CN117660881A - Electrochromic film with neutral coloring and preparation method and application thereof - Google Patents
Electrochromic film with neutral coloring and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electrochromic film with neutral coloring, and a preparation method and application thereof. The preparation method comprises the following steps: providing a W-Nb-O electrochromic material comprising Nb 2 O 5 And WO 3 Wherein Nb is 2 O 5 The content of (2) is 30-70 wt%; the W-Nb-O electrochromic film with neutral coloring is prepared by adopting a magnetron sputtering technology and combining a high-temperature thermal annealing technology which is optionally performed. The book is provided withThe W-Nb-O electrochromic film prepared by the invention has good optical modulation amplitude, circulation stability, excellent coloring neutral color and electrochromic performance, and can meet better application prospect in neutral electrochromic devices.
Description
Technical Field
The invention belongs to the technical field of electrochromic devices and applications, relates to an electrochromic material and a preparation method thereof, and particularly relates to an electrochromic film with neutral coloring, and a preparation method and application thereof.
Background
Electrochromic devices (ECD) will present great potential for use in the energy saving field of buildings, where the light radiation entering the interior of the building can be dynamically modulated by applying a voltage of 1 to 3V, which can reduce the energy consumption generated by the existing Heating Ventilation Air Conditioning (HVAC) of the interior of the building, thereby helping to reduce the emission of greenhouse gases. In general, a typical ECD includes a top transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and a bottom transparent conductive layer, where the electrochromic layer is the most critical one that determines not only the light modulation amplitude, cycle life, and response time, but also the coloration color and infrared blocking efficiency. The main classes of electrochromic substances to date are transition metal oxides (e.g. tungsten oxide), soluble small organic molecule compounds (e.g. viologen), conductive polymers (e.g. polyaniline) and complex coordination compounds (e.g. Prussian blue). These materials all exhibit a more pronounced deep blue color in their colored state, but, from the standpoint of architectural aesthetics and architectural occupant comfort, there are a number of adverse effects, for example, a lower Color Rendering Index (CRI) of the glazing in the blue state, which may be below 10, is generally unacceptable (in contrast, the CRI of gray or neutral colored glazings can exceed 90). Electrochromic devices that seek neutral colors, particularly in the colored state, have gained increased attention.
Tungsten oxide is used as a mainstream electrochromic material, has a larger light modulation range, higher coloring efficiency and superior environmental stability,has been used for over 50 years, but the blue color exhibited by the colored state of tungsten oxide (chromaticity values b-20 to-40) further limits the diverse applications of this material in different fields. To solve this problem, rvizu et al (chem. Mater.2017, 29, 2246-2253.) propose the use of reactive magnetron sputtering in WO 3 Co-doped MoO 3 And TiO 2 To achieve neutral color, a 300nm thick Mo and Ti co-doped film was found to have a color state chromaticity value of a=0.6 and b=3.7, which lies in the neutral color range of the CIE 1931 chromaticity diagram, but has relatively poor electrochemical cycling stability, and the light modulation amplitude and the color efficiency of the film were reduced by 50% for only 10 electrochemical cycles. Rougier et al (Electrochim. Acta.2001, 46, 1945-1950;Sol.Energy Mater Sol.Cells.2002, 71, 343-357.) prepared V-doped WO using a sol-gel method 3 A film in which the 10at.% doped system exhibits a neutral color in the colored state, the chromaticity parameter being b = -7.6, but the optical modulation amplitude is lower (T b /T t =1.6); rougier also proposed a doped tungsten oxide film containing 20wt.% niobium that exhibited a weakly neutral color (b = -13.9), but the electrochromic cycling performance was relatively poor (T b /T t =1.7, optical, electrical properties decay severely after 80 cycles). WO 2-20% Mo, nb or V doped by reactive magnetron sputtering is disclosed by the company SAGE Electrochromics in the U.S. patent No. 2023/0077782A1 3 The absolute value |b| of the chromaticity value b| of the single-layer film of the system is between 6 and 35, and finally the neutral color of the whole device is realized by means of the coloring efficiency matching of the nickel oxide ion storage layer.
