CN112558369A - All-solid-state electrochromic device and preparation method thereof - Google Patents
All-solid-state electrochromic device and preparation method thereof Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
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- Crystallography & Structural Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The application provides an all-solid-state electrochromic device and a preparation method thereof, the all-solid-state electrochromic device comprises a substrate and a multilayer film structure positioned on the same side of the substrate, and the multilayer film structure comprises: two conductive layers, wherein one conductive layer covers the substrate; an electrochromic layer, an ion conducting layer and an ion storage layer interposed between the two conductive layers; the density of the electrochromic layer tends to increase gradually in a direction away from the ion storage layer. The preparation method of the all-solid-state electrochromic device comprises the following steps: depositing and growing a conductive layer on one side of the substrate; depositing and growing an electrochromic layer on the conductive layer; depositing and growing an ionized ion storage layer on the electrochromic layer; depositing and growing a conductive layer on the ionized ion storage layer; and carrying out heat treatment after the film coating is finished. The films of the all-solid-state electrochromic device prepared by the method are stable in lattice matching and long in service life.
Description
Technical Field
The application relates to the field of electrochromic devices, in particular to an all-solid-state electrochromic device and a preparation method thereof.
Background
Electrochromism means that the optical properties of the material are changed stably and reversibly under the action of an applied electric field, and the material is shown as reversible change of color and transparency in appearance. Electrochromic devices are generally composed of a bottom transparent conductive layer, an electrochromic layer, an ion conducting layer, an ion storage layer, and a top transparent conductive layer. According to different materials, the materials are divided into organic electrochromism and inorganic electrochromism; depending on the ion conductive layer, it is classified into an all-solid type, a semi-solution type and a solution type.
The all-solid-state inorganic electrochromic device has the advantages of strong sunlight radiation resistance, safety, reliability and the like, and the preparation method generally comprises the step of sequentially depositing layers on a substrate. To simplify the process, the electrochromic layer and the ion storage layer may be in direct contact, without the need to deposit an ion conducting layer, with an interfacial region formed therebetween by heat treatment to serve as an ion conducting layer. Because the materials forming the all-solid-state inorganic electrochromic device are all solid, when ions migrate back and forth between the ion storage layer and the electrochromic layer under the action of an electric field, the ions are injected and released from the electrochromic layer for many times, so that lattice mismatch between film layers is easily caused, the quality of the film layers is deteriorated, and the service life of the device is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides an all-solid-state electrochromic device with the characteristics of difficult lattice mismatch, stable quality and long service life among membrane layers.
The all-solid-state electrochromic device comprises a substrate and a multilayer film structure positioned on the same side of the substrate, wherein the multilayer film structure comprises:
two conductive layers, wherein one conductive layer covers the substrate;
an electrochromic layer, an ion conducting layer and an ion storage layer interposed between the two conductive layers; the density of the electrochromic layer tends to become gradually greater in a direction away from the ion storage layer.
The density of the electrochromic layer is gradually increased in the direction away from the ion storage layer, namely, the film density of the area closer to the ion storage layer is smaller, and the film density of the area farther away from the ion storage layer is larger. The structure is characterized in that a green channel can be provided for the migration of ions in the ion storage layer into the electrochromic layer, the effect of ion conduction is favorably enhanced, the problem of color change functional failure of the device caused by poor film quality due to the fact that the electrochromic layer is injected and separated for many times is solved, and the service life of the device is effectively guaranteed.
Optionally, the electrochromic layer has a minimum density of 5.83g/cm3Maximum density of 7.59g/cm3. The density of the electrochromic layer has a gradual trend, which means that the density of the electrochromic layer changes along the thickness direction of the film layer, and the change range is a certain interval or a plurality of intervals between the minimum density and the maximum density.
The rate of change of the density may be linear or non-linear.
Optionally, the electrochromic layer is made of one or more of tungsten oxide, titanium oxide, vanadium oxide, zirconium oxide, niobium oxide, molybdenum oxide, and tantalum oxide.
The tungsten oxide is a cathode electrochromic material which generates color transition from transparent to blue through electrochemical reduction reaction, is colorless and transparent in a high-valence oxidation state, and is reduced to change color to blue after ion implantation, so that the electrochromic layer has a color change function.
Optionally, the thickness of the electrochromic layer is 300-1000 nm.
Optionally, the two conductive layers are made of one or more of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, nano silver mesh and graphene;
the thickness of the two conducting layers is 100-1000 nm, and the sheet resistance is 1-30 omega/□.
Optionally, the ion storage layer comprises a body and an ion source.
Optionally, the material of the body is one or more of nickel oxide, cobalt oxide, iron oxide, manganese oxide, chromium oxide, rhodium oxide, iridium oxide, nickel tungsten oxide, nickel vanadium oxide, nickel manganese oxide and nickel aluminum oxide;
wherein, the nickel oxide is an anode electrochromic material and has good electrochromic characteristics, and the nickel oxide is colorless in a low-valence reduction state and is colored in a high-valence oxidation state. The electrochromic layer and the ion storage layer are in complementary color change for the cathode and the anode. When ions migrate out of the ion storage layer and are injected into the electrochromic layer, the ion storage layer is oxidized and colored, and the electrochromic layer is reduced and also colored; when ions migrate out of the electrochromic layer back into the ion storage layer, the electrochromic layer fades and the ion storage layer also fades.
Optionally, the ion source is one or more of hydrogen ions, lithium ions, sodium ions, potassium ions and magnesium ions;
the ion source can be one or more of corresponding simple substance, oxide and peroxide.
Optionally, the thickness of the ion storage layer is 100-350 nm; the ion doping amount in the ion storage layer is 0.1-10%.
The ion source is deposited in the ion storage layer body, the deposition amount and the deposition uniformity of the ion source are related to the material, the structure, the thickness and the like of the ion storage layer body, the ion storage layer with the thickness needs to be ensured to be completely diffused into the ion storage layer, the ion storage layer and the ion storage layer body form the same layer of film, and ions cannot form a layer of film independently.
Optionally, the substrate is a transparent inorganic solid material.
Optionally, the substrate is one of soda-lime glass, high-alumina glass, borosilicate glass, quartz glass, and a resin film.
The electrochromic device is generally a five-layer structure, and comprises a bottom transparent conducting layer, an electrochromic layer, an ion conducting layer, an ion storage layer and a top transparent conducting layer, wherein the preparation method generally comprises the steps of sequentially arranging the layers on a substrate. The ion conducting layer can allow ions to pass through and prevent electrons from passing through. There are also devices in which an ion conductive layer is not separately provided, and a four-layer structure device is manufactured and then subjected to heat treatment or light treatment to form an interface region between the electrochromic layer and the ion storage layer, the interface region allowing ions to pass therethrough and preventing electrons from passing therethrough.
The application also provides a preparation method of the all-solid-state electrochromic device, which comprises the following steps:
(1) depositing and growing a conductive layer on one side of the substrate;
(2) depositing and growing an electrochromic layer on the conductive layer;
(3) depositing and growing an ionized ion storage layer on the electrochromic layer;
(4) depositing and growing a conductive layer on the ionized ion storage layer;
(5) and carrying out heat treatment after the film coating is finished to obtain the all-solid-state electrochromic device.
The film layers can be formed by vapor deposition methods, including Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), sol-gel method, etc., and magnetron sputtering, thermal evaporation, etc. are common methods in the physical vapor deposition methods.
The lower the density of the electrochromic layer is, the looser the film structure of the electrochromic layer is, so that ions in the ion storage layer can be rapidly injected into the electrochromic layer, but the density cannot be too small, otherwise, the film structure is too loose, and the adhesion between the conductive layer or the ion storage layer is not firm.
In order to take account of the problem of the adhesive capacity between the electrochromic layer and the adjacent layer, ensure the bonding capacity between the film layers and not influence the cycle service life of the all-solid-state electrochromic device, optionally, the density of the electrochromic layer in the step (2) is 5.83-7.59 g/cm3。
The density of the electrochromic layer is changed by regulating and controlling the total air pressure, oxygen partial pressure, power, substrate temperature and the like in a magnetron sputtering system.
The ion source in the step (3) can be doped when the ion storage layer is prepared or can be injected into the ion source through sputtering, a thermal evaporation method and a sol-gel method after the ion storage layer is prepared, so that the completely ionized ion storage layer is prepared.
The heat treatment in step (5) can adopt vacuum annealing, atmosphere annealing and the like.
The films of the all-solid-state electrochromic device prepared by the method are stable in lattice matching and long in service life.
