CN210038407U - All-solid-state electrochromic device and electrochromic glass - Google Patents
All-solid-state electrochromic device and electrochromic glass Download PDFInfo
- Publication number
- CN210038407U CN210038407U CN201920596859.1U CN201920596859U CN210038407U CN 210038407 U CN210038407 U CN 210038407U CN 201920596859 U CN201920596859 U CN 201920596859U CN 210038407 U CN210038407 U CN 210038407U
- Authority
- CN
- China
- Prior art keywords
- layer
- oxide
- solid
- electrochromic device
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The utility model provides an all-solid-state electrochromic device, pile up layer and the compound conducting layer of second including transparent basement, ion barrier layer, first compound conducting layer, EC of superpose in proper order, first compound conducting layer includes the first transparent conductive oxide layer and the first metal level of superpose. The utility model discloses can solve the long white point phenomenon of alleviating and overcoming the color-changing device of discolouring of time.
Description
Technical Field
The utility model relates to a glass technical field that discolours, concretely relates to full solid-state electrochromic device and electrochromic glass.
Background
The electrochromic is a phenomenon that under the action of an external voltage, charged ions and a material are doped and dedoped, so that the metal oxide electrochromic material is subjected to oxidation or reduction reaction, and further optical properties (transmittance, absorptivity and reflectivity) are subjected to reversible change in visible light and infrared regions. The electrochromic glass prepared by utilizing the performance can intelligently control and adjust the transmittance of visible light and infrared rays of solar radiation penetrating through the glass, selectively adjust the infrared radiation entering a room, and reduce the energy consumption of an air conditioner required by cooling a building in summer. At present, the following problems still exist in large-size electrochromic devices at home and abroad: long color change time and slow response speed; the transmittance of the transparent state is low; the emissivity of the EC film layer is low, and if hollow glass with low heat transfer coefficient is required to be obtained, low emissivity glass is required to be matched.
In addition, short circuit white spots sometimes occur in electrochromic devices, i.e., conductive impurities in the film layer locally make electrical connection to the conductive layers on both sides of the EC stack. The ion conducting layer in the EC stack is inherently ion conducting and electronically insulating, but once the conductive impurities cause a short circuit locally in the device, the current increases at the conductive impurities, and the nearby regions do not have sufficient potential to cause lithium ion movement, so the nearby regions no longer participate in the coloration. And with the repeated circulation of the device, the size of a short-circuit point is larger and larger near the conductive impurities due to the repeated burning of the current, and the size of a white point which does not participate in color change visually is also larger and larger. In the prior art, no method for effectively inhibiting the magnitude of the short-circuit white point current exists, and the further expansion of the short-circuit white point cannot be prevented.
SUMMERY OF THE UTILITY MODEL
In order to solve the long white point phenomenon of alleviating and overcoming the color-changing device of discolouring time, the utility model provides a full solid-state electrochromic device and electrochromic glass, concrete technical scheme is as follows:
an all-solid-state electrochromic device comprises a transparent substrate, an ion blocking layer, a first composite conducting layer, an EC stack layer and a second composite conducting layer which are sequentially stacked, wherein the first composite conducting layer comprises a first transparent conducting oxide layer and a first metal layer which are sequentially stacked.
The first composite conductive layer further comprises a first resistive layer disposed on a side of the first metal layer facing the EC stack.
Preferably, the second composite conductive layer includes a third transparent conductive oxide layer, a second metal layer, and a fourth transparent conductive oxide layer stacked in this order.
Preferably, the second composite conductive layer comprises a second metal layer and a fourth transparent conductive oxide layer stacked, wherein the second metal layer is disposed between the EC stack layer and the fourth transparent conductive oxide layer.
Further, the second composite conductive layer further includes a second resistance layer disposed on a side of the second metal layer facing the EC stack layer.
Preferably, the first resistance layer and the second resistance layer are made of transition metal oxide or nitride, and the resistivity of the transition metal oxide or nitride is 1000 Ω · M to 108omega.M, the thickness is 10nm to 1000 nm.
Preferably, the first resistance layer and the second resistance layer are any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide, and molybdenum oxide.
Preferably, the first metal layer and the second metal layer are made of gold, silver, copper or metal alloy, and the thickness of the first metal layer and the second metal layer is 1-30 nm.
The utility model provides an all-solid-state electrochromic device, includes transparent base, ion barrier layer, first compound conducting layer, EC that superpose in proper order and piles up layer and second compound conducting layer, first compound conducting layer is including the first transparent conductive oxide layer, first metal level and the transparent conductive oxide layer of second that superpose in proper order, the compound conducting layer of second includes superpose second resistance layer, second metal level and the transparent conductive oxide layer of fourth.
