CN108751737A - Tin dope nickel oxide-stannic oxide composite nanocrystalline film and preparation method thereof - Google Patents
Tin dope nickel oxide-stannic oxide composite nanocrystalline film and preparation method thereof Download PDFInfo
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- CN108751737A CN108751737A CN201810539137.2A CN201810539137A CN108751737A CN 108751737 A CN108751737 A CN 108751737A CN 201810539137 A CN201810539137 A CN 201810539137A CN 108751737 A CN108751737 A CN 108751737A
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- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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- C03C2217/24—Doped oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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Abstract
The invention discloses a kind of tin dope nickel oxide-stannic oxide composite nanocrystalline films, it is characterized in that, tin dope nickel oxide-stannic oxide composite nanocrystalline film is a kind of nickel oxide nano-crystal and the compound electrochomeric films of tin dioxide nanocrystal of the doping of+4 valence tin ions.The film can improve colour fading state NiOxThe transmissivity of film, the optical modulation amplitude for increasing film.Preparation method is：Step 1, the complex sol C of the element containing Sn-Ni is prepared；Step 2, lifting prepares gel film, the colloidal sol of the element containing Sn-Ni of acquisition is prepared gel film by dip-coating method on FTO electro-conductive glass, and drying is taken out after ten minutes at 100~150 DEG C by the gel film substrate of lifting preparation, is air-cooled to room temperature；Step 3, the gel film substrate in step 2 is positioned in Muffle furnace and is heat-treated, repeated after step 2 and step 3 obtain certain thickness film, take out and be air-cooled to room temperature to get.
Description
Technical field
The invention belongs to electrochomeric films preparing technical fields, and in particular to a kind of tin dope nickel oxide-stannic oxide
Composite nanocrystalline film；The invention further relates to the preparation methods of the tin dope nickel oxide-stannic oxide composite nanocrystalline film.
Background technology
Nickel oxide is one of most common anode electrochromic material of current research.It is a kind of common P-type semiconductor,
Energy gap at room temperature is 3.6~3.7eV, and electron conduction is poor.Crystalline state nickel oxide belongs to the closs packing face-centered cubic of NaCl
Crystal structure, inside typically contain a certain amount of Ni2+Usually can in nickel oxide for the positive and negative charge in balance crystal in vacancy
There are some Ni3+, in this way, the nickel oxide material under normality, which is one kind in fact, both contains Ni2+, also contain Ni3+NiOx.It is positive because
NiOxIn contain more Ni3+So that NiOxFilm generates visible light strong absorption, it is difficult to obtain the preferable oxygen of transparency
Change nickel material, this Ni3+Residual and lower transparency will directly affect the transmission of visible light of colour fading state nickel oxide film,
It is relatively low so as to cause the electrochromic property of nickel oxide film, be embodied in optical modulation amplitude is low, service life cycle is short,
The aspects such as coloration efficiency is low.Therefore, how to solve the problems, such as this, improve NiO film electrochromic properties and have become required concern
Emphasis.Research is found：In addition to improve preparation method, optimization preparation process other than, doping vario-property and prepare composite material be improve
The most direct most efficient method of nickel oxide film electrochromic property.
Invention content
The object of the present invention is to provide a kind of tin dope nickel oxide-stannic oxide composite nanocrystalline films, utilize tin element
Doping, can reduce NiOxNi in film3+Residual improves colour fading state NiOxThe transmissivity of film, the optical modulation for increasing film
Amplitude.
It is a further object to provide a kind of preparations of tin dope nickel oxide-stannic oxide composite nanocrystalline film
Method.
The technical solution adopted in the present invention is：A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline film, tin are mixed
Miscellaneous nickel oxide-stannic oxide composite nanocrystalline film is a kind of nickel oxide nano-crystal and titanium dioxide sijna of the doping of+4 valence tin ions
The brilliant compound electrochomeric films of rice, tin dope nickel oxide average grain size are 20~60 nanometers, stannic oxide average crystal grain
Size is 5~15 nanometers, and composite nanocrystalline film thickness is 300~500 nanometers.
