light wave band is converted into visible light wave range energy the most respectively, and (PL composes
Nano material film layer prepared by the line display present invention has strong absworption peak at about 280nm), to increase effective luminous flux, improve
The electricity conversion of battery.
As a kind of preferred implementation of the present invention, each component in preparation method of the present invention, by mass fraction
Meter includes:
Butyl titanate 2 parts～5 parts
Diethanolamine 1 part～3 parts
Isopropanol 40 parts～50 parts
Deionized water 20 parts～30 parts
Sodium silicate 4 parts～6 parts
Monosilane 10 parts～13 parts.
As the one more preferably embodiment of the present invention, each component in preparation method of the present invention, divide by quality
Number meter includes:
Butyl titanate 4 parts
Diethanolamine 1 part
Isopropanol 50 parts
Deionized water 30 parts
Sodium silicate 4 parts
Monosilane 12 parts.
As a kind of preferred implementation of the present invention, described preparation method comprises the steps:
(1)TiO2Prepared by solution:
Butyl titanate, diethanolamine, isopropanol are mixed by a certain percentage, stirs, make solution A, use agitator
Solution A is stirred continuously；
Isopropanol, deionized water are mixed by a certain percentage, stirs, make solution B, be slowly added in stirring
In solution A, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
By sodium silicate and step 1) the middle TiO obtained2Solution mixes by a certain percentage, stirs, and makes solution C, continues
After continuous stirring 1 hour, silane is mixed by a certain percentage with solution C, stirs, pH value is adjusted to 9.2, continue stirring 2
Hour, prepare the multi-functional TiO of the present invention2Nano paint.
Multi-functional TiO of the present invention2In the preparation method of nano paint, when solution B mixes with solution A, continue to strengthen
The ratio of solution B, prepared coating concentration can reduce accordingly.This can cause titanium dioxide concentration to reduce, its hydrophilic, automatically cleaning
Effect can reduce accordingly, but the minimizing of thicknesses of layers can increase light transmittance, thus increases photovoltaic generation.
As the present invention one preferred embodiment, wherein seek the optimum concentration range to each component, from
And achieve hydrophilic, the self_cleaning effect that can reach good, also can increase the technique effect of photovoltaic generation simultaneously.
As the preferred embodiment of one of the present invention, described preparation method comprises the steps:
(1)TiO2Prepared by solution:
By butyl titanate, diethanolamine, isopropanol 4:1:(20 by volume～30) mixing, stir, make solution
A, is stirred continuously solution A with agitator；
By isopropanol, deionized water 1:(1 by volume～5) mixing, stir, make solution B, be slowly added into and stir
In the solution A mixed, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
By sodium silicate and step 1) the middle TiO obtained2Solution is mixed in the ratio of 0.5g:100ml, stirs, makes
Solution C, after continuing stirring 1 hour, mixes silane with solution C 1.5:100 by volume, stirs, be adjusted to by pH value
9.2, continue stirring 2 hours, prepare the multi-functional TiO of the present invention2Nano paint.
As the preferred embodiment of one of the present invention, described preparation method comprises the steps:
(1)TiO2Prepared by solution:
By 40ml butyl titanate, 10ml diethanolamine, 300ml isopropanol mixes, stirs, make solution A, with stirring
Solution A is stirred continuously by device；
200ml isopropanol and 200ml～300ml deionized water are mixed, stirs, make solution B, be slowly added into
In solution A in stirring, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
4.0g～4.5g sodium silicate is added step 1) the middle TiO obtained2Solution mixes, and stirs, makes solution C,
After continuing stirring 1 hour, 12ml～13ml silane is mixed with solution C, stirs, pH value is adjusted to 9.2, continue stirring
2 hours, prepare the multi-functional TiO of the present invention2Nano paint.