Further, the first composite conductive layer further comprises a first resistance layer disposed on a side of the first metal layer facing the EC stack layer.
The utility model provides an all-solid-state electrochromic device, includes transparent base, ion barrier layer, first compound conducting layer, EC that superpose in proper order and piles up layer and the compound conducting layer of second, first compound conducting layer is including the first transparent conductive oxide layer, first metal level and the transparent conductive oxide layer of second that superpose in proper order, the compound conducting layer of second includes the second resistance layer of superpose, the transparent conductive oxide layer of third, second metal level and the transparent conductive oxide layer of fourth.
Further, the first composite conductive layer further comprises a first resistance layer disposed on a side of the first metal layer facing the EC stack layer.
An electrochromic glass is characterized by comprising a glass substrate for laminating, a film and the all-solid-state electrochromic device.
According to the above technical scheme, the utility model discloses a stack the layer at conducting layer and EC and set up the resistance layer between, carry out the current regulation to photochromic glass, reduce the current value to reduce the voltage drop of the production of potential distribution in-process on the conducting layer, effectively eliminate the color halo phenomenon.
The composite conductive film layer (DMD) of metal oxide-metal oxide is used for replacing metal conductive oxides such as ITO/FTO and the like commonly adopted by the existing all-solid-state electrochromic device, and the effects of:
1. the sheet resistance of the conductive layer is lower and the color change speed of the EC device is higher under the same transmittance; if the sheet resistance of the conducting layers is the same, the transmittance of the EC device is higher;
2. because the conductivity is enhanced, the electrochromic film layer is endowed with lower radiance and better heat insulation performance;
3. the first resistance layer and/or the second resistance layer with higher resistivity are/is arranged in the composite conductive layer and the EC stacked layer, so that the generation probability of short-circuit white spots can be reduced, the current of the short-circuit white spots can be reduced, and further growth of the short-circuit white spots can be inhibited.
Drawings
FIG. 1 is a schematic structural view of example 1;
FIG. 2 is a schematic structural view of example 2;
FIG. 3 is a schematic structural view of embodiment 3;
FIG. 4 is a schematic structural view of example 4;
FIG. 5 is a schematic structural view of example 5;
fig. 6 is a current trend graph of the all-solid-state electrochromic device of example 4.
Detailed Description
The present invention will be described in detail with reference to the drawings and specific embodiments, wherein prior to describing the technical aspects of the embodiments of the present invention in detail, the terms and the like are explained, and in the present specification, the components with the same names or the same reference numbers represent the similar or the same structures and are only used for illustrative purposes.
The electrical performance of the electrochromic device is abstracted, and the electrochromic device can be abstracted into a series circuit of a resistor and a capacitor. The current passing between the conductive layers can be regarded as a process of passing current through the resistor, while the ion conductive layer in the EC stack is an insulator of an ion conductor and basically an electron, so the EC stack can be regarded as a capacitor.
Suppose the power voltage is Vo, the resistance of the resistor is R, the capacitance of the capacitor is C, the voltage on the two sides of the capacitor is U, and the time is t.
Since the currents through the resistor and the capacitor are equal in the series circuit, there are:
voltage across the capacitor:
the time constant τ of the RC series circuit is RC, and when the time t is 3RC, U is 95% Vo, which can be equivalent to the discoloration time.
A certain point on the color-changing glass needs to go through two electrical processes, the first is a potential distribution process, namely, on the conductive layer, the potential is distributed from strong to weak at the electrode to the point, and then the EC stack layer at the point is subjected to an ion migration process, namely, ions are migrated in the molecules of the color-changing material under the driving of the potential in the direction perpendicular to the conductive layer. One of the main causes of the halo phenomenon is the voltage drop that occurs during the potential distribution on the conductive layer.
In order to reduce this voltage drop, work can be done from two points of view, one being to reduce the resistance of the conductive layer. The calculation formula of the resistance is as follows:
in the formula, rho is the resistivity of the material; l is equal to the length of the conductor in the direction of current flow; s is the cross-sectional area of the conductor perpendicular to the current direction.
Therefore, the closer to the bus bar, the smaller L, the smaller R1The smaller the voltage drop, R1C is small, and the color change time is short. Similarly, the point at the middle of the conductive layer is far from the electrodes at both sides, so that the resistance R is2Larger, R2C is large, so the color change speed is slow. If a material with lower sheet resistance is used as the conductive layer, R is reduced1And R2The color change is not uniform, and the phenomenon of color change is effectively relieved.