Another technical solution of the present invention is：A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline is thin
The preparation method of film, which is characterized in that be as follows：
Step 1, the complex sol C of the element containing Sn-Ni is prepared
Step 1.1, the Sol A of the element containing Ni is prepared：Its process for preparation is that nickel acetate is added in absolute methanol, room
It is stirred well to clarification under temperature, adds appropriate acrylic acid, continues stirring 2 hours, obtains bottle green clear sol A；
Step 1.2, the sol B of the element containing Sn is prepared：Its process for preparation be butter of tin is mixed with acetylacetone,2,4-pentanedione, and
It is stirred 15 minutes in 45 DEG C~60 DEG C, acetic anhydride is then added thereto, and stir 15 minutes in 45 DEG C, is cooled to room temperature, most
After ethanol in proper amount is added, continue stirring and obtain clear sol B in 20 minutes；
Step 1.3, Sol A and sol B are mixed at normal temperatures, stirring contains Sn-Ni elements in 1 hour to get clear
Complex sol C；
Step 2, lifting prepares gel film
The colloidal sol of the element containing Sn-Ni of acquisition is prepared into gel film by dip-coating method on FTO electro-conductive glass, and
By the gel film substrate of lifting preparation, drying is taken out after ten minutes at 100~150 DEG C, is air-cooled to room temperature；
Step 3, the gel film substrate in step 2 is positioned in Muffle furnace at 450~550 DEG C and is heat-treated 10 points
After clock, taking-up, repetition step 2 and step 3 obtain certain thickness film, it is heat-treated 90 minutes at a temperature of 450~550 DEG C,
It takes out and is air-cooled to room temperature to get tin dope nickel oxide-stannic oxide composite nanocrystalline film.
It is a feature of the present invention that
In step 1, butter of tin used, nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid, acetic anhydride, absolute methanol, ethyl alcohol
Molar ratio is 0.25~0.4:1:1.68~2.69:3:0.37~0.59:40:9.
In step 2, lifting film uses Best-Effort request technology vertically evenly to be carried with the speed of 3.3mm/s~4.0mm/s
Pull out colloidal sol liquid level.
In step 3, the tin dope nickel oxide-stannic oxide composite nanocrystalline film being prepared is a kind of+4 valence tin ions
The nickel oxide nano-crystal of doping and the compound electrochomeric films of tin dioxide nanocrystal, tin dope nickel oxide average grain size
It it is 20~60 nanometers, stannic oxide average grain size is 5~15 nanometers, and composite nanocrystalline film thickness is received for 300~500
Rice.
The beneficial effects of the invention are as follows：
(1) compared to pure nickel oxide film, due to Sn4+Doping so that the transmission of tin dope nickel oxide film colour fading state
Rate obviously increases, and solves the problems, such as relatively low about bleaching state nickel oxide film transmitance；In addition, tin atom extra in colloidal sol
It is nanocrystalline that tin dioxide transparent is formed during heat treatment, not only increases laminated film electronic conduction ability, and improve
The specific surface area of composite material, improves the conducting power of required ion in electrochromic process, due to electronics and ion
Transmittability has obtained effective enhancing, the electroluminescent change such as the optical modulation amplitude of laminated film, service life cycle, coloration efficiency
Color performance has larger promotion.
(2) the tin dope nickel oxide-stannic oxide composite nanocrystalline film is adulterated using tin element, reduces NiOxIn film
Ni3+Residual improves colour fading state NiOxThe transmissivity of film, the optical modulation amplitude for increasing film；Stannic oxide is utilized simultaneously
Electric conductivity and the higher specific surface area of nano-particle, raising composite nanocrystalline thin film electronic and ion are injected and extracted from, effectively
Promoted film electrochromic property, solve existing nickel oxide film optical modulation amplitude is low, service life cycle is short, coloring effect
Rate is low and the incomplete problem of fading.