As a kind of most preferably embodiment of the present invention, described preparation method comprises the steps:
(1)TiO2Prepared by solution:
By 40ml butyl titanate, 10ml diethanolamine, 300ml isopropanol mixes, stirs, make solution A, with stirring
Solution A is stirred continuously by device；
200ml isopropanol and 300ml deionized water are mixed, stirs, make solution B, be slowly added in stirring
Solution A in, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
4.2g sodium silicate is added step 1) the middle TiO obtained2Solution mixes, and stirs, makes solution C, continues to stir
After mixing 1 hour, 12.7ml silane is mixed with solution C, stirs, pH value is adjusted to 9.2, continue stirring 2 hours, prepare
The multi-functional TiO of the present invention2Nano paint.
Another aspect of the present invention is to provide a kind of multi-functional TiO prepared by said method2Nano paint.
Multi-functional TiO of the present invention2Nano paint is a kind of activated water based sols, through the base at such as glass
Material surface spraying, can quickly form the film layer of inorganic nanostructures without heat treatment.Such as, by the multi-functional TiO of the present invention2
The glass plate of nano paint spraying photovoltaic module, TiO2Can be bonded completely with glass at short notice, film forming has super hydrophilic
Property and photocatalysis effect, the most effectively, increase photovoltaic module generated energy.
Preferably, multi-functional TiO of the present invention2TiO in nano paint2For anatase type nano TiO2Particle.Above-mentioned
Film layer not only can increase the light transmittance of glass, improves the generating efficiency of assembly, moreover it is possible to make photovoltaic component glass surface have super parent
Outlet capacity and automatically cleaning ability, eliminate dust and the greasy filth impact on assembly, it will help promotes the generating of photovoltaic module
Amount.Under the joint effect of instantaneous and long-term additional issue mechanism, generated energy promotes amplitude 3-5%.Additionally, due to it is of the present invention
Multi-functional TiO2Modified TiO in nano paint2Nanoparticle can fully absorb and utilize ultraviolet to carry out catalytic reaction, thus
Reduce photovoltaic module ultra-violet absorption amount, delay that assembly backboard EVA's is aging, extend assembly service life.Preferably, described many
Function TiO2Nano paint forms, at substrate surface, the colourless transparent film that a layer thickness is about 150nm.
Multi-functional TiO of the present invention2After nano paint is sprayed at assembly glass surface, with nanoparticle mixture form
Combine with glass chemistry, it is possible to glass surface roughness is greatly reduced, reduce the diffuse-reflectance effect impact on light transmittance.Preferably
Ground, is coated with multi-functional TiO of the present invention2The roughness of the assembly glass surface of nano paint is 40-60nm.
Multi-functional TiO of the present invention2After nano paint is sprayed at assembly glass surface, can be effective within the unit interval
Ground degradation of organic substances.Preferably, it is coated with multi-functional TiO of the present invention2The average light of the assembly glass surface of nano paint
Solution index is 38.3nmol/L/min.
Multi-functional TiO of the present invention2Nano paint utilizes wherein modified TiO2Composition, makes film layer be applied to group
After part glass surface, produce luminescence generated by light and upper conversion (UC gain), lower conversion (DC gain) luminescent effect, the most respectively by red
The energy of outer wave band energy and ultraviolet light wave band is converted into visible light wave range energy, and (prepared by the PL spectral line display present invention multi-functional
TiO2Nano paint film layer has strong absworption peak at about 280nm), to increase effective luminous flux, improve the photoelectric conversion of battery
Efficiency.
The third aspect of the invention is to provide a kind of multi-functional TiO of the present invention2The using method of nano paint,
Including at normal temperatures by multi-functional TiO of the present invention2Nano paint direct spraying is in assembly glass surface, described multi-functional
TiO2Nano paint directly carries out with glass reacting film-forming.
Multi-functional TiO of the present invention2After nano paint is sprayed on glass surface, automatically it is bonded with glass substrate, is allowed to
Forever, securely " grow " at assembly glass surface.Said method is simple to operate, saves human cost, is prepared by said method
Film clarity good, quality is high, the cohesive force of stable performance and base material is very strong, weatherability is very strong, can keep more than 25 years
Service life.