In the prior art, the sheet resistance of common ITO can be reduced from 30 omega.M/□ to less than 10 from the viewpoint of sputtering thicker ITO.
In order to further reduce the sheet resistance, the utility model discloses in adopt metal oxide-metal oxide's compound conductive film layer (DMD) to replace metal conductive oxide such as ITO FTO that present all-solid-state electrochromic device generally adopted.
On the other hand, in order to alleviate and overcome the white point phenomenon of the color-changing device, the utility model discloses in set up first resistance layer or/and second resistance layer. The current vertically passes through the high-resistance protective layer, and the resistance layer has the following characteristics:
the resistance of the glass has little influence on large-size electrochromic glass devices, and the color change time is hardly influenced;
the high-resistance layer has a good inhibiting effect on local short circuits.
As will be explained below, it is assumed that the high-resistance protective layer has a thickness of 100nm and a resistivity of 106Ω · M for example, for an electrochromic device of 1M by 1M, according to the formula for the calculation of the resistance:
R＝(ρ*L)/S
in the formula, rho is the resistivity of the material; l is equal to the length of the conductor in the direction of current flow; s is the cross-sectional area of the conductor perpendicular to the current direction. The vertical resistance of the high-resistance protective layer was 0.1 ohm. According to the relationship t of the electrochromic device color changing time and the series resistance being 3RC, the increase of the resistance layer has no obvious influence on the color changing time
If the film structure of the device is locally poor, 1mm is caused2When the local current increases, the resistance of the high-resistance protective layer at the local position becomes 105And ohm can well inhibit the increase of current locally, prevent the further sintering of the film layer and further avoid the further expansion of the short-circuit area.
Example 1
As shown in fig. 1, the all-solid electrochromic device includes a transparent substrate 1, an ion blocking layer 2, a first composite conductive layer 3, an EC stacked layer 4, and a second composite conductive layer 5, which are sequentially stacked.
The first composite conductive layer 3 includes a first transparent conductive oxide layer 31 and a first metal layer 32 stacked in this order, and a first resistance layer 7 may be provided on a side of the first metal layer facing the EC stack layer.
The first resistance layer 7 is made of transition metal oxide or nitride, specifically any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide and molybdenum oxide, and has a resistivity of 1000 Ω · M to 108omega.M, the thickness is 10nm to 1000 nm.
The second composite conductive layer 5 includes a third transparent conductive oxide layer 51, a second metal layer 52, and a fourth transparent conductive oxide layer 53 stacked in this order.
The first transparent conductive oxide layer 31, the second transparent conductive oxide layer 33, the third transparent conductive oxide layer 51 and the fourth transparent conductive oxide layer 53 are made of any one of indium tin oxide, fluorine-doped tin oxide, gallium zinc oxide, gallium indium tin oxide and aluminum zinc oxide, the first metal layer 32 and the second metal layer 52 are made of gold, silver, copper or metal alloy, and the thickness of the first metal layer and the second metal layer is 1-30 nm.
The outer side of the second composite conductive layer 5 is further plated with a protective layer 6, which is made of any one of oxide or nitride of silicon, oxide or nitride of aluminum, and oxide or nitride of titanium. The protective layer has the function of forming an insulating compact structure and slowing down the pollution of water vapor, oxygen and organic molecules to the functional film layer under the protective layer in the processes of storage, processing and transportation.
Example 2
As shown in fig. 2, embodiment 2 differs from embodiment 1 in that: a second resistance layer 8 is disposed between the third transparent conductive oxide layer 51 and the EC stack layer 4. The two metal layers can be the same or different in material, and the four transparent conductive oxide layers can be the same or different in material.
Example 3
As shown in fig. 3, embodiment 3 differs from embodiment 2 in that: the third transparent conductive oxide layer 51 is omitted.
Example 4
As shown in fig. 4, the all-solid electrochromic device includes a transparent substrate 1, an ion blocking layer 2, a first composite conductive layer 3, an EC stacked layer 4, and a second composite conductive layer 5, which are sequentially stacked.
The first composite conductive layer 3 includes a first transparent conductive oxide layer 31, a first metal layer 32, and a second transparent conductive oxide layer 33, which are sequentially stacked.
The second composite conductive layer 5 includes a second resistance layer 8, a second metal layer 52, and a fourth transparent conductive oxide layer 53 stacked in this order.
The first transparent conductive oxide layer 31, the second transparent conductive oxide layer 33 and the fourth transparent conductive oxide layer 53 are made of any one of indium tin oxide, fluorine-doped tin oxide, gallium zinc oxide, gallium indium tin oxide and aluminum zinc oxide, and the first metal layer 32 and the second metal layer 52 are made of gold, silver, copper or metal alloy, and the thickness of the metal alloy is 1-30 nm.