(3) method used by the laminated film is prepared --- sol-gel technique can realize big face in atmospheric environment
Product film, the tin dope nickel oxide-stannic oxide composite nanocrystalline film surface prepared is smooth, uniform ground.This method has
It hopes and is applied to industrial mass production, be of great immediate significance.
Description of the drawings
Fig. 1 is the XRD spectrum of tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel in the present invention；
Fig. 2 is transmission electron microscope (TEM) photo of tin dope nickel oxide-stannic oxide composite nanocrystalline film in the present invention；
Fig. 3 is the selective electron diffraction (SAED) of tin dope nickel oxide-stannic oxide composite nanocrystalline film in the present invention
Photo；
Fig. 4 is tin dope nickel oxide-stannic oxide composite nanocrystalline film in the present invention and pure nickel about Sn elements
High-resolution XPS collection of illustrative plates；
Fig. 5 is tin dope nickel oxide-stannic oxide composite nanocrystalline film in the present invention and pure nickel in colour fading shape
Transmittance test result comparison diagram under state；
Fig. 6 is the negative and positive extreme value of tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel in the present invention
Electric current with cycle-index change curve；
Fig. 7 is that the optical density of tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel becomes in the present invention
Change the change curve of (Δ OD) with charge density.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The present invention provides a kind of tin dope nickel oxide-stannic oxide composite nanocrystalline films, such as Fig. 1-6, tin dope oxygen
It is a kind of nickel oxide nano-crystal and tin dioxide nanocrystal of the doping of+4 valence tin ions to change nickel-stannic oxide composite nanocrystalline film
Effectively compound electrochomeric films, tin dope nickel oxide average grain size are 20~60 nanometers, stannic oxide average crystal grain
Size is 5~15 nanometers, and composite nanocrystalline film thickness is 300~500 nanometers.
The present invention also provides a kind of preparation methods of tin dope nickel oxide-stannic oxide composite nanocrystalline film, special
Sign is, is as follows：
Step 1, the complex sol C of the element containing Sn-Ni is prepared
Step 1.1, the Sol A of the element containing Ni is prepared：Its process for preparation is that nickel acetate is added in absolute methanol, room
It is stirred well to clarification under temperature, adds appropriate acrylic acid, continues stirring 2 hours, obtains bottle green clear sol A；
Step 1.2, the sol B of the element containing Sn is prepared：Its process for preparation be butter of tin is mixed with acetylacetone,2,4-pentanedione, and
It is stirred 15 minutes in 45 DEG C~60 DEG C, acetic anhydride is then added thereto, and stir 15 minutes in 45 DEG C, is cooled to room temperature, most
After ethanol in proper amount is added, continue stirring and obtain clear sol B in 20 minutes；
Step 1.3, Sol A and sol B are mixed at normal temperatures, stirring contains Sn-Ni elements in 1 hour to get clear
Complex sol C；
In step 1, butter of tin used, nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid, acetic anhydride, absolute methanol, ethyl alcohol
Molar ratio is 0.25~0.4:1:1.68~2.69:3:0.37~0.59:40:9；
Step 2, lifting prepares gel film
The colloidal sol of the element containing Sn-Ni of acquisition is prepared into gel film by dip-coating method on FTO electro-conductive glass, and
By the gel film substrate of lifting preparation, drying is taken out after ten minutes at 100~150 DEG C, is air-cooled to room temperature；In step 2, carry
Drawing film uses Best-Effort request technology vertically evenly to lift out colloidal sol liquid level with the speed of 3.3mm/s~4.0mm/s；
Step 3, the gel film substrate in step 2 is positioned in Muffle furnace at 450~550 DEG C and is heat-treated 10 points
After clock, taking-up, repetition step 2 and step 3 obtain certain thickness film, it is heat-treated 90 minutes at a temperature of 450~550 DEG C,
It takes out and is air-cooled to room temperature to get tin dope nickel oxide-stannic oxide composite nanocrystalline film；
In step 3, the tin dope nickel oxide-stannic oxide composite nanocrystalline film being prepared is a kind of+4 valence tin ions
The nickel oxide nano-crystal of doping and the compound electrochomeric films of tin dioxide nanocrystal, tin dope nickel oxide average grain size
It it is 20~60 nanometers, stannic oxide average grain size is 5~15 nanometers, and composite nanocrystalline film thickness is received for 300~500
Rice.