Preferably, described spraying can be carried out by specialty spray gun.
Preferably, photovoltaic module can be sprayed by following two spraying method: photovoltaic module factory sprays and photovoltaic plant
In-situ spraying.
The fourth aspect of the invention is to provide one to be coated with multi-functional TiO of the present invention2The light of nano paint
Photovoltaic assembly glass.
Preferably, it is coated with multi-functional TiO of the present invention2The roughness of the described assembly glass surface of nano paint is
40-60nm。
Preferably, it is coated with multi-functional TiO of the present invention2The average photodissociation of the described assembly glass surface of nano paint
Index is 38.3nmol/L/min.
It is coated with multi-functional TiO of the present invention2The described assembly glass of nano paint, produces luminescence generated by light and upper conversion
(UC gain), lower conversion (DC gain) luminescent effect, convert the energy of infrared band energy and ultraviolet light wave band the most respectively
For visible light wave range energy, (PL spectral line shows multi-functional TiO of the present invention2The film layer of nano paint has by force at about 280nm
Strong absworption peak), to increase effective luminous flux, improve the electricity conversion of battery.
Invention advantage
1, the water-soluble multifunctional TiO prepared by the inventive method2Nano paint, has preferable dispersibility, during storage
Depositional phenomenon will not be produced, in substrate surface, during spraying, can have preferable uniformity by direct spraying at normal temperatures；Spraying photovoltaic
After the glass plate of assembly, TiO2Can completely be bonded with glass at short notice, there is the stronger cohesive force with base material, anti-scratch
Wash, good endurance, will not because of matter of time or with environmental activity and peeling base.
2, the multi-functional TiO prepared by the inventive method2Nano paint formed film layer, have ultrahydrophilic and from
Cleaning function so that the pollutant of substrate surface can be rinsed easily；
3, the multi-functional TiO prepared by the inventive method2The film layer that nano paint is formed has photocatalysis effect, can have
The Organic substance of effect ground degraded substrate surface, keeps the surface cleaning of photovoltaic module；
4, the multi-functional TiO prepared by the inventive method2The film layer that nano paint is formed, can reduce substrate surface thick
Rugosity, strengthens substrate surface light transmittance, and utilizes luminescence generated by light and upper conversion, lower conversion light characteristic, it is possible to effectively strengthen light
Optoelectronic conversion ratio；And
5, the preparation method of the present invention is simple to operate, cost-effective, by the inventive method prepare film clarity good,
Quality is high, stable performance, very strong with the cohesive force of base material, weatherability is very strong, can keep the service life of more than 25 years.
Accompanying drawing explanation
Fig. 1 is multi-functional TiO of the present invention in embodiment 12The step of the preparation method of nano paint；
Fig. 2 is multi-functional TiO prepared by the spraying present invention2After nano paint film layer, glass surface roughness improves situation；
Fig. 3 is multi-functional TiO prepared by the spraying present invention2After nano paint, glass transmission rate rises situation；
Fig. 4 is multi-functional TiO prepared by the present invention2Nano paint luminescence generated by light effect detection collection of illustrative plates；
Fig. 5 is to be coated with multi-functional TiO prepared by the present invention2The hydrophilic angle detection case of the glass of nano paint；
Fig. 6 is multi-functional TiO prepared by the present invention2Modified TiO in nano paint2Nanoparticle decomposing organic matter principle
Figure.
Detailed description of the invention
The multi-functional TiO of embodiment 1 present invention2The preparation method of nano paint
1.1 test procedures:
The multi-functional TiO of table 1 present invention2The consumption of each component in the preparation method of nano paint
Table 1 shows the multi-functional TiO organizing 1～3 in the present embodiment2The consumption of each component of nano paint.With group 3 it is
Example, prepares the multi-functional TiO organizing 3 in the present embodiment according to the following step2Nano paint.