The outer side of the second composite conductive layer 5 is further plated with a protective layer 6, which is made of any one of oxide or nitride of silicon, oxide or nitride of aluminum, and oxide or nitride of titanium. The protective layer has the function of forming an insulating compact structure and slowing down the pollution of water vapor, oxygen and organic molecules to the functional film layer under the protective layer in the processes of storage, processing and transportation.
Example 5
As shown in fig. 5, example 5 differs from example 4 in that: a first resistive layer 7 is arranged between the first composite conductive layer 3 and the EC stack layer 4.
The first resistance layer 7 and the second resistance layer 8 are made of transition metal oxide or nitride, specifically any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide and molybdenum oxide, and the resistivity thereof is 1000 Ω · M to 108omega.M, the thickness is 10nm to 1000 nm.
The two metal layers can be the same or different in material, and the four transparent conductive oxide layers can be the same or different in material.
The utility model discloses electrochromic glass can be applied to different base plates for combination products such as electrochromic doubling glass, electrochromic cavity glass all should regard as within the protection scope of the utility model. The utility model provides electrochromic glass, which comprises a glass substrate for laminating, a film and an all-solid-state electrochromic device in any one of the embodiments 1 to 5.
Fig. 6 shows a current trend diagram for an all-solid-state electrochromic device having a first composite conductive layer 3 and a second composite conductive layer 5, where in an EC device per unit area current first completes the lateral transfer on the second composite conductive layer 5 and then acts vertically through the second resistive layer 8 on the EC stack 4. Namely, resistance R1 in the planar direction of the second composite conductive layer < resistance R2 in the perpendicular direction of the second resistance layer.
R1 < R2, which can be deduced:
W1and W2On the same order of magnitude, approximately divided to yield:
d1and d2Respectively, the thickness of the second composite conductive layer and the second resistance layer, wherein d2Is the distance in the direction of current flow in the resistive layer. Generally on the order of hundreds of nanometers, up to microns, and down to 2 nanometers; l is1And L2Respectively, the lengths of the second composite conductive layer and the second resistance layer, wherein L1The distance in the direction of current flow in the second current layer is typically in the order of centimeters to meters.
ρ1Is a resistivity of ITO, typically 10-6To 10-7In the order of Ω · M.
In summary, the resistivity ρ of the second resistive layer2Should be greater than 1000 Ω. M and less than 108Ω·M。
The above-mentioned embodiments are only to describe the preferred embodiments of the present invention, but not to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art without departing from the design spirit of the present invention should fall into the protection scope defined by the claims of the present invention.
Claims (13)
1. The all-solid-state electrochromic device is characterized by comprising a transparent substrate, an ion barrier layer, a first composite conducting layer, an EC stack layer and a second composite conducting layer which are sequentially stacked, wherein the first composite conducting layer comprises a first transparent conducting oxide layer and a first metal layer which are stacked.
2. The all-solid-state electrochromic device according to claim 1, wherein the first composite conductive layer further comprises a first resistive layer disposed on a side of the first metal layer facing the EC stack.
3. The all-solid electrochromic device of claim 1, wherein the second composite conductive layer comprises a third transparent conductive oxide layer, a second metal layer, and a fourth transparent conductive oxide layer stacked in this order.
4. The all-solid-state electrochromic device of claim 1, the second composite conductive layer comprising a second metal layer and a fourth transparent conductive oxide layer in a stack, wherein the second metal layer is disposed between the EC stack and the fourth transparent conductive oxide layer.
5. The all-solid-state electrochromic device according to claim 2, the second composite conductive layer further comprising a second resistive layer disposed on a side of the second metal layer facing the EC stack.
6. The all-solid electrochromic device according to claim 5, wherein the first and second resistive layers are made of transition metal oxide or nitride, and have a resistivity of 1000 Ω, M to 10 Ω8Omega, M, the thickness is 10 nm-1000 nm.
7. The all-solid electrochromic device according to claim 5, wherein the first and second resistance layers are any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide, and molybdenum oxide.
8. The all-solid-state electrochromic device according to claim 3 or 4, wherein the first metal layer and the second metal layer are made of gold, silver, copper or metal alloy, and the thickness of the first metal layer and the second metal layer is 1-30 nm.