Fig. 1 is to prepare tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel using the method for the present invention
The XRD spectrum of film, it will be apparent from this figure that after adding tin element in nickel oxide film, film still keeps the crystalline substance of NiO
Type structure, but diffraction peak intensity is lower, halfwidth narrows, and illustrates that the addition of tin element hinders growing up for oxidation nickel crystallite, obtains
To laminated film in oxidation nickel crystallite become smaller, in addition, illustration be two kinds of sample (200) crystal faces high resolution diffraction peak, compare
It is inclined to low-angle in (200) face diffraction maximum of pure nickel oxide film, tin dope nickel oxide-stannic oxide composite nanocrystalline film
It moves, illustrates that tin element doping enters NiO lattices.Therefore, the laminated film that prepared by the method for the present invention is nanocrystalline structure, therein
Aoxidize the tin ion containing doping into NiO lattices in nickel crystallite.
Fig. 2 is the TEM photos that tin dope nickel oxide-stannic oxide composite nanocrystalline film is prepared using the method for the present invention,
As can be seen that the laminated film sample prepared is nano-crystal film from the photo, crystallite dimension is about 15~20nm.
Fig. 3 is the SAED photos that tin dope nickel oxide-stannic oxide composite nanocrystalline film is prepared using the method for the present invention,
Contain two phase structure from the film that can be seen that preparation in the photo, is NiO structures and SnO respectively2Structure, in conjunction with Fig. 1,
Fig. 2, Fig. 3 can illustrate that the laminated film of preparation is the compound phase of tin dope nickel oxide and tin dioxide nanocrystal.
Fig. 4 is to prepare tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel using the method for the present invention
High-resolution XPS collection of illustrative plates of the film about Sn elements is deposited in two forms from can be seen that Sn elements in laminated film in the collection of illustrative plates
, one is enter NiO lattices in Sn4+, another kind is SnO2, in conjunction with Fig. 1, Fig. 2, Fig. 3 and Fig. 4, further illustrate this hair
Laminated film prepared by bright method is the film that tin dope nickel oxide is combined with tin dioxide nanocrystal.
Fig. 5 is to prepare tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel using the method for the present invention
The electrochromism optic test of film as a result, it can be seen from the figure that laminated film colour fading contrast compared to pure oxygen
Change nickel film is big, and optical modulation amplitude is wider.
Fig. 6 is to prepare tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel using the method for the present invention
The negative and positive extreme current of film with cycle-index change curve.For characterizing the service life cycle of the film, from figure
As can be seen that after 100,000 discoloration cycles, the anode and cathode extreme current of laminated film still keeps higher numerical value, but pure oxygen
The negative and positive extreme current for changing nickel film tapers into, and illustrates the service life cycle higher of laminated film.
Fig. 7 is to prepare tin dope nickel oxide-stannic oxide composite nanocrystalline film and pure nickel using the method for the present invention
The optical density of film changes the change curve of (Δ OD) with charge density.Can be immediately arrived at from the figure two kinds of films
Colour efficiency, the wherein coloration efficiency of laminated film are 45cm2/ C, and the coloration efficiency of pure nickel film only has 25cm2/C.Knot
Fig. 5, Fig. 6 and Fig. 7 test result are closed, illustrates that tin dope nickel oxide-stannic oxide composite nanocrystalline prepared by the method for the present invention is thin
For film compared to pure nickel film, electrochromic property is more preferable.
Embodiment 1
A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline electrochomeric films, structure feature are：Tin dope oxygen
It is 60 nanometers to change nickel average grain size, and stannic oxide average grain size is 5 nanometers, and film thickness is 300 nanometers.
The preparation method of laminated film with the above structure feature, is as follows：
First, the complex sol of the element containing Ni and Sn is prepared.Technical process is as follows：
4.604 grams of nickel acetates are mixed with 30 milliliters of absolute methanols, clarification is stirred well at room temperature, adds 4 milliliters
Acrylic acid continues stirring 2 hours to get bottle green clear sol A.
1.622 grams of butters of tin are mixed with 3.113 grams of acetylacetone,2,4-pentanediones, and in 45 DEG C stir 15 minutes, then thereto
0.698 gram of acetic anhydride is added, and is stirred 15 minutes in 45 DEG C, is cooled to room temperature, is eventually adding 10 milliliters of ethyl alcohol, continues stirring 20
Minute is up to clear sol B.
Sol A and sol B are mixed 1 hour to get the complex sol C of the element containing Ni and Sn at room temperature.
Secondly, lifting prepares gel film.Technical process is as follows：
The colloidal sol of the element containing Sn-Ni is prepared into gel film, pull rate by dip-coating method on FTO electro-conductive glass
For 3.3mm/s, by the gel film substrate of lifting preparation, drying is taken out after ten minutes at 100 DEG C later, is air-cooled to room temperature.
Finally, prepared gel film substrate is heat-treated, technical process is as follows：
Gel film substrate is positioned in Muffle furnace and is heat-treated 10 minutes at 450 DEG C, is taken out.Aforesaid operations are repeated to obtain
It to after certain thickness gel film, is heat-treated 90 minutes at a temperature of being put into 450 DEG C, is finally air-cooled to room temperature, obtain one kind+4
The nickel oxide nano-crystal (average grain size is about 60 nanometers) and tin dioxide nanocrystal (average crystal grain ruler of valence tin ion doping
Very little about 5 nanometers) effective compound electrochomeric films.
Optical modulation amplitude of the laminated film at 550nm wavelength is 59%, coloration efficiency 45cm2/ C is thin by this
For film after 100,000 discoloration cycles, negative and positive extreme current only declines 9%, compared with pure nickel film, optical modulation amplitude
Increase by 156%, coloration efficiency improves 80%, and service life cycle improves 150%.
Embodiment 2
A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline electrochomeric films, structure feature are：Tin dope oxygen
It is 50 nanometers to change nickel average grain size, and stannic oxide average grain size is 8 nanometers, and film thickness is 350 nanometers.
The preparation method of laminated film with the above structure feature, is as follows：
First, the complex sol of the element containing Ni and Sn is prepared.Technical process is as follows：
4.604 grams of nickel acetates are mixed with 30 milliliters of absolute methanols, clarification is stirred well at room temperature, adds 4 milliliters
Acrylic acid continues stirring 2 hours to get bottle green clear sol A.
1.816 grams of butters of tin are mixed with 3.487 grams of acetylacetone,2,4-pentanediones, and in 48 DEG C stir 15 minutes, then thereto
0.783 gram of acetic anhydride is added, and is stirred 15 minutes in 45 DEG C, is cooled to room temperature, is eventually adding 10 milliliters of ethyl alcohol, continues stirring 20
Minute is up to clear sol B.
Sol A and sol B are mixed 1 hour to get the complex sol C of the element containing Ni and Sn at room temperature.
Secondly, lifting prepares gel film.Technical process is as follows：
The colloidal sol of the element containing Sn-Ni is prepared into gel film, pull rate by dip-coating method on FTO electro-conductive glass
For 3.5mm/s, by the gel film substrate of lifting preparation, drying is taken out after ten minutes at 115 DEG C later, is air-cooled to room temperature.