(1) primary TiO2The preparation of solution:
Prepare environment 25 DEG C.
By 40ml butyl titanate, 10ml diethanolamine, 300ml isopropanol mixes, and mixing stirs, makes solution A,
With agitator, solution A is stirred 1 hour；
200ml isopropanol and 300ml deionized water are mixed, stirs, make solution B, be slowly added in stirring
Solution A in, container maintain stirring；
Continue stirring after having mixed and obtain TiO in 1 hour2Primary solution.
(2)TiO2The dispersion of nanometer solution and surface modification:
A. silicate dispersant is added
Take 4.2g sodium silicate, join the TiO in the stirring that step 1 obtains2In primary solution, and continue to stir 1 hour.
B. silane coupler is added
Take 12.7ml monosilane, the TiO being slowly added in stirring2In primary solution.The pH value of detection solution, and use salt
Acid and the TiO of sodium hydrate regulator solution2PH value is to 9.2.Continue stirring 2 hours afterwards, prepare the multi-functional TiO of the present invention2Receive
Rice coating.
Take the multi-functional TiO prepared2Nano paint, sprays to mother glass plate, carries out the spraying effect of following example
Fruit test.Test through spraying effect, group 1～the multi-functional TiO of group 32Nano paint has similar spraying effect test knot
Really, will not repeat in this manual.The multi-functional TiO that following example obtain with group 32The spraying effect of nano paint
The present invention will be described for result of the test.
Multi-functional TiO prepared by embodiment 2 present invention2The impact of photovoltaic module conversion efficiency is tested by nano paint
2.1 light transmittance detection tests
2.1.1 test material: according to the multi-functional TiO of embodiment 1 preparation2Nano paint, assembly energy ultrawhite figured glass, business
Industry TiO2Class automatically cleaning product
2.1.2 test procedure:
1) roughness test
2) light transmittance contrast experiment instrument GST3 air-flotation type spectrophotometer
2.1.4 result
1) glass surface roughness reduces
Spraying rear surface is improved situation and is seen Fig. 2.As in figure 2 it is shown, before spraying the roughness on substrate (glass) surface be 200～
300nm, uses multi-functional TiO prepared by the present invention2After nano paint spraying, roughness is decreased to 40-60nm, thus reduces unrestrained
Reflections affect, increases light transmittance.
The multi-functional TiO prepared mainly due to the present invention2After nano paint is sprayed at assembly surface, mix with nanoparticle
Solvate form and glass chemistry combine, it is possible to glass surface roughness is greatly reduced, and reduce the diffuse-reflectance effect shadow to light transmittance
Ring.
2) self-cleaning glass light transmittance increases
Anti-reflection test result is shown in Fig. 3.As it is shown on figure 3, glass-coating TiO of the prior art2After class automatically cleaning product,
The absorbance of glass is substantially reduced (reduction amplitude reaches about 10%), and sprays multi-functional TiO prepared by the present invention2Nano paint
Self-cleaning glass, it is possible to glass surface roughness is greatly reduced so that assembly energy ultrawhite figured glass absorbance improve
About 1%.
2.2 luminescence generated by light tests
2.2.1 test material:
Multi-functional TiO according to embodiment 1 preparation2Nano paint, assembly energy ultrawhite figured glass.
2.2.2 test procedure: detect by F-4600FL Spectrophotometer fluorescence spectrophotometer, use 360nm ultraviolet
Light irradiates the energy ultrawhite figured glass scribbling SSG, finds to go out to have peak value at 420nm, and remaining is smooth curve, and luminescence generated by light has been described
Effect.