Drawings
FIG. 1 is a schematic structural diagram of an all-solid-state electrochromic device;
FIG. 2 is a cyclic voltammogram of the all-solid electrochromic device of example 1;
FIG. 3 is a cyclic voltammogram of the all-solid electrochromic device of example 2;
FIG. 4 is a cyclic voltammogram of the all-solid electrochromic device of example 3;
FIG. 5 is a cyclic voltammogram of the all-solid electrochromic device of example 4;
FIG. 6 is a cyclic voltammogram of the all-solid electrochromic device of example 5;
fig. 7 is a cyclic voltammogram of the all-solid electrochromic device of comparative example 1.
The reference numerals in the figures are illustrated as follows:
1. a substrate; 2. a conductive layer; 3. an electrochromic layer; 4. an ion conducting layer; 5. an ion storage layer; 51. an ion source; 6. and a conductive layer.
Detailed Description
The technical solutions described in the present application will be further described with reference to the following embodiments, but the present application is not limited thereto.
FIG. 1 depicts a schematic diagram of a multilayer film structure of an all-solid-state electrochromic device, and the coating processes in examples 1 to 5 are all completed in a magnetron sputtering system, and the method comprises the following steps:
(1) depositing and growing a conductive layer 2 on a transparent substrate 1;
(2) depositing and growing an electrochromic layer 3 on the conductive layer 2;
(3) depositing the body of the ion storage layer 5 on the electrochromic layer 3, and then injecting the ion source 51 to ionize the body;
(4) after the ionization is finished, depositing a conductive layer 6 on the ion storage layer 5;
(5) an interface region 4 is formed between the ion storage layer and the electrochromic layer by a heat treatment.
Example 1
The substrate 1 is glass; the conducting layer 2 is Indium Tin Oxide (ITO) with the thickness of 350 nm; the electrochromic layer 3 is tungsten oxide (WO)x) The volume fraction of oxygen at the beginning of sputtering is 30%, the volume fraction of oxygen is continuously increased in the deposition process, the volume fraction of oxygen at the end of sputtering is 60%, and the thickness is 550 nm; the bulk material of the ion storage layer 5 is nickel tungsten oxide, the thickness is 250nm, lithium is used as an ion source 51 to ionize the ion storage layer 5, the ion doping amount is 8%, and the product is blue; indium Tin Oxide (ITO) was deposited as a conductive layer 6 on the fully ionized nickel tungsten oxide to a thickness of 380 nm.
Vacuum annealing at 450 deg.C for 10min after coating, with vacuum degree of 10-6torr, atmospheric annealing at 350 c for 1h, forming an interfacial region 4 between the electrochromic layer 3 and the ion storage layer 5.
The tungsten oxide film layer prepared in this example had a gradually increasing atomic ratio of tungsten oxide from the surface on the ITO conductive layer side to the surface on the nickel tungsten oxide layer side, the atomic ratio of tungsten oxide being from 2: 1 was gradually changed to 3.2: 1.
the density (ρ) of the tungsten oxide film layer was calculated from the Lorentz-Lorenz formula by testing the refractive index of the film layer:
wherein n isfRefractive index of the film layer, np-the refractive index of the bulk is 2.5 ρ0The density of the block is 7.60g/cm3。
In the tungsten oxide film prepared by the embodiment, when the percentage of oxygen is gradually increased from 30% to 60%, the density of the film is increased from 7.29g/cm3Gradually reduced to 6.46g/cm3As shown in table 1, it is explained that the electrochromic layer is more porous in the region closer to the ion storage layer and more dense in the region farther from the ion storage layer.
The prepared 620mm 840mm electrochromic glass can be completely discolored within 4min, the transmittance at 550nm in a visible light region after coloring is less than 1.5%, and the transmittance after discoloring is about 55%. Fig. 2 is a cyclic voltammetry curve of the device prepared in this example, the device has almost unchanged ion storage capacity after 10 ten thousand cycles, and the cycle life of the device can reach more than 10 ten thousand cycles.
Table 1 example 1 density of electrochromic layer as a function of oxygen content of the coating film
Note: in table 1, the densities of the tungsten oxide film layers prepared at oxygen contents of 30%, 40%, 50% and 60% were calculated, respectively, and the results showed that the greater the oxygen content, the lower the density of the tungsten oxide film layer, from which it can be deduced that the tungsten oxide film layer with gradually changed density can be prepared by controlling the change of oxygen content during the deposition of tungsten oxide.
Example 2
The substrate 1 is glass, the conducting layer 2 is Indium Tin Oxide (ITO) and the thickness is 350 nm; the electrochromic layer 3 is tungsten oxide (WO)x) The volume fraction of oxygen at the beginning of sputtering is 35%, the volume fraction of oxygen is continuously increased in the deposition process, the volume fraction of oxygen at the end of sputtering is 68%, and the thickness is 550 nm; the bulk material of the ion storage layer 5 is nickel tungsten oxide, the thickness is 250nm, lithium is used as an ion source 51 to ionize the ion storage layer 5, the ion doping amount is 5%, and the product is yellow; indium Tin Oxide (ITO) was deposited as a conductive layer 6 on the fully ionized nickel tungsten oxide to a thickness of 400 nm.
Vacuum annealing at 450 deg.C for 10min after coating, with vacuum degree of 10-6torr, atmospheric annealing at 350 c for 1h, forming an interfacial region 4 between the electrochromic layer 3 and the ion storage layer 5.
The tungsten oxide film layer prepared in this example had a gradually increasing atomic ratio of tungsten oxide from the surface on the ITO conductive layer side to the surface on the nickel tungsten oxide layer side, the atomic ratio of tungsten oxide being from 2.5: 1 was gradually changed to 3.5: 1. when the oxygen is hundredsThe content of the tungsten oxide film is gradually increased from 35 percent to 68 percent, and the density of the tungsten oxide film is 7.20g/cm3Gradually reduced to 6.38g/cm3As shown in table 2, it is demonstrated that the electrochromic layer has a more porous film layer in the region closer to the ion storage layer and a more dense film layer in the region farther from the ion storage layer.
The prepared electrochromic glass with the thickness of 370mm multiplied by 470mm can be completely discolored within 2min, the transmittance at 550nm in a visible light region after coloring is less than 5%, and the transmittance after discoloring is about 70%. Fig. 3 is a cyclic voltammetry curve of the device prepared in the example, the capability of storing ions of the device is almost unchanged after 10 ten thousand cycles, and the cyclic life of the device can reach more than 10 ten thousand cycles.
Table 2 example 2 density of electrochromic layer as a function of oxygen content of the coating film
Note: in table 2, the densities of the tungsten oxide films prepared at oxygen contents of 35%, 45%, 55% and 68% were calculated, respectively, and the results showed that the greater the oxygen content, the lower the density of the tungsten oxide film, from which it can be deduced that the tungsten oxide film having a gradually changing density can be prepared by controlling the change in oxygen content during the deposition of tungsten oxide.
Example 3
The substrate 1 is glass; the conducting layer 2 is made of Indium Tin Oxide (ITO) and has the thickness of 300 nm; the electrochromic layer 3 is tungsten oxide (WO)x) The gas pressure at the start of sputtering was 3X 10-3torr, increasing the gas pressure during deposition, the gas pressure at the end of sputtering is 5X 10-3torr, the thickness of tungsten oxide is 700 nm; the bulk material of the ion storage layer 5 is nickel tungsten oxide with a thickness of 320nm, lithium is used as an ion source 51 to ionize the ion storage layer 5, and Indium Tin Oxide (ITO) is deposited on the completely ionized nickel tungsten oxide to form a conductive layer 6 with a thickness of 350 nm.
Vacuum annealing at 400 deg.C for 20min with vacuum degree of 10-6torr, an interfacial region 4 is formed between the electrochromic layer 3 and the ion storage 5.
The tungsten oxide film prepared by the example has the total pressure of 3 multiplied by 10-3the torr is gradually increased to 5X 10-3torr, the density of the tungsten oxide film layer is from 7.33g/cm3Gradually reduced to 7.02g/cm3As shown in table 3, it is demonstrated that the electrochromic layer is more porous in the region closer to the ion storage layer and more dense in the region farther from the ion storage layer.
The prepared electrochromic glass has the transmittance of less than 3 percent at the visible light region of 550nm after being colored and the transmittance of about 68 percent after being discolored. Fig. 4 is a cyclic voltammetry curve of the device prepared in the example, the capability of storing ions of the device is almost unchanged after 9 ten thousand cycles, and the cyclic life of the device can reach more than 9 ten thousand cycles.
Table 3 example 3 density of electrochromic layer as a function of total coating pressure
Note: in Table 3, the total pressure was calculated to be 3X 10-3torr、4×10-3torr and 5X 10-3the density of the tungsten oxide film layer prepared under the torr indicates that the larger the total pressure is, the smaller the density of the tungsten oxide film layer is, so that the tungsten oxide film layer with gradually changed density can be prepared by controlling the change of the total pressure in the tungsten oxide deposition process.
Example 4
The substrate 1 is glass; the conducting layer 2 is made of Indium Tin Oxide (ITO) and has the thickness of 300 nm; the electrochromic layer 3 is tungsten oxide (WO)x) The power is 8kW when sputtering is started, the power is continuously reduced in the deposition process, the power is 2kW when sputtering is finished, and the thickness is 650 nm; the bulk material of the ion storage layer 5 is nickel tungsten oxide with a thickness of 300nm, lithium is used as an ion source 51 to ionize the ion storage layer, and Indium Tin Oxide (ITO) is deposited on the completely ionized nickel tungsten oxide to form a conductive layer 6 with a thickness of 380 nm.
Vacuum annealing at 450 deg.C for 30min with vacuum degree of 10-6torr, atmospheric annealing at 350 deg.C, annealing for 2h, in electrochromic layer 3 and ionThe sub-memory layer 5 forms the interface region 4.
The tungsten oxide film prepared in the example has a density of 7.55g/cm when the sputtering power is gradually reduced from 5kW to 3kW3Gradually reduced to 6.08g/cm3As shown in table 4, it is demonstrated that the electrochromic layer is more porous in the region closer to the ion storage layer and more dense in the region farther from the ion storage layer.
The prepared electrochromic glass has the transmittance of less than 4 percent at the visible light region of 550nm after being colored and the transmittance of about 65 percent after being discolored. Fig. 5 is a cyclic voltammetry curve of the device prepared in this example, the device has almost unchanged ion storage capacity after 9.5 ten thousand cycles, and the cyclic lifetime of the device can reach more than 9.5 ten thousand cycles.
Table 4 example 4 density of electrochromic layer as a function of coating power
Note: in table 4, the densities of the tungsten oxide film layers prepared at powers of 3kW, 4kW, and 5kW were calculated, respectively, and the results showed that the higher the power, the higher the density of the tungsten oxide film layer, from which it can be deduced that the tungsten oxide film layer with gradually changed density can be prepared by controlling the change in power during the deposition of tungsten oxide.
Example 5
The substrate 1 is glass; the conducting layer 2 is made of Indium Tin Oxide (ITO) and is 350nm thick; the electrochromic layer 3 is tungsten oxide (WO)x) The film plating temperature is reduced from 400 ℃ to 250 ℃, and the thickness is 600 nm; the ion storage layer 5 is nickel tungsten oxide with a thickness of 280nm, the ion storage layer is ionized by using lithium as an ion source 51, and Indium Tin Oxide (ITO) is deposited on the completely ionized nickel tungsten oxide to be a conductive layer 6 with a thickness of 400 nm.
And after the film coating is finished, annealing for 3h at 250 ℃ in the atmosphere, and forming an interface region 4 between the electrochromic layer 3 and the ion storage layer 5.
When the coating temperature of the tungsten oxide film layer prepared by the embodiment is gradually reduced from 400 ℃ to 250 ℃, the density of the tungsten oxide film layer is reduced from 7.27g/cm3Gradually reduced to 6.98g/cm3As shown in table 5, it is demonstrated that the electrochromic layer has a more porous film layer in the region closer to the ion storage layer and a more dense film layer in the region farther from the ion storage layer.
The obtained electrochromic glass had a transmittance of 3% at 550nm in the visible light range after coloring and a transmittance of 64% after discoloration. Fig. 6 is a cyclic voltammetry curve of the device prepared in this example, the device has almost unchanged ion storage capacity after 9 ten thousand cycles, and the device cycle life can reach more than 9 ten thousand cycles.
Table 5 example 5 variation of density of electrochromic layer with coating temperature
Note: in table 5, the densities of the tungsten oxide films prepared at the temperatures of 250 ℃, 300 ℃, 350 ℃ and 400 ℃ were calculated, respectively, and the results showed that the higher the temperature was, the higher the density of the tungsten oxide film was, and thus it can be deduced that the tungsten oxide film having a gradually changed density could be prepared by controlling the temperature change during the deposition of tungsten oxide.
Comparative example 1
The substrate 1 is glass; the conducting layer 2 is made of Indium Tin Oxide (ITO) and has the thickness of 300 nm; the electrochromic layer 3 is tungsten oxide (WO)x) The gas pressure during sputtering is 3X 10-3torr, the thickness of tungsten oxide is 700 nm; the bulk material of the ion storage layer 5 is nickel tungsten oxide with a thickness of 320nm, lithium is used as an ion source 51 to ionize the ion storage layer 5, and Indium Tin Oxide (ITO) is deposited on the completely ionized nickel tungsten oxide to form a conductive layer 6 with a thickness of 350 nm.
Vacuum annealing at 400 deg.C for 20min with vacuum degree of 10-6torr, an interfacial region 4 is formed between the electrochromic layer 3 and the ion storage 5.
The tungsten oxide film layer prepared in this example had a density of 7.33g/cm3. The cyclic voltammetry curve of the prepared electrochromic device is shown in figure 7, and the cyclic stability of the device is poor. Over 5000 cycles, the device's ability to store ions has significantly decreased and devices have emergedThe blue color could not be faded after coloring. The devices prepared in this comparative example were significantly less cycle-life than the devices prepared in example 3 with increasing gas pressure during the tungsten oxide preparation. The reason is that the tungsten oxide film layer is relatively dense, when ions migrate back and forth between the ion storage layer and the electrochromic layer under the action of an electric field, the ions are injected and extracted for many times in the electrochromic layer to cause lattice mismatch between the film layers, so that the quality of the film layers is poor, and the service life of the device is influenced.
Claims (10)
1. An all-solid-state electrochromic device comprising a substrate and a multilayer film structure on the same side of the substrate, wherein the multilayer film structure comprises:
two conductive layers, wherein one conductive layer covers the substrate;
an electrochromic layer, an ion conducting layer and an ion storage layer interposed between the two conductive layers; the density of the electrochromic layer tends to become gradually greater in a direction away from the ion storage layer.
2. The all-solid electrochromic device according to claim 1, wherein the material of the electrochromic layer is one or more of tungsten oxide, titanium oxide, vanadium oxide, zirconium oxide, niobium oxide, molybdenum oxide, tantalum oxide.
3. The all-solid electrochromic device according to claim 1, wherein the electrochromic layer has a thickness of 300 to 1000 nm.
4. The all-solid-state electrochromic device according to claim 1, wherein the material of the two conductive layers is one or more of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, nano silver mesh and graphene.
5. The all-solid-state electrochromic device according to claim 1, wherein the ion storage layer comprises a body and an ion source.
6. The all-solid-state electrochromic device according to claim 5, wherein the material of the body is one or more of nickel oxide, cobalt oxide, iron oxide, manganese oxide, chromium oxide, rhodium oxide, iridium oxide, nickel tungsten oxide, nickel vanadium oxide, nickel manganese oxide, nickel aluminum oxide;
the ion source is one or more of hydrogen ions, lithium ions, sodium ions, potassium ions and magnesium ions.
7. The all-solid-state electrochromic device according to claim 5, wherein the thickness of the ion storage layer is 100 to 350 nm; the ion doping amount in the ion storage layer is 0.1-10%.
8. The all-solid electrochromic device according to claim 1, wherein an interface region that blocks the passage of electrons and allows the passage of ions is formed between the ion storage layer and the electrochromic layer.
9. The method for preparing an all-solid-state electrochromic device according to any one of claims 1 to 8, comprising the steps of:
(1) depositing and growing a conductive layer on one side of the substrate;
(2) depositing and growing an electrochromic layer on the conductive layer;
(3) depositing and growing an ionized ion storage layer on the electrochromic layer;
(4) depositing and growing a conductive layer on the ionized ion storage layer;
(5) and carrying out heat treatment after the film coating is finished to obtain the all-solid-state electrochromic device.
10. The method for producing an all-solid electrochromic device according to claim 9, wherein the density of the electrochromic layer in the step (2) is 5.83g/cm3～7.59g/cm3。
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