Finally, prepared gel film substrate is heat-treated, technical process is as follows：
Gel film substrate is positioned in Muffle furnace and is heat-treated 10 minutes at 480 DEG C, is taken out.Aforesaid operations are repeated to obtain
To after certain thickness gel film, it is put under 480 DEG C of heat treatment temperatures and is heat-treated 90 minutes, be finally air-cooled to room temperature, obtain
The nickel oxide nano-crystal (average grain size is about 50 nanometers) and tin dioxide nanocrystal of one kind+4 valence tin ions doping are (average
Crystallite dimension is about 8 nanometers) effective compound electrochomeric films.
Optical modulation amplitude of the laminated film at 550nm wavelength is 60%, coloration efficiency 48cm2/ C is thin by this
For film after 100,000 discoloration cycles, negative and positive extreme current only declines 8%, compared with pure nickel film, optical modulation amplitude
Increase by 161%, coloration efficiency improves 92%, and service life cycle improves 155%.
Embodiment 3
A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline electrochomeric films, structure feature are：Tin dope oxygen
It is 40 nanometers to change nickel average grain size, and stannic oxide average grain size is 10 nanometers, and film thickness is 400 nanometers.
The preparation method of laminated film with the above structure feature, is as follows：
First, the complex sol of the element containing Ni and Sn is prepared.Technical process is as follows：
4.604 grams of nickel acetates are mixed with 30 milliliters of absolute methanols, clarification is stirred well at room temperature, adds 4 milliliters
Acrylic acid continues stirring 2 hours to get bottle green clear sol A.
1.946 grams of butters of tin are mixed with 3.736 grams of acetylacetone,2,4-pentanediones, and in 52 DEG C stir 15 minutes, then thereto
0.840 gram of acetic anhydride is added, and is stirred 15 minutes in 45 DEG C, is cooled to room temperature, is eventually adding 10 milliliters of ethyl alcohol, continues stirring 20
Minute is up to clear sol B.
Sol A and sol B are mixed 1 hour to get the complex sol C of the element containing Ni and Sn at room temperature.
Secondly, lifting prepares gel film.Technical process is as follows：
The colloidal sol of the element containing Sn-Ni is prepared into gel film, pull rate by dip-coating method on FTO electro-conductive glass
For 3.6mm/s, by the gel film substrate of lifting preparation, drying is taken out after ten minutes at 125 DEG C later, is air-cooled to room temperature.
Finally, prepared gel film substrate is heat-treated, technical process is as follows：
Gel film substrate is positioned in Muffle furnace and is heat-treated 10 minutes at 500 DEG C, is taken out.Aforesaid operations are repeated to obtain
To after certain thickness gel film, it is put under 500 DEG C of heat treatment temperatures and is heat-treated 90 minutes, be finally air-cooled to room temperature, obtain
The nickel oxide nano-crystal (average grain size is about 40 nanometers) and tin dioxide nanocrystal of one kind+4 valence tin ions doping are (average
Crystallite dimension is about 10 nanometers) effective compound electrochomeric films.
Optical modulation amplitude of the laminated film at 550nm wavelength is 56%, coloration efficiency 40, by the film through 10
After ten thousand discoloration cycles, negative and positive extreme current only declines 9%, and compared with pure nickel film, optical modulation amplitude increases
143%, coloration efficiency improves 60%, and service life cycle improves 150%.
Embodiment 4
A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline electrochomeric films, structure feature are：Tin dope oxygen
It is 30 nanometers to change nickel average grain size, and stannic oxide average grain size is 13 nanometers, and film thickness is 450 nanometers.
The preparation method of laminated film with the above structure feature, is as follows：
First, the complex sol of the element containing Ni and Sn is prepared.Technical process is as follows：
4.604 grams of nickel acetates are mixed with 30 milliliters of absolute methanols, clarification is stirred well at room temperature, adds 4 milliliters
Acrylic acid continues stirring 2 hours to get bottle green clear sol A.
2.270 grams of butters of tin are mixed with 4.358 grams of acetylacetone,2,4-pentanediones, and in 56 DEG C stir 15 minutes, then thereto
0.980 gram of acetic anhydride is added, and is stirred 15 minutes in 45 DEG C, is cooled to room temperature, is eventually adding 10 milliliters of ethyl alcohol, continues stirring 20
Minute is up to clear sol B.
Sol A and sol B are mixed 1 hour to get the complex sol C of the element containing Ni and Sn at room temperature.
Secondly, lifting prepares gel film.Technical process is as follows：
The colloidal sol of the element containing Sn-Ni is prepared into gel film, pull rate by dip-coating method on FTO electro-conductive glass
For 3.8mm/s, by the gel film substrate of lifting preparation, drying is taken out after ten minutes at 138 DEG C later, is air-cooled to room temperature.
Finally, prepared gel film substrate is heat-treated, technical process is as follows：
Gel film substrate is positioned in Muffle furnace and is heat-treated 10 minutes at 530 DEG C, is taken out.Aforesaid operations are repeated to obtain
To after certain thickness gel film, it is put under 530 DEG C of heat treatment temperatures and is heat-treated 90 minutes, be finally air-cooled to room temperature, obtain
The nickel oxide nano-crystal (average grain size is about 30 nanometers) and tin dioxide nanocrystal of one kind+4 valence tin ions doping are (average
Crystallite dimension is about 13 nanometers) effective compound electrochomeric films.
Optical modulation amplitude of the laminated film at 550nm wavelength is 57%, coloration efficiency 42cm2/ C is thin by this
For film after 100,000 discoloration cycles, negative and positive extreme current only declines 8%, compared with pure nickel film, optical modulation amplitude
Increase by 148%, coloration efficiency improves 68%, and service life cycle improves 155%.
Embodiment 5
A kind of tin dope nickel oxide-stannic oxide composite nanocrystalline electrochomeric films, structure feature are：Tin dope oxygen
It is 20 nanometers to change nickel average grain size, and stannic oxide average grain size is 15 nanometers, and film thickness is 500 nanometers.
The preparation method of laminated film with the above structure feature, is as follows：
First, the complex sol of the element containing Ni and Sn is prepared.Technical process is as follows：
4.604 grams of nickel acetates are mixed with 30 milliliters of absolute methanols, clarification is stirred well at room temperature, adds 4 milliliters
Acrylic acid continues stirring 2 hours to get bottle green clear sol A.
2.594 grams of butters of tin are mixed with 4.981 grams of acetylacetone,2,4-pentanediones, and in 60 DEG C stir 15 minutes, then thereto
1.121 grams of acetic anhydrides are added, and are stirred 15 minutes in 45 DEG C, is cooled to room temperature, is eventually adding 10 milliliters of ethyl alcohol, continues stirring 20
Minute is up to clear sol B.
Sol A and sol B are mixed 1 hour to get the complex sol C of the element containing Ni and Sn at room temperature.
Secondly, lifting prepares gel film.Technical process is as follows：
The colloidal sol of the element containing Sn-Ni is prepared into gel film, pull rate by dip-coating method on FTO electro-conductive glass
For 4.0mm/s, by the gel film substrate of lifting preparation, drying is taken out after ten minutes at 150 DEG C later, is air-cooled to room temperature.
Finally, prepared gel film substrate is heat-treated, technical process is as follows：
Gel film substrate is positioned in Muffle furnace and is heat-treated 10 minutes at 550 DEG C, is taken out.Aforesaid operations are repeated to obtain
To after certain thickness gel film, it is put under 550 DEG C of heat treatment temperatures and is heat-treated 90 minutes, be finally air-cooled to room temperature, obtain
The nickel oxide nano-crystal (average grain size is about 20 nanometers) and tin dioxide nanocrystal of one kind+4 valence tin ions doping are (average
Crystallite dimension is about 15 nanometers) effective compound electrochomeric films.
Optical modulation amplitude of the laminated film at 550nm wavelength is 62%, coloration efficiency 50cm2/ C is thin by this
For film after 100,000 discoloration cycles, negative and positive extreme current only declines 9%, compared with pure nickel film, optical modulation amplitude
Increase by 170%, coloration efficiency improves 100%, and service life cycle improves 150%.
Claims (5)
1. tin dope nickel oxide-stannic oxide composite nanocrystalline film, which is characterized in that tin dope nickel oxide-stannic oxide is multiple
Close the nickel oxide nano-crystal and the compound electrochromism of tin dioxide nanocrystal that nano-crystal film is one kind+4 valence tin ions doping
Film, tin dope nickel oxide average grain size are 20~60 nanometers, and stannic oxide average grain size is 5~15 nanometers, multiple
It is 300~500 nanometers to close nano-crystalline thin film thickness.
2. the preparation method of tin dope nickel oxide-stannic oxide composite nanocrystalline film, which is characterized in that be as follows：
Step 1, the complex sol C of the element containing Sn-Ni is prepared
Step 1.1, the Sol A of the element containing Ni is prepared：Its process for preparation is that nickel acetate is added in absolute methanol, at room temperature
It is stirred well to clarification, adds appropriate acrylic acid, continues stirring 2 hours, obtains bottle green clear sol A；
Step 1.2, the sol B of the element containing Sn is prepared：Its process for preparation is to mix butter of tin with acetylacetone,2,4-pentanedione, and in 45
DEG C~60 DEG C stir 15 minutes, be then added acetic anhydride thereto, and stir 15 minutes in 45 DEG C, be cooled to room temperature, finally plus
Enter ethanol in proper amount, continues stirring and obtain clear sol B in 20 minutes；
Step 1.3, Sol A and sol B are mixed at normal temperatures, stirs 1 hour to get clear answering containing Sn-Ni elements
Close colloidal sol C；
Step 2, lifting prepares gel film
The colloidal sol of the element containing Sn-Ni of acquisition is prepared into gel film by dip-coating method on FTO electro-conductive glass, and will be carried
It draws the drying at 100~150 DEG C of standby gel film substrate to take out after ten minutes, is air-cooled to room temperature；
Step 3, the gel film substrate in step 2 is positioned in Muffle furnace and is heat-treated 10 minutes at 450~550 DEG C, taken
Go out, after repeatedly step 2 and step 3 obtain certain thickness film, be heat-treated 90 minutes at a temperature of 450~550 DEG C, is taken out simultaneously
Room temperature is air-cooled to get tin dope nickel oxide-stannic oxide composite nanocrystalline film.
3. the preparation method of tin dope nickel oxide according to claim 2-stannic oxide composite nanocrystalline film, feature
Be, in step 1, butter of tin used, nickel acetate, acetylacetone,2,4-pentanedione, acrylic acid, acetic anhydride, absolute methanol, ethyl alcohol mole
Than being 0.25~0.4:1:1.68~2.69:3:0.37~0.59:40:9.
4. the preparation method of tin dope nickel oxide according to claim 2-stannic oxide composite nanocrystalline film, feature
It is, in step 2, lifting film uses Best-Effort request technology vertically evenly to be lifted out with the speed of 3.3mm/s~4.0mm/s
Colloidal sol liquid level.
5. the preparation method of tin dope nickel oxide according to claim 2-stannic oxide composite nanocrystalline film, feature
It is, in step 3, the tin dope nickel oxide-stannic oxide composite nanocrystalline film being prepared is that+4 valence tin ions of one kind are mixed
Miscellaneous nickel oxide nano-crystal and the compound electrochomeric films of tin dioxide nanocrystal, tin dope nickel oxide average grain size are
20~60 nanometers, stannic oxide average grain size is 5~15 nanometers, and composite nanocrystalline film thickness is 300~500 nanometers.
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