Overall, the above-described work on electrochromic materials based on neutral coloured tungsten oxide systems also presents the following problems:
(1) Neutral coloration of the monolayer films is still inadequate, most of the absolute values of b, i.e., |b| are typically between 6 and 35, whereas neutral color requires |b| 5, so the results reported in the prior art do not ensure achievement of this goal;
(2) The electrochromic property of the neutral coloring film sample is relatively poor, the modulation amplitude is low, and the cycle stability is poor;
(3) In the preparation method, the reactive sputtering or sol-gel mode of the metal target is mainly adopted, the reactive sputtering deposition efficiency of the metal target is relatively low, and the surface of the target is easy to be poisoned due to the fact that a large amount of oxygen is introduced in the sputtering process, so that the quality of the coating film is influenced. In addition, sol-gel is difficult to achieve deposition of large area, high quality films.
Therefore, there is an urgent need to find an electrochromic material based on a tungsten oxide system, which has both a neutral color in a colored state and excellent electrochromic properties, and a preparation method thereof with large area and high quality.
Disclosure of Invention
The invention mainly aims to provide an electrochromic film with neutral coloring, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an electrochromic film with neutral coloring, which comprises the following steps:
providing a W-Nb-O electrochromic material comprising Nb 2 O 5 And WO 3 Wherein Nb is 2 O 5 The content of (2) is 30-70 wt%;
and preparing the W-Nb-O electrochromic material into an electrochromic film with neutral coloring by adopting a magnetron sputtering technology and combining a high-temperature thermal annealing technology which is optionally performed.
In some embodiments, the preparation method specifically includes:
pressing the W-Nb-O electrochromic material into a blank, and sintering to obtain the Nb-doped WO to be sputtered 3 A ceramic target;
doping WO with Nb 3 Taking ceramic as a target material, taking a substrate deposited with a transparent conductive layer as a matrix, and adopting a magnetron sputtering technology to deposit and form a film on the substrate deposited with the transparent conductive layer;
Annealing the film deposited by magnetron sputtering to obtain the electrochromic film with neutral coloring.
The embodiment of the invention also provides the electrochromic film with neutral coloring prepared by the method.
Further, the electrochromic film is neutral black in a coloring state, and b is less than or equal to 5.
The embodiment of the invention also provides application of the electrochromic film with neutral coloring in preparation of a neutral electrochromic device.
Compared with the prior art, the invention has the advantages that:
1) The invention provides an electrochromic material based on a tungsten oxide system and having both neutral coloring state and high cycle stability, and a preparation method thereof with large area and high quality, wherein the prepared W-Nb-O electrochromic material has better optical modulation amplitude, cycle stability, excellent neutral coloring state and electrochromic performance, and can meet better application prospect in neutral electrochromic devices;
2) The sputtering method provided by the invention adopts the oxide ceramic target material to replace the traditional metal target material for reactive sputtering, avoids the introduction of oxygen in the sputtering process, further improves the sputtering stability, the coating quality and the coating speed, and is suitable for rapid deposition of large-area high-quality films.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIGS. 1a and 1b are a colored state transmittance chart and an appearance chart, respectively, of a comparative example;
FIG. 2 is an XRD pattern of the film of example 1 of the present invention and of the film sample of example 2;
FIGS. 3a and 3b are XPS patterns of a colored film prepared in example 1 of the present invention, respectively;
FIGS. 4a and 4b are TEM sectional morphology diagrams of the prepared film of the present example 1 and the prepared film of the example 2, respectively;
FIGS. 5a and 5b are optical transmittance spectra before and after cycling of the niobium-doped tungsten oxide electrochromic film prepared in example 1 and the niobium-doped tungsten oxide film prepared in example 2, respectively;
FIGS. 6a and 6b are graphs showing light modulation changes at 550nm for the thin film prepared in example 1 and the thin film prepared in example 2, respectively;
fig. 7a and 7b are a colored state transmittance chart and an external appearance chart, respectively, of the film prepared in example 1.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long-term research and a great deal of practice, and has proposed the technical scheme of the present invention, which mainly provides an electrochromic material based on a tungsten oxide system with both neutral color in a colored state and high cycle stability, and a preparation method thereof with large area and high quality. The technical scheme, the implementation process, the principle and the like are further explained as follows.
One aspect of the embodiment of the invention provides a method for preparing an electrochromic film with neutral coloring, which comprises the following steps:
providing a W-Nb-O electrochromic material comprising Nb 2 O 5 And WO 3 Wherein Nb is 2 O 5 The content of (2) is 30-70 wt%;
and preparing the W-Nb-O electrochromic material into an electrochromic film with neutral coloring by adopting a magnetron sputtering and high temperature thermal annealing technology.
The specific operation steps of the high-temperature thermal annealing technology are that a W-Nb-O electrochromic film prepared by magnetron sputtering is put into a rapid thermal annealing furnace, heating temperature, heating time and heating rate are set, and the W-Nb-O electrochromic film with neutral coloring is prepared after the furnace is cooled to room temperature.
Further, the present invention may not perform the step of high temperature thermal annealing.
In some embodiments, the present invention provides a composition having neutral colorationIs Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) The mass ratio of the W-Nb-O material is 30-70 wt%.
In some embodiments, the method of making comprises:
pressing the W-Nb-O electrochromic material into a blank, and sintering to obtain the Nb-doped WO to be sputtered 3 A ceramic target;
doping WO with Nb 3 Taking ceramic as a target material, taking a substrate deposited with a transparent conductive layer as a matrix, and adopting a magnetron sputtering technology to deposit and form a film on the substrate deposited with the transparent conductive layer;
annealing the film deposited by magnetron sputtering to obtain the electrochromic film with neutral coloring.
In a more preferred embodiment, the Nb to be sputtered is doped with WO 3 The preparation method of the ceramic target material specifically comprises the following steps: nb is set to 2 O 5 And WO 3 Mixing the powder with water (such as deionized water), ball milling to obtain mixed powder, pressing the mixed powder into blank under 70-150 MPa, and sintering to obtain Nb-doped WO 3 The ceramic target material has the temperature rising rate of 3-5 ℃/min, the sintering temperature of 1200-1350 ℃ and the heat preservation time of 2-6 h.
Further, the water and Nb 2 O 5 And WO 3 The mass ratio of the combination of the powder is 2-3:1.
Further, the ball milling time is 4-10 hours.
In a more preferred embodiment, the preparation method specifically comprises: placing a substrate deposited with a transparent conductive layer into a magnetron sputtering coating cavity by adopting a magnetron sputtering technology, and doping WO with Nb 3 The ceramic target is used as a target, inert gas is used as working gas, a radio frequency or medium frequency sputtering method is adopted to deposit and form a film on the substrate deposited with the transparent conductive layer, wherein the background vacuum degree of the magnetron sputtering coating cavity is 5 multiplied by 10 -2 ～5×10 -4 Pa, the working air pressure is 0.6-2.0 Pa, and the sputtering power is 100-250W.
Further, the thickness of the thin film is 200 to 500nm according to the difference of sputtering time.
Further, the substrate on which the transparent conductive layer is deposited includes any one of an ITO glass substrate, an FTO glass substrate, and the like.
Further, the inert gas includes Ar, but is not limited thereto.
In some embodiments, the process parameters of the annealing treatment include: the annealing temperature is 300-500 ℃, the heat preservation time is 1-15 min, the heating rate is 5-20 ℃/s, and the cooling rate is 0.5-2 ℃/s. The invention adopts high temperature thermal annealing, which can lead the electrochromic material to have better electrochromic performance.
The preparation method of the electrochromic film based on the tungsten oxide system, which is provided by the invention and has the advantages of both neutral color in a coloring state and high cycle stability, can be used for preparing the electrochromic film with large area and high quality, and specifically comprises the following steps:
(1) Nb-doped WO 3 Preparing a ceramic target:
according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) The ratio of =30 to 70wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the mass of 2-3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4-10 h to fully mix the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, compacting the powder into a green body under 70-150 MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3-5 ℃/min, the sintering temperature is 1200-1350 ℃, the heat preservation time is 2-6 h, and taking out the ceramic target after the annealing furnace temperature is reduced to normal temperature;
(2) Nb-doped WO 3 Magnetron sputtering coating of ceramic targets:
the substrate (such as ITO glass substrate, FTO glass substrate, etc.) deposited with the transparent conductive layer is placed in a magnetron sputtering coating film by adopting a magnetron sputtering technology In the cavity, sintered niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) 30-70 wt.%) ceramic body is used as target material and placed in a magnetron sputtering cavity for coating, inert gas Ar is used as working gas, and a radio frequency or intermediate frequency sputtering means is adopted, wherein in the sputtering process, the background vacuum degree of the coating cavity is 5 multiplied by 10 -2 ～5×10 -4 Pa, the working air pressure value is 0.6-2.0 Pa, the sputtering power is 100-250W, the substrate is unintentionally heated, and the film is formed by the difference of sputtering timeThickness is as follows200～500nm。
(3) Post-annealing of deposited films
And (3) placing the film sample deposited by magnetron sputtering in an annealing furnace for annealing treatment, wherein the annealing temperature is 300-500 ℃, the heat preservation time is 1-15 min, the heating rate is 5-20 ℃/s, and the cooling rate is 0.5-2 ℃/s.
In summary, the method for preparing the electrochromic material by combining magnetron sputtering with high-temperature thermal annealing adopts the oxide ceramic target to replace the traditional metal target reactive sputtering, avoids the introduction of oxygen in the sputtering process, further improves the sputtering stability, the coating quality and the coating speed, and is suitable for rapid deposition of large-area and high-quality films.
Another aspect of an embodiment of the present invention also provides an electrochromic film with neutral coloring prepared by the aforementioned preparation method.
Further, the electrochromic film has a better colored neutral color. The concrete steps are as follows: the electrochromic film prepared by the invention presents more excellent neutral black in a coloring state, namely |b|is less than or equal to 5, which is far less than that of the traditional WO 3 The coloration state (-20 to-40) of the material is smaller than the value reported in the prior art for tungsten oxide films with a coloration neutral state (6-35).
Further, the electrochromic film has excellent electrochromic property. The concrete steps are as follows: the film sample has larger modulation amplitude (up to 70%) at 550nm optical wavelength, and the film still has higher cycling stability after 2000 electrochemical cycling tests, especially has higher retention rate (up to 97%) of modulation amplitude.
Another aspect of an embodiment of the present invention also provides an application of the electrochromic film with neutral coloring in preparing a neutral electrochromic device (preferably an electrochromic smart window).
In particular, neutral coloration allows better comfort to the person when applied to electrochromic smart windows, relative to the dark blue coloration exhibited by traditional tungsten oxides; the electrochromic material has better electrochromic property by high-temperature thermal annealing; the W-Nb-O electrochromic material prepared by the invention has good optical modulation amplitude, circulation stability and excellent coloring neutral color, and can meet better application prospect in neutral color electrochromic devices.
In order to more clearly illustrate the technical features, objects and advantages of the present invention, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Unless otherwise indicated, all starting materials and reagents in the examples herein were purchased commercially.
Comparative example 1
Commercially available pure tungsten oxide films were used.
Example 1
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=40 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =40 wt.%) ceramic body as target, targetThe material is according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =40 wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 2 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 6 hours, fully mixing the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 100MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 5 ℃/min, the sintering temperature is 1275 ℃, the heat preservation time is 4 hours, taking out after the annealing furnace temperature is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, working air pressure of 0.8Pa, sputtering power of 250W, substrate being unintentionally heated, thinFilm thickness350nm. And then placing a film sample deposited by magnetron sputtering into an annealing furnace for annealing treatment, wherein the annealing temperature is 350 ℃, the heat preservation time is 5min, the heating rate is 11.6 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 2000 electrochemical cycles: the modulation amplitude is reduced from 63.9% to 62.2% before circulation; the b of the colored state of the sample before circulation is 1.0, and after circulation, the b of the colored state is 1.9, and still accords with the expectation of neutral color.
Example 2
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=40 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =40 wt.%) ceramic body as target, target was according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =40 wt.% will weigh Nb 2 O 5 And WO 3 Placing the powder into a ball milling tank, then adding deionized water with the mass of 2 times of the powder,after sealing, placing the mixture in a planetary ball mill for ball milling for 6 hours to fully mix two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 100MPa by using hydraulic forming equipment, placing the green body in a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 5 ℃/min, the sintering temperature is 1275 ℃, the heat preservation time is 4 hours, taking out the ceramic target material after the annealing furnace temperature is reduced to normal temperature, placing the ceramic target material into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5 multiplied by 10 in the sputtering process -2 Pa, working air pressure of 0.8Pa, sputtering power of 250W, substrate being unintentionally heated, thinFilm thickness350nm.
The film obtained in this example was subjected to 2000 electrochemical cycles: the modulation amplitude is reduced from 65.4% before circulation to 49.8%; the b of the sample before circulation is-1.8, and after circulation, the b of the coloring state is-1.5, and the expected neutral color is still met.
Example 3
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=50 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =50 wt.%) ceramic body as target, the target is according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =50wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight being 2 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 6 hours, fully mixing the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 100MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 5 ℃/min, the sintering temperature is 1275 ℃, the heat preservation time is 4 hours, and taking out after the annealing furnace temperature is reduced to normal temperature, and taking out the green body for sputtering The ceramic target material of the (2) is placed in a magnetron sputtering cavity for coating, inert gas Ar is used as working gas, a radio frequency sputtering method is adopted, and in the sputtering process, the background vacuum degree of the coating cavity is 5 multiplied by 10 -2 Pa, working air pressure of 0.8Pa, sputtering power of 250W, substrate being unintentionally heated, thinFilm thickness350nm.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 65.5% before circulation to 49.1%; the b of the colored state of the sample before circulation is 3.1, and after circulation, the b of the colored state is-2.4, and the expected neutral color is still met.
Example 4
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of system=50wt.% and subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter niobium-doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =50 wt.%) ceramic body as target, the target is according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =50wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 150MPa by using hydraulic forming equipment, sintering the green body in a muffle furnace, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 5 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nrn, then the film is put into an annealing furnace for annealing treatment, and the annealing temperature is the same as that of the film sample deposited by magnetron sputteringThe temperature is 350 ℃, the heat preservation time is 5min, the heating rate is 11.6 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 65.9% to 60.2% before circulation; the b of the sample before circulation is 3.6, and after circulation, the b of the coloring state is-1.9, which still accords with the expectation of neutral color.
Example 5
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system =60 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =60 wt.%) ceramic body as target, the target was according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =60 et.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 150MPa by using hydraulic forming equipment, sintering the green body in a muffle furnace, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1350 ℃, the heat preservation time is 6 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, working air pressure of 0.8Pa, sputtering power of 250W, substrate being unintentionally heated, thinFilm thickness350nm.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 57.8% to 15.5% before circulation; the b of the colored state of the sample before circulation is 6.4, and after circulation, the b of the colored state is-1.1, and the expected neutral color is still met.
Example 6
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of system of =60 wt.% and subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter niobium-doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =60 wt.%) ceramic body as target, the target was according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =60 wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in a baking oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 350 ℃, the heat preservation time is 5min, the heating rate is 11.6 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 64.2% to 50.7% before circulation; the b of the colored state of the sample before the circulation is 6.4, and after the circulation, the b of the colored state is-1.7, and the expected neutral color is still met.
Example 7
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=30 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =30 wt.%) ceramic body as target, the target was according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =30wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in a baking oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, working air pressure of 0.8Pa, sputtering power of 250W, substrate being unintentionally heated, thinFilm thickness350nm.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 55.8% to 20.5% before circulation; the b of the sample before circulation is 6.8, and after circulation, the b of the coloring state is-2.4, which still accords with the expectation of neutral color.
Example 8
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of 70wt.% system+subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing the powder into a ball milling tank, adding deionized water with the mass of 3 times of the powder, sealing, placing into a planetary ball mill, and ball milling for 4 hours to realize the filling of the two substancesMixing, ball milling, stoving the mixture in an oven, rolling to form powder, pressing the powder into green body under 70MPa with hydraulic forming equipment, sintering in a muffle furnace at temperature raising rate of 3 deg.c/min and sintering temperature of 1200 deg.c for 2 hr, cooling to normal temperature, taking out to obtain ceramic target, coating in a magnetron sputtering cavity with inert gas Ar as working gas, and RF sputtering to obtain coating cavity with background vacuum degree of 5×10 -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 350 ℃, the heat preservation time is 5min, the heating rate is 11.6 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 60.2% to 50.7% before circulation; the b of the sample before circulation is 3.5, and after circulation, the b of the coloring state is-2.7, which still accords with the expectation of neutral color.
Example 9
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=70 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing the powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours to fully mix the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using a hydraulic forming device, sintering the green body in a muffle furnace, wherein the temperature rising rate in the sintering process is 3 ℃/min, and sintering The temperature is 1200 ℃, the heat preservation time is 2 hours, after the annealing furnace temperature is reduced to normal temperature, the ceramic target material is taken out and used as a ceramic target material to be sputtered, the ceramic target material is placed in a magnetron sputtering cavity for coating, inert gas Ar is used as working gas, a radio frequency sputtering means is adopted, and the background vacuum degree of the coating cavity is 5 multiplied by 10 in the sputtering process -2 Pa, working air pressure of 0.6Pa, sputtering power of 250W, substrate being unintentionally heated, thinFilm thickness350nm.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 50.8% to 20.5% before circulation; the b of the sample before circulation is 6.5, and after circulation, the b of the coloring state is-2.5, which still accords with the expectation of neutral color.
Example 10
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=70 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in a baking oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -4 Pa, working air pressure of 2.0Pa, sputtering power of 100W, substrate being unintentionally heated, thinFilm thickness100nm.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 30.8% to 20.5% before circulation; the b of the sample before circulation is 8.5, and after circulation, the b of the coloring state is 8.6, which still accords with the expectation of neutral color.
Example 11
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of the system=70 wt.%. Placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium-doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in a baking oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -3 Pa, working air pressure of 0.8Pa, sputtering power of 200W, substrate being unintentionally heated, thinFilm thickness270nm.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 50.8% to 20.5% before circulation; the b of the sample before circulation is-5.8, and after circulation, the b of the coloring state is-5.2, and the expected neutral color is still met.
Example 12
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.% of systemThe film and the subsequent high temperature annealing, the cleaned ITO glass substrate is placed in a magnetron sputtering coating cavity to sinter the niobium doped tungsten oxide (Nb) 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in a baking oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 300 ℃, the heat preservation time is 5min, the heating rate is 9.1 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 50.2% to 40.7% before circulation; the b of the colored state of the sample before circulation is 5.2, and after circulation, the b of the colored state is-2.3, and the expected neutral color is still met.
Example 13
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of 70wt.% system+subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as targetThe target material is according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing powder into a ball milling tank, adding deionized water with the weight of 3 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in a baking oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out after the temperature of an annealing furnace is reduced to normal temperature, taking out the ceramic target as a ceramic target to be sputtered, placing the ceramic target into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering means, wherein the background vacuum degree of the coating cavity is 5×10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 300 ℃, the heat preservation time is 15min, the heating rate is 5 ℃/s, and the cooling rate is 0.2 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 55.2% to 45.7% before circulation; the b of the colored state of the sample before circulation is 5.5, and after circulation, the b of the colored state is-2.5, and the expected neutral color is still met.
Example 14
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of 70wt.% system+subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =70 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of=70 wt.% will weigh Nb 2 O 5 And WO 3 Placing the powder into a ball milling tank, and then adding the powder quality3 times of deionized water, sealing, placing into a planetary ball mill, ball milling for 4 hours to fully mix two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using a hydraulic forming device, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 3 ℃/min, the sintering temperature is 1200 ℃, the heat preservation time is 2 hours, taking out the ceramic target material after the annealing furnace temperature is reduced to normal temperature, placing the ceramic target material into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, and adopting a radio frequency sputtering method, wherein the background vacuum degree of the coating cavity is 5 multiplied by 10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 500 ℃, the heat preservation time is 1min, the heating rate is 20 ℃/s, and the cooling rate is 2 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 58.2% to 40.7% before circulation; the b of the colored state of the sample before circulation is 5.5, and after circulation, the b of the colored state is-2.5, and the expected neutral color is still met.
The inventors also performed performance characterization on each sample of the examples obtained above, specifically as follows:
the method comprises the steps of observing the phase structure of a film by an X-ray diffractometer (XRD), observing the valence state of an element by photoelectron spectroscopy (XPS), observing the internal structure and crystal phase of the film by a Transmission Electron Microscope (TEM), measuring the optical modulation amplitude and electrochromic response time of the film by an ultraviolet-visible spectrophotometer, measuring the electrochemical properties, the electrochromic properties such as the cycling stability and the like of the film by an electrochemical workstation, and measuring the b-value of the film by a colorimeter.
Fig. 1a and 1b are a colored state transmittance chart and an external appearance chart of comparative example 1. Pure WO 3 After the film is colored, the film is found to be typical of deep blue due to a strong optical transmission peak at a wavelength of 480nm (FIG. 1 a), which corresponds to blue lightAn area. The b-value was-25.7 as measured by a colorimeter.
FIG. 2 is an XRD pattern of the film of example 1 of the present invention and of the film sample of example 2; it can be seen that no other diffraction peaks, except those from the ITO substrate, were found, indicating that both films were amorphous structures, which helped to promote the modulation amplitude of the electrochromic reaction.
FIGS. 3a and 3b are XPS spectra of colored films of the samples prepared in example 1, showing that the niobium doped tungsten oxide electrochromic film has a large W 5+ /(W 5+ +W 6+ ) And Nb (Nb) 4+ /(Nb 4+ +Nb 5+ ) Ratio of W 5+ And Nb (Nb) 4+ Is an active substance participating in electrochromic reaction, more W 5+ And Nb (Nb) 4+ Presence means a larger optical modulation amplitude; nb (Nb) 4+ The amorphous niobium oxide film of (2) is dark brown, and the maximum absorption band is about 400nm, so that in the colored state of the W-Nb-O film in which Nb and W substances are highly uniformly mixed, the partially reduced niobium oxide weakens the transmittance of a colored tungsten oxide part in a short wavelength (300-500 nm) region, and the color neutrality of the colored state color is realized.
Fig. 4a and fig. 4b are TEM cross-sectional profiles of the prepared film of example 1 and the prepared film of example 2, respectively, both of which exhibit columnar structures that help to maintain more lithium ion binding sites in the electrochromic film, and to promote the optical modulation amplitude and electrochemical stability of the film.
FIGS. 5a and 5b are optical transmittance spectra before and after cycling of the niobium doped tungsten oxide electrochromic film prepared in example 1 and the niobium doped tungsten oxide film prepared in example 2; as can be seen from fig. 5a to 5b, the colored state transmittance of example 2 is lower, the optical modulation amplitude is larger, and the color state transmittance is better than that of example 1 in the wavelength range of 300nm to 2500 nm; also, neither sample of examples 1 and 2 exhibited a sharper transmittance peak at about 480nm compared to comparative example 1.
FIGS. 6 a-6 b are graphs showing the light modulation change at 550nm of the films prepared in example 1 and example 2, respectively; as can be seen from fig. 6 a-6 b, the color state transmittance of example 2 is 15.5% after 2000 cycles of electrochemical cycling at a wavelength of 550nm, the optical modulation amplitude is 49.8% (as shown in fig. 6 b), and the color state transmittance of example 1 is 16.5%, the optical modulation amplitude is 62.2% (as shown in fig. 6 a), which indicates that the niobium doped tungsten oxide electrochromic film of example 1 significantly improves the electrochemical cycling stability after high temperature annealing, and the high temperature annealing has little influence on the EC performance in the initial state, but plays a role in the following electrochemical cycling stability, stability of b-value, and the like.
FIG. 7a is a graph of the film prepared in example 1 in the colored state, with the colored state transmittance exhibiting a flattened trend, illustrating the color neutrality of the film in the colored state. FIG. 7b is an external view of the film prepared in example 1.
Table 1 shows CIE chromaticity b values of each of the film-colored samples of comparative example 1 and examples 1 to 6 before recycling
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Comparative example 2
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of system of =20wt.% and subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =20 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =20wt.% will weigh Nb 2 O 5 And WO 3 Placing the powder into a ball milling tank, adding deionized water with the weight being 2 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours to fully mix the two substances, drying the mixture in an oven after ball milling, and rolling the mixture into powder, and utilizingThe powder is pressed into a green body by hydraulic forming equipment under 70MPa, then the green body is placed in a muffle furnace for sintering, the temperature rising rate in the sintering process is 5 ℃/min, the sintering temperature is 1275 ℃, the heat preservation time is 4h, after the temperature of an annealing furnace is reduced to normal temperature, the ceramic target material is taken out and used as a ceramic target material to be sputtered, the ceramic target material is placed in a magnetron sputtering cavity for coating, inert gas Ar is used as working gas, a radio frequency sputtering means is adopted, and the background vacuum degree of the coating cavity is 5 multiplied by 10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 300 ℃, the heat preservation time is 5min, the heating rate is 9.1 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 60.2% to 50.7% before circulation; the b-x of the colored state of the sample before the cycle is-11.2, and after the cycle, the b-x value of the colored state is-13.2, which does not meet the expectations of neutral color.
Comparative example 3
Preparation of Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) Film of system of 80wt.% +subsequent high temperature annealing, placing the cleaned ITO glass substrate in a magnetron sputtering coating cavity to sinter the niobium doped tungsten oxide (Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) =80 wt.%) ceramic body as target, target according to Nb 2 O 5 /(Nb 2 O 5 +WO 3 ) A ratio of =80 wt.% will weigh Nb 2 O 5 And WO 3 Placing the powder into a ball milling tank, adding deionized water with the weight being 2 times of that of the powder, sealing, placing into a planetary ball mill, ball milling for 4 hours, fully mixing the two substances, drying the mixture in an oven after ball milling, rolling the mixture into powder, pressing the powder into a green body under 70MPa by using hydraulic forming equipment, placing the green body into a muffle furnace for sintering, wherein the temperature rising rate in the sintering process is 5 ℃/min, the sintering temperature is 1275 ℃, the heat preservation time is 4 hours, and after the temperature of an annealing furnace is reduced to normal temperature, Taking out the ceramic target material to be sputtered, placing the ceramic target material into a magnetron sputtering cavity for coating, taking inert gas Ar as working gas, adopting a radio frequency sputtering method, wherein the background vacuum degree of the coating cavity is 5 multiplied by 10 in the sputtering process -2 Pa, the working air pressure value is 0.8Pa, the sputtering power is 250W, the substrate is unintentionally heated, the thickness of the film is 350nm, then the film is subjected to annealing treatment by placing a film sample deposited by magnetron sputtering in an annealing furnace, the annealing temperature is 300 ℃, the heat preservation time is 5min, the heating rate is 9.1 ℃/s, and the cooling rate is 1 ℃/s.
The film obtained in this example was subjected to 300 electrochemical cycles: the modulation amplitude is reduced from 60.2% to 50.7% before circulation; the b of the sample before cycling was 9.6, and after cycling, the b of the colored state was 10.4, which did not meet the expectations of neutral color.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. A method for producing an electrochromic film having neutral coloring, comprising:
providing a W-Nb-O electrochromic material comprising Nb 2 O 5 And WO 3 Wherein Nb is 2 O 5 The content of (2) is 30-70 wt%;
and preparing the W-Nb-O electrochromic material into an electrochromic film with neutral coloring by adopting a magnetron sputtering technology and combining a high-temperature thermal annealing technology which is optionally performed.
2. The method of manufacturing according to claim 1, comprising:
the saidPressing the W-Nb-O electrochromic material into a blank, and sintering to obtain the Nb-doped WO to be sputtered 3 A ceramic target;
doping WO with Nb 3 Taking ceramic as a target material, taking a substrate deposited with a transparent conductive layer as a matrix, and adopting a magnetron sputtering technology to deposit and form a film on the substrate deposited with the transparent conductive layer;
annealing the film deposited by magnetron sputtering to obtain the electrochromic film with neutral coloring.
3. The method of manufacturing according to claim 2, comprising: nb is set to 2 O 5 And WO 3 Mixing the powder with water, ball milling to form mixed powder, pressing the mixed powder into a green body under 70-150 MPa, and finally sintering to obtain the Nb-doped WO to be sputtered 3 The ceramic target material has the temperature rising rate of 3-5 ℃/min, the sintering temperature of 1200-1350 ℃ and the heat preservation time of 2-6 h.
4. A method of preparation according to claim 3, characterized in that: the water and Nb 2 O 5 And WO 3 The mass ratio of the combination of the powder is 2-3:1; and/or the ball milling time is 4-10 h.
5. The method of manufacturing according to claim 2, comprising: placing a substrate deposited with a transparent conductive layer into a magnetron sputtering coating cavity by adopting a magnetron sputtering technology, and doping WO with Nb 3 Ceramic is used as a target material, inert gas is used as working gas, a radio frequency or medium frequency sputtering method is adopted to deposit and form a film on a substrate deposited with a transparent conductive layer, wherein the background vacuum degree of a magnetron sputtering coating cavity is 5 multiplied by 10 -2 ～5×10 -4 Pa, the working air pressure is 0.6-2.0 Pa, and the sputtering power is 100-250W.
6. The method of manufacturing according to claim 5, wherein: the thickness of the film is 200-500 nm;
and/or the substrate deposited with the transparent conductive layer comprises any one of an ITO glass substrate and an FTO glass substrate;
and/or the inert gas comprises Ar.
7. The method of claim 2, wherein the process parameters of the annealing process include: the annealing temperature is 300-500 ℃, the heat preservation time is 1-15 min, the heating rate is 5-20 ℃/s, and the cooling rate is 0.5-2 ℃/s.
8. An electrochromic film having neutral coloration produced by the production process of any one of claims 1 to 7.
9. The electrochromic film with neutral coloring according to claim 8, wherein: the electrochromic film presents neutral black in a coloring state, and b is less than or equal to 5.
10. Use of an electrochromic film with neutral coloration according to claim 8 or 9 for the preparation of a neutral electrochromic device.
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