9. The all-solid-state electrochromic device is characterized by comprising a transparent substrate, an ion barrier layer, a first composite conducting layer, an EC stack layer and a second composite conducting layer which are sequentially superposed, wherein the first composite conducting layer comprises a first transparent conducting oxide layer, a first metal layer and a second transparent conducting oxide layer which are sequentially superposed, and the second composite conducting layer comprises a second resistance layer, a second metal layer and a fourth transparent conducting oxide layer which are superposed.
10. The all-solid-state electrochromic device according to claim 9, wherein the first composite conductive layer further comprises a first resistive layer disposed on a side of the first metal layer facing the EC stack.
11. The all-solid-state electrochromic device is characterized by comprising a transparent substrate, an ion barrier layer, a first composite conducting layer, an EC stack layer and a second composite conducting layer which are sequentially superposed, wherein the first composite conducting layer comprises a first transparent conductive oxide layer, a first metal layer and a second transparent conductive oxide layer which are sequentially superposed, and the second composite conducting layer comprises a second resistance layer, a third transparent conductive oxide layer, a second metal layer and a fourth transparent conductive oxide layer which are superposed.
12. The all-solid-state electrochromic device according to claim 11, wherein the first composite conductive layer further comprises a first resistive layer disposed on a side of the first metal layer facing the EC stack.
13. An electrochromic glass comprising a glass substrate for laminating, a film and an all-solid electrochromic device according to any one of claims 1 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920596859.1U CN210038407U (en) | 2019-04-28 | 2019-04-28 | All-solid-state electrochromic device and electrochromic glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920596859.1U CN210038407U (en) | 2019-04-28 | 2019-04-28 | All-solid-state electrochromic device and electrochromic glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN210038407U true CN210038407U (en) | 2020-02-07 |
Family
ID=69362507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201920596859.1U Active CN210038407U (en) | 2019-04-28 | 2019-04-28 | All-solid-state electrochromic device and electrochromic glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN210038407U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180500A (en) * | 2020-02-26 | 2020-05-19 | 京东方科技集团股份有限公司 | Display substrate and electroluminescent display device |
-
2019
- 2019-04-28 CN CN201920596859.1U patent/CN210038407U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180500A (en) * | 2020-02-26 | 2020-05-19 | 京东方科技集团股份有限公司 | Display substrate and electroluminescent display device |
| CN111180500B (en) * | 2020-02-26 | 2023-10-24 | 京东方科技集团股份有限公司 | Display substrate and electroluminescent display device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1359626B1 (en) | Substrate for transparent electrodes | |
| EP2100335B1 (en) | Zinc oxide based front electrode doped with yttrium for use in photovoltaic device or the like | |
| US8102587B2 (en) | Electrochromic device having controlled infrared reflection | |
| US20080169021A1 (en) | Method of making TCO front electrode for use in photovoltaic device or the like | |
| Higuchi et al. | Largest highly efficient 203× 203 mm2 CH3NH3PbI3 perovskite solar modules | |
| KR101352779B1 (en) | Transparent electrode for solar cell and method for preparing the same | |
| EP2994946B1 (en) | Method of manufacturing photovoltaic device using perovskites | |
| US20080223430A1 (en) | Buffer layer for front electrode structure in photovoltaic device or the like | |
| KR102072882B1 (en) | Conductive structure and electrochromic device comprising same | |
| CN105552231A (en) | Perovskite solar cell and preparation method therefor | |
| CN202153290U (en) | Electrochromic device with multiple ionic conduction layers and optical property adjustable device | |
| JP2011222167A (en) | Transparent conducting film and photoelectric conversion device | |
| US20110108104A1 (en) | Photoelectric conversion device | |
| CN210038407U (en) | All-solid-state electrochromic device and electrochromic glass | |
| JP2000285974A (en) | Photosensitized photovolatic power generation element | |
| Meng et al. | Flexible smart photovoltaic foil for energy generation and conservation in buildings | |
| CN208737169U (en) | A kind of electrochomeric glass with resistive layer, doubling glass, hollow glass | |
| JP2010517313A (en) | Translucent crystalline silicon thin film solar cell | |
| CN210038408U (en) | All-solid-state electrochromic device and electrochromic glass | |
| Iencinella et al. | Thin-film solar cells on commercial ceramic tiles | |
| JP2015195341A (en) | Photoelectric conversion element and method of manufacturing photoelectric conversion element | |
| KR20150105798A (en) | Transparent electrode and manufacturing method thereof | |
| JP2008077924A (en) | Photoelectric converter | |
| CN210742648U (en) | Composite conductive substrate, all-solid-state electrochromic device and electrochromic glass | |
| Abrol et al. | Selection of glass substrates to be used as electrodes in dye-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant |