CN105382268B - The preparation method of the vanadium pentoxide nanowires of Ag doping, its preparation method and electrochromic device - Google Patents
The preparation method of the vanadium pentoxide nanowires of Ag doping, its preparation method and electrochromic device Download PDFInfo
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Abstract
The invention provides a kind of preparation method of the vanadium pentoxide nanowires of Ag doping, comprise the following steps：Vanadium source, template, water, nitric acid are mixed with silver nitrate, obtain mix precursor；The mix precursor is subjected to hydro-thermal reaction, obtains the vanadium pentoxide nanowires of Ag doping.Present invention also provides a kind of preparation method of electrochromic device, comprise the following steps：A the solution of Ag doping vanadium pentoxide nanowires) is plating to conductive glass surface, obtains to surface the electro-conductive glass for the vanadium pentoxide nanowires film for being coated with Ag doping；B) by step A) obtained electro-conductive glass and another electro-conductive glass bonded by band, then inject electrolyte between two electro-conductive glass, obtain electrochromic device.The application improves the electric conductivity and interlamellar spacing of vanadic anhydride by Ag doping, and forms the Ag doping vanadium pentoxide nanowires with high-aspect-ratio, therefore improves the electrochromic property of material.
Description
Technical field
The present invention relates to technical field prepared by inorganic material, more particularly to a kind of vanadic anhydride nanometer of Ag doping
The preparation method of line, its preparation method and electrochromic device.
Background technology
Electrochromism is in the presence of extra electric field, and ion or electronics in material are extracted or injected, and make electroluminescent change
Reversible change occurs for color material oxidation state, so as to the optical property such as reflectivity, light transmittance and color of material occur therewith it is reversible
Change.Electrochromic material is divided into organic electrochromic material and inorganic electrochromic material, inorganic electrochromic material due to
Have the advantages that chemical stability is good and preparation technology is simple, be constantly subjected to the pro-gaze of researcher for a long time.At present research compared with
More inorganic electrochromic materials mainly includes WO3、Nb2O5And V2O5Deng transition metal oxide.In view of inorganic electrochromic material
Material can modulation optical property, electrochromic material is assembled into electrochromic device has great application value, at present
The electrochromic device being widely used includes smart window, advanced display, non-glare rearview mirror of automobile, vehicle dormer window and traffic letter
Signal lamp etc..
In the transition metal oxide with electrochromism function, vanadic anhydride has double staining characteristic, that is, exists
Negative electrode and anode can colour；The vanadium pentoxide nanowires of one-dimentional structure have special physico-chemical property simultaneously, such as：Compare table
Area is big, adsorption capacity is strong, ion implanting and extracted amount is larger and lithium ion storage density is high.Above-mentioned physico-chemical property is advantageous to
The electrical property of vanadic anhydride is improved, it is had wider application in electrochromism field.
At present, the preparation method of vanadium pentoxide nanowires mainly has electrodeposition process, sol-gel process and hydro-thermal method etc.,
Wherein hydro-thermal method is the most ripe.Hydro-thermal method prepare vanadium pentoxide nanowires vanadium source include ammonium metavanadate, vanadic anhydride or
Hypovanadic oxide powder.The method for preparing vanadic anhydride is a lot, such as：Publication No. CN102826603A Chinese patent uses
Hypovanadic oxide powder is vanadium source, and hydro-thermal reaction obtains vanadium pentoxide nanowires in aqueous solution of nitric acid, is about 10~60 μm, directly
Footpath is 10~50nm, but its hydrothermal temperature is 140~250 DEG C, and temperature is higher；Publication No. CN103966638A China is specially
Profit discloses a kind of method for preparing vanadium pentoxide nanowires, and it is existed using colloidal crystal as template by the method for electro-deposition
Deposited in template, obtain vanadium pentoxide nanowires with good conductivity；Publication No. CN103351027A Chinese patent
Disclose a kind of method for preparing vanadic anhydride, its using P123 as template direction agent, prepared by air anneal be about~
20 μm, a diameter of 50~100nm vanadium pentoxide nanowires；Publication No. CN103208619A Chinese patent proposition, will
Vanadic anhydride powder is dissolved in potassium hydroxide aqueous solution, and having obtained vanadic anhydride after hydro-thermal and Muffle furnace heat treatment receives
Rice noodles.
The above method prepare vanadium pentoxide nanowires length-width ratio it is small, electric conductivity is poor, layer structure is easily caved in
Defect, its electrochromic property is had a strong impact on.
The content of the invention
Present invention solves the technical problem that it is the vanadic anhydride that a kind of preferable Ag doping of electrochromic property is provided
The preparation method of nano wire.
In view of this, this application provides a kind of preparation method of the vanadium pentoxide nanowires of Ag doping, including it is following
Step：
Vanadium source, template, water, nitric acid are mixed with silver nitrate, obtain mix precursor；
The mix precursor is subjected to hydro-thermal reaction, obtains the vanadium pentoxide nanowires of Ag doping.
Preferably, also include after the hydro-thermal reaction：
Product after hydro-thermal reaction is washed and dried successively.
Preferably, the vanadium source is ammonium metavanadate, and the template is selected from EO20PO70EO20、EO18PO58EO18、
EO106PO70EO106、EO11PO70EO11、EO42PO16EO42, one or more in ethylene glycol and glycerine.
Preferably, the preparation of the mix precursor is specially：
Vanadium source and template are dissolved in distilled water, add nitric acid, is eventually adding silver nitrate.
Preferably, content of the vanadium source in water is 5~20g/L；Content of the template in water be 10~
30g/L；The concentration of the nitric acid is 0.5~3mol/L；The silver nitrate and the mass ratio in vanadium source are (0.05~0.5)：1.
Preferably, described wash is specially：
By the product after hydro-thermal reaction using being cleaned again using ethanol or acetone after deionized water cleaning, repeat 3~5 times.
Present invention also provides the vanadium pentoxide nanowires of the Ag doping prepared by the preparation method described in such scheme.
Preferably, the length of the vanadium pentoxide nanowires of the Ag doping is~50 μm, a diameter of 5~30nm, silver
Grain size is 1~8nm.
Present invention also provides a kind of preparation method of electrochromic device, comprise the following steps：
A), the Ag doping vanadic anhydride described in prepared by the preparation method described in such scheme or such scheme is received
The solution of rice noodles is plating to conductive glass surface, obtains to surface the conductive glass for the vanadium pentoxide nanowires film for being coated with Ag doping
Glass；
B), by step A) the obtained surface of the vanadium pentoxide nanowires film for being coated with Ag doping of electro-conductive glass with it is another
The surface of one electro-conductive glass conductive coating is relative, and is bonded by band, then electric to being injected between two electro-conductive glass
Xie Zhi, obtain electrochromic device.
Preferably, the electro-conductive glass is ito glass, FTO glass or TCO glass.
This application provides a kind of preparation method of the vanadium pentoxide nanowires of Ag doping, it is first by vanadium source, template
Agent, water, nitric acid are mixed with silver nitrate, and obtained mix precursor then is carried out into hydro-thermal reaction, that is, obtains Ag doping
Vanadium pentoxide nanowires.During the vanadium pentoxide nanowires of Ag doping are prepared, in hydro-thermal reaction, silver nitrate
Being reduced to obtain silver by template, vanadium source decomposes to obtain vanadic anhydride, simultaneously because the presence of template, therefore obtained silver and mixed
Miscellaneous stratiform vanadium pentoxide nanowires.
Because vanadic anhydride has layer structure, after silver-doped Nano silver grain can be made to enter interlayer and play branch
Support acts on, and increases the interlamellar spacing of vanadic anhydride, improves the stability of structure；Simultaneously because silver has good conduction
Property, the electric conductivity of vanadic anhydride can be improved, therefore, the vanadium pentoxide nanowires of Ag doping prepared by the application are as electroluminescent
The electrochromic layer of Electrochromic device, the defects of small poorly conductive of vanadic anhydride, interlamellar spacing and structural instability can be improved,
Improve its electrochromic property.
Brief description of the drawings
Fig. 1 is the SEM figures of Ag doping vanadium pentoxide nanowires prepared by the embodiment of the present invention 1；
Fig. 2 is the Ag doping vanadium pentoxide nanowires of vanadium pentoxide nanowires and the preparation of embodiment 1 undoped with silver
TEM figure, bottom right insertion figure be its HRTEM figure；
Fig. 3 is the vanadic anhydride nanometer of the Ag doping of vanadium pentoxide nanowires and the preparation of embodiment 1 undoped with silver
Line color change figure before and after colour fading；
Fig. 4 is the response time figure of Ag doping vanadium pentoxide nanowires base film prepared by embodiment 1；
Fig. 5 is the CV figures of Ag doping vanadium pentoxide nanowires base film prepared by embodiment 1；
Fig. 6 is the electrochromic device illustraton of model based on the assembling of Ag doping vanadium pentoxide nanowires.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of the vanadium pentoxide nanowires of Ag doping, including following step
Suddenly：
Vanadium source, template, water, nitric acid are mixed with silver nitrate, obtain mix precursor；
The mix precursor is subjected to hydro-thermal reaction, obtains the vanadium pentoxide nanowires of Ag doping.
The application is made by improving the electric conductivity and interlamellar spacing of vanadic anhydride in stratiform vanadic anhydride silver-doped
The standby vanadium pentoxide nanowires into the Ag doping with high-aspect-ratio, improve the electrochromic property of material.
According to the present invention, vanadium source, template, water, nitric acid are mixed with silver nitrate first, obtain mix precursor.For
Raw material is well mixed, and raw material prematurely reacts, the preparation of the mix precursor is specially：
Vanadium source and template are dissolved in distilled water, add nitric acid, silver nitrate is added after stirring and is further continued for stirring, is obtained
Mix precursor.
In above process, the vanadium source is preferably ammonium metavanadate, and the template is preferably selected from P123
(EO20PO70EO20)、P104(EO18PO58EO18)、F127(EO106PO70EO106)、L122(EO11PO70EO11)、F38
(EO42PO16EO42), the one or more in ethylene glycol and glycerine.The solution of distilled water formation is dissolved in vanadium source and template
In, content of the vanadium source in water is preferably 5~20g/L, and content of the template in water is preferably 10~30g/L.
For the nitric acid to adjust the pH value of solution, the concentration of the nitric acid is preferably 0.5~3mol/L, add nitric acid after stir when
Between be preferably 2~48h.Herein described silver nitrate and the mass ratio in the vanadium source are preferably (0.05~0.5)：1, in some realities
Apply in example, the mass ratio in the silver nitrate and the vanadium source is preferably (0.1~0.3)：1.
Then the mix precursor is carried out hydro-thermal reaction by the application, obtain the vanadic anhydride nanometer of Ag doping
Line.The present invention also includes after hydro-thermal reaction：
Product after hydro-thermal reaction is washed, dried.
In said process, the washing is in order to by template washes clean.The washing is specially：The product is adopted
Cleaned, repeated 3~5 times using ethanol or acetone again after being cleaned with distilled water.The temperature of the drying is preferably 60 DEG C~120
℃.Product after hydro-thermal reaction can just obtain the vanadium pentoxide nanowires of pure Ag doping after washing and drying.
In herein described hydrothermal reaction process, silver nitrate is reduced to obtain silver by template, and the vanadium source is in thermal and hydric environment
Middle decomposition obtains vanadic anhydride, due to the presence of template, therefore forms the nano wire of stratiform, and Ag doping is in five oxidations
In the layer structure of two vanadium nano wires.The temperature of herein described hydro-thermal reaction is preferably 100~170 DEG C, the hydro-thermal reaction
Time be preferably 12~72h.
The application such scheme prepare Ag doping vanadium pentoxide nanowires length it is reachable~50 μm, a diameter of 5
~30nm, silver nano-grain size are 1~8nm, Ag and V2O5Mass ratio be (0.01~0.3)：1.
The application prepare Ag doping vanadium pentoxide nanowires can as the electrochromic material of electrochromic device,
Thus, the invention provides a kind of preparation method of electrochromic device, comprise the following steps：
A), the solution of the Ag doping vanadium pentoxide nanowires described in prepared by such scheme or such scheme is plating to
Conductive glass surface, the electro-conductive glass for the vanadium pentoxide nanowires film for being coated with Ag doping is obtained to surface；
B), by step A) the obtained surface of the vanadium pentoxide nanowires film for being coated with Ag doping of electro-conductive glass with it is another
The surface of one electro-conductive glass conductive coating is relative, and is bonded by band, then electric to being injected between two electro-conductive glass
Xie Zhi, obtain electrochromic device.
During electrochromic device is prepared, the application first plates the surface of electro-conductive glass five oxygen of Ag doping
Change two vanadium nano wires, this process specifically includes following steps：
The vanadium pentoxide nanowires of Ag doping are scattered in solvent, obtained solution is concentrated；
The vanadic anhydride solution of Ag doping after concentration is spin-coated on conductive glass surface, carries out spin coating after drying again,
The number of spin coating is repeated, obtains being coated with the electro-conductive glass of the vanadium pentoxide nanowires of Ag doping.
In above process, the solvent is preferably ethanol, the vanadium pentoxide nanowires of the Ag doping and ethanol
Mass ratio is preferably (0.01~0.05)：1.The concentration, which specifically uses, to be exposed the solution in air, and long agitation
What mode was carried out.The content of the vanadium pentoxide nanowires of Ag doping in the solution is 0.2~2g/ml after concentration.This Shen
Please the electro-conductive glass be preferably ito glass, FTO glass or TCO glass.The electro-conductive glass is revolved again after over cleaning
Apply, the ultrasonic cleaning repeatedly including distilled water, ethanol, the acetone the step of cleaning.The temperature of the drying is preferably 60~
100 DEG C, the time of the drying is preferably 10~30min.
Conductive glass surface be coated with Ag doping vanadium pentoxide nanowires prepare after, the application then by its with it is another
Electro-conductive glass is bonded by band, is then injected electrolyte between two electro-conductive glass, is obtained electrochromic device.Above-mentioned mistake
Cheng Zhong, it should be noted that two pieces of electro-conductive glass should make the electrochromic layer and conduction of electro-conductive glass during bonding
The conductive layer of glass is relative.Because the band has certain width, therefore gap be present between two electro-conductive glass, can be to
Electrolyte is injected between two electro-conductive glass.Herein described band is preferably silica gel, and the width of the silica gel is preferably 1~
3mm.The electrolyte is well known to those skilled in the art, and the application is preferably LiClO4/PC.Herein described electrochromism
The structural representation of device is as shown in fig. 6,1 be glass in Fig. 6,2 be ITO layer, and 3 is thin for the vanadium pentoxide nanowires of Ag doping
Film, 4 be electrolyte, and 5 be band.
The application is prepared for the vanadium pentoxide nanowires of Ag doping using hydrothermal synthesis method.Because vanadic anhydride has
Layer structure, silver-doped can make Nano silver grain enter interlayer, play a supporting role, increase interlamellar spacing, improve structure
Stability, while silver has good electric conductivity, can improve the electric conductivity of vanadic anhydride, which thereby enhance five oxygen of Ag doping
Change the electrochromic property of two vanadium.The application prepare Ag doping vanadium pentoxide nanowires length it is reachable~50 μm, a diameter of 5
~30nm, silver nano-grain are 1~8nm, Ag and V2O5Mass ratio be (0.01~0.3)：1.By the vanadic anhydride of Ag doping
Nano wire is assembled into electrochromic device, studies its electrochromic property, as a result shows：Lithium ion diffusion rate can reach~
10-9cm2s-1；Response time can reach 0.2/0.1s (coloring/colour fading).
For a further understanding of the present invention, the vanadic anhydride of Ag doping provided by the invention is received with reference to embodiment
Rice noodles are described in detail with electrochromic device, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
0.3g ammonium metavanadates and 0.5g P123 are dissolved in 30ml distilled water, 2ml1mol/L nitric acid is added, is stirred under normal temperature
7h is mixed, 0.1g silver nitrates are added into above-mentioned solution, continues to stir 1h.Obtained precursor solution is transferred to 50ml crystallizing kettles
In, the hydro-thermal reaction 24h at 120 DEG C, treat that crystallizing kettle naturally cools to room temperature, product is taken out into filtering and with distilled water and ethanol
Washing, in triplicate, until P123 is cleaned completely, finally washed product is dried overnight at 80 DEG C, obtains the five of Ag doping
V 2 O nano wire.
Fig. 1 is the SEM photograph of the vanadium pentoxide nanowires of Ag doping manufactured in the present embodiment, and Fig. 2 is undoped with silver
The TEM figures of Ag doping vanadium pentoxide nanowires prepared by vanadium pentoxide nanowires and embodiment 1, bottom right insertion figure is it
HRTEM schemes；Fig. 2 a are the TEM figures of the Ag doping vanadium pentoxide nanowires of embodiment 1, and bottom right insertion figure is its HRTEM figures；Figure
2b is the TEM figures undoped with vanadium pentoxide nanowires, and bottom right insertion figure is its HRTEM figures；As shown in Figure 2, vanadic anhydride
After silver-doped, interlamellar spacing significantly increases nano wire.Fig. 3 is vanadium pentoxide nanowires and embodiment 1 undoped with silver
The vanadium pentoxide nanowires of the Ag doping of preparation color change figure before and after colour fading；It can be seen from Fig. 3, five oxidations of Ag doping
Two vanadium nano wires colour fading performance be substantially better than undoped with vanadium pentoxide nanowires.
The 0.25g vanadium pentoxide nanowires of Ag doping prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.Fig. 4 is that silver prepared by embodiment 1 is mixed
The response time figure of miscellaneous vanadium pentoxide nanowires base film；As seen from the figure, the vanadic anhydride basement membrane of Ag doping discoloration
Performance sensitive.Fig. 5 is the CV curve maps of Ag doping vanadium pentoxide nanowires base film prepared by embodiment 1；According to CV curves
Lithium ion diffusion rate can be calculated, speed is faster, shows that electrochromic property is better.
Embodiment 2
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g P123 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.2g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until P123 is cleaned completely, finally stayed overnight washed product at 80 DEG C
Dry, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C,
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 3
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g P123 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.3g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until P123 is cleaned completely, finally stayed overnight washed product at 80 DEG C
Dry, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 4
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g P123 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.1g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 150 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until P123 is cleaned completely, finally stayed overnight washed product at 80 DEG C
It is dried to obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 5
According to the scheme of embodiment 1,0.5g ammonium metavanadates and 0.5g P123 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.1g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until P123 is cleaned completely, finally stayed overnight washed product at 80 DEG C
Dry, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 6
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g P123 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.1g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 48h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until P123 is cleaned completely, finally stayed overnight washed product at 80 DEG C
Dry, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 7
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g P104 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 12h is stirred under normal temperature, then 0.1g silver nitrates are added into above-mentioned solution, continue to stir 2h；The forerunner that will be obtained
Liquid solution is transferred in the brilliant magnificent kettles of 50ml, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken
Go out to filter and washed repeatedly with distilled water and ethanol, in triplicate, until P104 is cleaned completely, finally by washed product at 80 DEG C
Under be dried overnight, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 8
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g F127 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 12h is stirred under normal temperature, then 0.1g silver nitrates are added into above-mentioned solution, continue to stir 2h；The forerunner that will be obtained
Liquid solution is transferred in the brilliant magnificent kettles of 50ml, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken
Go out to filter and washed repeatedly with distilled water and ethanol, in triplicate, until F127 is cleaned completely, finally by washed product at 80 DEG C
Under be dried overnight, obtain the vanadium pentoxide nanowires of Ag doping.
0.25g vanadium pentoxide nanowires prepared by such scheme are dispersed in 20ml ethanol, are stirred vigorously at room temperature
Until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；Take again another
Block ito glass, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M LiClO thereto4/ PC is electrolysed
It is upright to arrive all air whole emptyings, obtain electrochromic device.
Embodiment 9
According to the scheme of embodiment 4,0.3g ammonium metavanadates and 0.5g L122 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 12h is stirred under normal temperature, then 0.1g silver nitrates are added into above-mentioned solution, continue to stir 2h；The forerunner that will be obtained
Liquid solution is transferred in the brilliant magnificent kettles of 50ml, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken
Go out to filter and washed repeatedly with distilled water and ethanol, in triplicate, until L122 is cleaned completely, finally by washed product at 80 DEG C
Under be dried overnight, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/ PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 10
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g F38 are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.1g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until F38 is cleaned completely, finally stayed overnight washed product at 80 DEG C
Dry, obtain the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
Embodiment 11
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g ethylene glycol are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.1g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until ethylene glycol completely clean, finally by washed product at 80 DEG C mistake
Night is dried, and obtains the vanadium pentoxide nanowires of Ag doping.
0.25g vanadium pentoxide nanowires prepared by such scheme are dispersed in 20ml ethanol, are stirred vigorously at room temperature
Until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；Take again another
Block ito glass, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M LiClO thereto4/ PC is electrolysed
It is upright to arrive all air whole emptyings, obtain electrochromic device.
Embodiment 12
According to the scheme of embodiment 1,0.3g ammonium metavanadates and 0.5g glycerine are dissolved in 30ml distilled water, add 2ml
1mol/L nitric acid, 7h is stirred under normal temperature, 0.1g silver nitrates are added into above-mentioned solution, continue to stir 1h；The presoma that will be obtained
Solution is transferred in 50ml crystallizing kettles, the hydro-thermal reaction 24h at 120 DEG C, treats that crystallizing kettle naturally cools to room temperature, product is taken out
Filter and washed with distilled water and ethanol, in triplicate, until glycerine completely clean, finally by washed product at 80 DEG C mistake
Night is dried, and obtains the vanadium pentoxide nanowires of Ag doping.
The vanadium pentoxide nanowires of 0.25g Ag dopings prepared by such scheme are dispersed in 20ml ethanol, at room temperature
It is stirred vigorously until liquor capacity is concentrated to 5ml, gained suspension is spun on ito glass and 10min is dried at 80 DEG C；
Take another piece of ito glass again, with band thick 1mm by two pieces of glassy bonds together, finally inject 1M's thereto
LiClO4/PC electrolyte is until by all air whole emptyings, obtaining electrochromic device.
The performance data table of the vanadium pentoxide nanowires of Ag doping prepared by the embodiment 1~12 of table 1
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (8)
1. a kind of preparation method of the vanadium pentoxide nanowires of Ag doping, comprises the following steps：
Vanadium source and template are dissolved in distilled water, add nitric acid, is eventually adding silver nitrate, obtains mix precursor；Institute
It is 5~20g/L to state content of the vanadium source in water；Content of the template in water is 10~30g/L；The concentration of the nitric acid
For 0.5~3mol/L；The silver nitrate and the mass ratio in vanadium source are (0.05~0.5)：1；The template is selected from
EO20PO70EO20、EO18PO58EO18、EO106PO70EO106、EO11PO70EO11And EO42PO16EO42In one or more；
The mix precursor is subjected to hydro-thermal reaction, obtains the vanadium pentoxide nanowires of Ag doping.
2. preparation method according to claim 1, it is characterised in that also include after the hydro-thermal reaction：
Product after hydro-thermal reaction is washed and dried successively.
3. preparation method according to claim 1 or 2, it is characterised in that the vanadium source is ammonium metavanadate.
4. preparation method according to claim 2, the washing are specially：
By the product after hydro-thermal reaction using being cleaned again using ethanol or acetone after deionized water cleaning, repeat 3~5 times.
5. the vanadium pentoxide nanowires of the Ag doping prepared by preparation method described in any one of Claims 1 to 4.
6. the vanadium pentoxide nanowires of Ag doping according to claim 5, it is characterised in that five oxygen of the Ag doping
The length for changing two vanadium nano wires is~50 μm, a diameter of 5~30nm, and Argent grain size is 1~8nm.
7. a kind of preparation method of electrochromic device, comprises the following steps：
A), by prepared by the preparation method described in any one of Claims 1 to 4 or any one of claim 5~6 described in silver
The solution of doping vanadium pentoxide nanowires is plating to conductive glass surface, obtains to surface and is coated with the vanadic anhydride nanometer of Ag doping
The electro-conductive glass of line film；
B), by step A) the obtained surface of the vanadium pentoxide nanowires film for being coated with Ag doping of electro-conductive glass leads with another
The surface of electric glass conductive coating is relative, and is bonded by band, then injects electrolyte between two electro-conductive glass,
Obtain electrochromic device.
8. preparation method according to claim 7, it is characterised in that the electro-conductive glass be ito glass, FTO glass or
TCO glass.
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