2.2.3 result
Multi-functional TiO prepared by the present invention2Nano paint luminescence generated by light is shown in Fig. 4 at the tested collection of illustrative plates of Chinese Academy of Sciences's physics and chemistry. as
Shown in Fig. 4, use 360nm ultraviolet excitation, the multi-functional TiO prepared through the present invention2The collection of illustrative plates of optical attenuation after nano paint,
Figure is found out and occurs in that peak value in 420nm blue light position.Demonstrate multi-functional TiO prepared by the present invention2Nano paint absorbs purple
After outer energy, part energy is converted to blue light energy.
Nano level TiO2There is luminescence generated by light and upper conversion (UC gain), lower conversion (DC gain) light characteristic can have
Effect improves light utilization efficiency, makes battery conversion efficiency increase.This is owing to the spectral response of silicon solar cell is mainly at 300-
Between 1100nm, and focus primarily upon in visible-range, and solar spectrum is actually distributed in a relative broad range, and
Long wave (infrared) and shortwave (ultraviolet) part accounting are respectively close to 5% and 50%.Therefore, in order to preferably mate photovoltaic cell
Spectral response curve, multi-functional TiO prepared by the present invention2Nano paint utilizes wherein modified TiO2Composition, makes film layer answer
After assembly surface, produce luminescence generated by light and upper conversion (UC gain), lower conversion (DC gain) luminescent effect, the most respectively will
The energy of infrared band energy and ultraviolet light wave band is converted into visible light wave range energy (many merits prepared by the PL spectral line display present invention
Can TiO2Nano paint film layer has strong absworption peak at about 280nm), to increase effective luminous flux, the photoelectricity improving battery turns
Change efficiency.
2.3 power additional issue effects
2.3.1. test method
Test under standard test condition according to Nan De TUV authentication center
Numbering: No.70.406.15.189.01
Test temperature: 25 DEG C of radiant illuminations: 1000W/ spectral distribution: AM1.5G
2.3.2 test material:
Multi-functional TiO according to embodiment 1 preparation2Nano paint, solar components are (purchased from Trina Solar (Trina
Solar) company), solar simulator
2.3.3 test procedure:
1. by the multi-functional TiO of preparation2Nano paint is sprayed on the front surface of 4 groups of photovoltaic modulies, then in standard testing
Under the conditions of test
2. drawing IV curve, the parameters such as Voc, Vmp, Isc, Imp, Pmp, FF, contrasts its battery and component efficiency is surveyed
Examination.
2.3.4 result
According to the test result of Nan De TUV authentication center, multi-functional TiO prepared by the spraying present invention2After nano paint, too
Sun can assembly mean power be instantaneous improves 1.39%.Further illustrate by above-mentioned raising light transmittance and luminescence generated by light effect
Approach, multi-functional TiO prepared by the present invention2Nano paint can quickly improve the conversion efficiency of photovoltaic module.
The multi-functional TiO of embodiment 3 present invention2The photodissociation index testing experiment of nano paint
3.1 test method
Nan De TUV authentication center tests
Numbering: No.70.406.15.189.02-01
3.2 test materials:
Multi-functional TiO according to embodiment 1 preparation2Nano paint, 3 pieces of Sample assemblies energy ultrawhite figured glass
3.3 test procedures: according to JC/T2168-2013 " self-cleaning coated glass " standard, spraying is made according to embodiment 1
Standby multi-functional TiO2The photovoltaic component glass of nano paint carries out methylene blue test, to test photodissociation index.3.0 ±
Irradiate six times under the ultraviolet of 0.10mW/, continue 20 minutes every time
3.4 result
Defining according to JC/T2168-2013 " self-cleaning coated glass " standard, photodissociation index characterizes photocatalytic multifunctional
TiO2The numerical value of nano paint photocatalysis performance, i.e. photocatalytic multifunctional TiO2Nano paint is degradation of organic substances within the unit interval
The eigenvalue of ability.According to standard-required, self-cleaning cleanliness film glass photodissociation index should be not less than 7nmol/L/min.
Table 2 sprays the multi-functional TiO of the present invention2The glass of nano paint and the static contact angle test result of comparison glass
| Sample number | Photodissociation index, nmol/L/min |
| 1 | 41.1 |
| 2 | 36.4 |
| 3 | 37.5 |
According to the test result (seeing table 2) of Nan De TUV authentication center, multi-functional TiO prepared by 3 pieces of present invention2Nanometer
The photodissociation index of coating sample glass is respectively 41.1nmol/L/min, 36.4nmol/L/min, 37.5nmol/L/min, averagely
Value is 38.3nmol/L/min, far above standard-required (not less than 7nmol/L/min).Illustrate that the present invention coats according to enforcement
The multi-functional TiO of example 1 preparation2The photovoltaic component glass of nano paint can degradation of organic substances effectively within the unit interval.
Under light illumination, nano-TiO2Can with the steam in air and oxygen generation chemical reaction, generate Strong oxdiative ability-
OH high activity group.Do not consuming multi-functional TiO2In the case of nano paint self, most organic compound can be caused
Thing molecule generation oxidation reaction, generates CO2And H2O.Decomposing organic matter is embodied in the decomposition birds droppings of glass surface, industrial pollution is given up
Gas, vehicle exhaust etc..
This is because nano-TiO2Band-gap energy be about 3.2eV, correspond approximately to the energy of 387.5nm photon.When by ripple
When length is less than the irradiation of the ultraviolet light of 387.5nm, valence shell electron can be excited to conduction band, and produce and have the most strongly active electricity
Son-hole pair:
After these electron-hole pairs move to surface, redox reaction can be participated in, accelerate light degradation reaction.These
Reaction includes: produced electron-hole can be by absorption at TiO2The hydroxyl of particle surface and hydrone are oxidized to OH-freely
Base:
Ti4++OH+h+→Ti4+OH·
Ti4+-H2O+h+→Ti4+OH·+H+
Association is strong oxidizer at the OH-free radical of titanic ion surface, it is possible to aoxidize adjacent Organic substance, it is also possible to
It is diffused into oxidation of organic compounds in liquid phase.Many Organic substances also can be aoxidized by hole.Absorption is at TiO2The oxygen on surface can lead to
Cross capture electronics, formed negative oxygen ion and stoped the compound of electronics and hole, then improve its oxidation activity:
O2+e-→O2 -
Hydrogen peroxide can individually and peroxide effect or capture electronics and produce hydroxyl radical free radical.
H2O2→2OH·
H2O2+O2 -→OH·+OH-+O2
H2O2+e-→OH·+OH-
Fig. 6 is the multi-functional TiO of the present invention2Described TiO in nano paint2Nanoparticle decomposing organic matter schematic diagram.
The multi-functional TiO of embodiment 4 present invention2The hydrophilic angle testing experiment of nano paint
4.1 test method
Nan De TUV authentication center foundation JC/T2168-2013 has carried out the test of hydrophilic angle.
Numbering: 70.406.15.189.02-00.
4.2 test materials:
Multi-functional TiO according to embodiment 1 preparation2Nano paint, 4 block assembly energy ultrawhite figured glass
4.3 test procedures:
1. the multi-functional TiO that will prepare according to embodiment 12Nano paint is sprayed on 3 pieces of Sample assemblies energy ultrawhite figured glass
On, another block normal specimens glass is as controlled trial glass；
2. observe hydrophilic angle with CCD instrument and equipment, choose on every piece of sample 5 differences and be repeated test.
4.4 result
According to the test result (seeing table 3) of Nan De TUV authentication center, multi-functional TiO prepared by the spraying present invention2Nanometer
After coating, the averaged static contact angle of glass is 6.1 °, compared with the static contact angle 23.1 ° of comparison glass, reduces
73.6%.
Table 3 sprays the multi-functional TiO of the present invention2The glass of nano paint and the static contact angle test result of comparison glass
| Sample number | Static contact angle |
| 1 | 6.4 |
| 2 | 5.6 |
| 3 | 6.4 |
| Comparison glass | 23.1 |
Test case is shown in Fig. 5.Illustrate that the present invention coats multi-functional TiO prepared by the inventive method2The light of nano paint
Photovoltaic assembly glass surface, under the irradiation of light, declining to a great extent in the hydrophilic angle of water droplet, presents ultrahydrophilic.In action of gravity
Under, it is more easy to take away the pollutant of sheet.So just can be clear by the dust of glass surface, sandy soil with less clear water or rainwater
Remove.
Under ultraviolet light irradiates, TiO2Valence-band electrons is excited to conduction band, at Surface Creation electron hole pair, electronics and Ti4 +Reaction, hole is then reacted with surface bridging oxygen, makes Surface Oxygen hollow, thus Ti nearby4+Turn to Ti3+, Ti3+Be suitable to free water inhale
Attached.Now, the hydrolysis ionic adsorption in air, in Lacking oxygen, becomes chemical absorbed water (surface formation hydroxyl), chemisorbed
Water can adsorb the moisture in air further, forms mechanical water adsorption layer, i.e. at Ti3+The microcell of highly-hydrophilic is formed around defect
(Ti-OH), and surface residual region still keeps hydrophobicity, so at TiO2Surface constitutes the nano-scale being evenly distributed and separates
Hydrophilic microcell, be similar to two dimension capillarity.Owing to the size of water droplet is far longer than the area of hydrophilic microcell, thus macroscopical
Upper TiO2Surface exhibits goes out water-wet behavior, thus invades profit surface；Stop ultraviolet light irradiating.The hydroxyl of chemisorbed is by air
Oxygen replaces, and again appears as hydrophobic state, and after stopping illumination, its surface super hydrophilic can maintain a few hours to about one week, with
After slowly return to according to front hydrophobic state, then with ultraviolet lighting, show as again hydrophilic.
Additionally, multi-functional TiO prepared by the spraying present invention2After nano paint, it is the most flat that glass substrate becomes on microcosmic
Whole, dust granule relative adhesion area reduces, it is easier to landing is got off.
Meanwhile, nano-TiO2Quasiconductor electronics under light illumination separates with hole, has certain electric conductivity, coordinates antistatic
Agent composition, has antistatic absorbability.Dust can be stoped from source to greatest extent in the attachment of glass surface, stop
Glass is dirty, changes from passive to active, and is glass with clean truly.
The above is only the preferred embodiments of the present invention, and the present invention not does any pro forma restriction, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people being familiar with this specialty
Member, in the range of without departing from technical solution of the present invention, when the technology contents of available the disclosure above makes a little change or repaiies
Decorations are the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technology according to the present invention is real
Any simple modification, equivalent variations and the modification that confrontation above example is made, all still falls within the scope of technical solution of the present invention
In.
Claims (10)
1. a multi-functional TiO2The preparation method of nano paint, comprises the steps:
1)TiO2Prepared by solution: with butyl titanate for titanium source, and isopropanol is solvent, and diethanolamine is prepared by hydrolysis inhibitor
TiO2Solution, and
2)TiO2The dispersion of nanometer solution and surface modification: to step 1) the middle TiO obtained2Solution, does dispersant with sodium silicate,
Silane makees coupling agent, to TiO2Modifying surface, obtain the multi-functional TiO of the present invention2Nano paint.
Preparation method the most according to claim 1, it is characterised in that each component in described preparation method, is divided by quality
Number meter includes:
Butyl titanate 2 parts～5 parts
Diethanolamine 1 part～3 parts
Isopropanol 40 parts～50 parts
Deionized water 20 parts～30 parts
Sodium silicate 4 parts～6 parts
Monosilane 10 parts～13 parts.
Preparation method the most according to claim 2, it is characterised in that each component in described preparation method, is divided by quality
Number meter includes:
Butyl titanate 4 parts
Diethanolamine 1 part
Isopropanol 50 parts
Deionized water 30 parts
Sodium silicate 4 parts
Monosilane 12 parts.
Preparation method the most according to claim 1, it is characterised in that described preparation method comprises the steps:
(1)TiO2Prepared by solution:
Butyl titanate, diethanolamine, isopropanol are mixed by a certain percentage, stirs, make solution A, with agitator to molten
Liquid A is stirred continuously；
Isopropanol, deionized water are mixed by a certain percentage, stirs, make solution B, the solution being slowly added in stirring
In A, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
By sodium silicate and step 1) the middle TiO obtained2Solution mixes by a certain percentage, stirs, and makes solution C, continues stirring
After 1 hour, silane is mixed by a certain percentage with solution C, stir, pH value is adjusted to 9.2, continue stirring 2 hours, system
Obtain the multi-functional TiO of the present invention2Nano paint.
Preparation method the most according to claim 4, it is characterised in that described preparation method comprises the steps:
(1)TiO2Prepared by solution:
By butyl titanate, diethanolamine, isopropanol 4:1:(20 by volume～30) mixing, stir, make solution A, use
Solution A is stirred continuously by agitator；
By isopropanol, deionized water 1:(1 by volume～5) mixing, stir, make solution B, be slowly added in stirring
Solution A in, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
By sodium silicate and step 1) the middle TiO obtained2Solution is mixed in the ratio of 0.5g:100ml, stirs, makes solution C,
After continuing stirring 1 hour, silane is mixed with solution C 1.5:100 by volume, stirs, pH value is adjusted to 9.2, continue
Continuous stirring 2 hours, prepares the multi-functional TiO of the present invention2Nano paint.
Preparation method the most according to claim 4, it is characterised in that described preparation method comprises the steps:
(1)TiO2Prepared by solution:
By 40ml butyl titanate, 10ml diethanolamine, 300ml isopropanol mixes, stirs, make solution A, with agitator pair
Solution A is stirred continuously；
200ml isopropanol and 200ml～300ml deionized water are mixed, stirs, make solution B, be slowly added into stirring
In solution A in, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
4.0g～4.5g sodium silicate is added step 1) the middle TiO obtained2Solution mixes, and stirs, makes solution C, continues to stir
After mixing 1 hour, 12ml～13ml silane is mixed with solution C, stirs, pH value is adjusted to 9.2, continue stirring 2 hours,
Prepare the multi-functional TiO of the present invention2Nano paint.
Preparation method the most according to claim 6, it is characterised in that described preparation method comprises the steps:
(1)TiO2Prepared by solution:
By 40ml butyl titanate, 10ml diethanolamine, 300ml isopropanol mixes, stirs, make solution A, with agitator pair
Solution A is stirred continuously；
200ml isopropanol and 300ml deionized water being mixed, stir, make solution B, be slowly added in stirring is molten
In liquid A, and obtain TiO after continuing to stir 1 hour2Solution；
(2)TiO2The dispersion of nanometer solution and surface modification:
4.2g sodium silicate is added step 1) the middle TiO obtained2Solution mixes, and stirs, and makes solution C, continues stirring 1 little
Shi Hou, mixes 12.7ml silane with solution C, stirs, and pH value is adjusted to 9.2, continues stirring 2 hours, prepares this
Bright multi-functional TiO2Nano paint.
8. the multi-functional TiO according to claim 1～7 preparation2Nano paint；Preferably, described multi-functional TiO2Nanometer is coated with
TiO in material2Particle is anatase type nano TiO2Particle.
9. one kind is coated with multi-functional TiO according to claim 82The assembly glass of nano paint；Preferably, described group
The roughness of part glass surface is 40-60nm.
Assembly glass the most according to claim 9, it is characterised in that the average photodissociation index of described assembly glass surface
For 38.3nmol/L/min.
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