CN108254989A - Full-solid electrochromic window and solid-state electrochromic mirror and preparation method thereof - Google Patents
Full-solid electrochromic window and solid-state electrochromic mirror and preparation method thereof Download PDFInfo
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- CN108254989A CN108254989A CN201611244662.9A CN201611244662A CN108254989A CN 108254989 A CN108254989 A CN 108254989A CN 201611244662 A CN201611244662 A CN 201611244662A CN 108254989 A CN108254989 A CN 108254989A
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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
- G02F1/1506—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
- G02F1/1508—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
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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
Abstract
The present invention relates to a kind of solid electrolyte material, chemical composition is：LixSiyRezSmOnWherein 2≤x≤3,0.5≤y≤2,0.3≤z≤0.6, (x+4y+3z)/2.1≤m+n≤(x+4y+3z)/1.8, Re is selected from rare earth element y, Gd, Gy or Sm, and the lithium ion conductivity of solid electrolyte material of the invention is high, electron conductivity is low, electrochemical window mouth width and temperature tolerance are good；The invention further relates to solid-state electrochromic devices, its electrolyte is selected from above-mentioned solid electrolyte material, electrochromic layer is selected from least one of tungsten oxide, bismuth oxide, molybdenum trioxide or nickel oxide, ion storage is selected from least one of embedding lithium vanadic anhydride, embedding lithium titanium dioxide, embedding lithium tungstic acid or embedding lithium nickel oxide, and solid-state electrochromic device of the invention has the advantages that the discoloration response time is short and performance is stablized.
Description
Technical field
The present invention relates to electrochromism fields, relate more particularly to the solid state electrolysis material of full-solid electrochromic device
Material, solid-state electrochromic window and solid-state electrochromic mirror and preparation method thereof.
Background technology
Electrochromism refers to material under DC Electric Field, produces and is sent out inside redox reaction or molecular structure
Charge is given birth to（Electronics or ion）Injection or extraction variation, optical property such as transmissivity so as to cause material absorb
Reversible variation occurs in the regions such as visible ray, infrared light or ultraviolet light for rate and reflectivity etc..The technology is in building glass, vehicle
With fields such as intelligent color-changing window, aircraft windows, color-changing solar glasses, the anti-string mesh rearview mirror of automobile, presentation of information and military technologies
With very important application value.
Typical full-solid electrochromic device composition includes：（1）Substrate is the outermost layer of electrochromic device, is made
With being support and device inner layers protected not to be affected by, the generally flexible substrates of transparence or common glass
Glass；（2）Conductive layer, the electrode material as electrochromic device are connect with additional driving electric field；（3）Electrochromic layer, also known as
Working electrode is responsible for electrochromic process；（4）Ion storage layer, also known as to electrode, for assist electrochromic layer dead electricity
Subprocess, to play the role of balancing charge, can also be used with stronger ion storage ability electrochromic material be used as from
Sub- accumulation layer, so as to strengthen the color of the modulation depth of spectrum, the coloration efficiency of raising device or abundant device；（5）Electrolysis
Matter layer plays transmission ion between electrochromic layer and ion storage（Such as H+、 Li+、Na+）And the effect of barrier electronics.
Important composition of the electrolyte layer as electrochromic device, it will not only ensure required during electrochromic material discoloration
Ion channel, also to ensure not form short circuit between positive and negative anodes.It sums up, electrolyte layer need to have following property：（1）From
Sub- conductivity is high, to realize the migration of ion and transmission；（2）Electron conductivity is low, to reduce direct electron electric current in device；
（3）With enough physics and chemical stability, do not occur in whole work process with other functional layers or external environment
Side reaction；（4）Electrochemical stability is good, to ensure that electrochromic device can be in outer steady operation under adding driving electric field；（5）Have
Higher mechanical strength, film forming and adhesiveness is good, with ensure electrochromic device easy processing, should not come off, impact resistance, the service life
It is long；（6）Manufacture it is of low cost, be easy to market exploitation；（7）It is safe and non-toxic.
Solid lithium ion conductive electrolyte is widely studied in full-solid electrochromic device, but also there are lithium from
Sub- conductivity is low（Influence discoloration rate）And cyclical stability it is poor the deficiencies of.For example the preparation structures such as Cogan are [glass（Lining
Bottom）/ tin indium oxide（Transparency conducting layer）/LixLiyCrO2+x（Ion storage）/Li2O-B2O3（Electrolyte layer）/ tungstic acid
（Electrochromic layer）/ tin indium oxide（Transparency conducting layer）] electrochromic device, colour fading conversion time up to more than ten seconds
It is significantly reduced to a few minutes, and with the colour fading switch speed that increases of cycle-index, the reason is that electrolyte Li2O-B2O3's
Lithium ion conductivity is only 10-9S/cm and by micro-moisture influenced significantly (Cogan SF, Rauh RD, Klein JD,
Nguyen NM, Jones RB, Plant TD. Variable transmittance coatings using
electrochromic lithium chromate and amorphous WO3 thin films. J. Flectrochem.
Soc., 1997, 144(3):956-960)；[glass is made by magnetron sputtering in Wu etc.（Substrate）/ tin indium oxide（Electrically conducting transparent
Layer）/ tungstic acid（Electrochromic layer）/LiNbO3（Electrolyte layer）/ nickel oxide（Ion storage）/ tin indium oxide（It is transparent to lead
Electric layer）] structure electrochromic device, electrolyte LiNbO3Ionic conductivity be 2 × 10-7S/cm, electron conductivity 2
×10-11S/cm, the device coloring process and colour fading process also need tens of seconds（Wu Zhonghou, Diao Xungang,
Dong Guobo . Preparation and properties of all-solid-state inorganic thin
film glass/ITO/WO3/LiNbO3/NiOx/ITO electrochromic device. *Proc. of SPIE Vol.
9796 979612-1）.
Invention content
For the deficiency of above-mentioned technology, the present invention provides a kind of solid state electrolysis materials of full-solid electrochromic device
Material.In addition, the present invention also provides solid-state electrochromic windows and solid-state electrochromic mirror comprising the solid electrolyte material；
And the preparation method of solid-state electrochromic window and solid-state electrochromic mirror.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of solid electrolyte material of full-solid electrochromic device has following chemical expression：LixSiyRezSmOn,
In 2≤x≤3,0.5≤y≤2,0.3≤z≤0.6, (x+4y+3z)/2.1≤m+n≤(x+4y+3z)/1.8, Re be selected from rare earth
At least one of element Y, Gd, Gy or Sm.
Lithium ion conductivity is more than 7 × 10 to the solid electrolyte material at room temperature-5S/cm, electron conductivity are less than
10-13S/cm, electrochemical window is higher than 5.7 V and can stablize use in 40 ~ 210 oC temperature ranges.
The present invention also provides a kind of using full-solid electrochromic device made from the solid electrolyte material.It is described
Full-solid electrochromic device be, for example, build gradual change glass, vehicle intelligent color-changing window, aircraft windows, color-changing solar glasses,
The anti-string mesh rearview mirror of automobile.In addition, also solid electrolyte material of the present invention can be prepared presentation of information and military technology
The electrochromic device in the fields of grade.
The present invention also provides a kind of solid-state electrochromic windows, are followed successively by substrate, the first conductive layer, electrochromic layer, electrolysis
Matter layer, ion storage and the second conductive layer；The electrolyte layer uses the solid electrolyte material.
Preferably, in the solid-state electrochromic window, the Re in the electrolyte layer is selected from rare earth element y or Sm.
In the solid-state electrochromic window, first conductive layer and the second conductive layer are selected from transparent conductive material,
Preferably tin oxide, zinc oxide, indium tin oxide target, indium gallium zinc complexes, fluorine doped tin oxide, Al-Doped ZnO and fluorine doped oxidation
At least one of zinc composition.
In the solid-state electrochromic window, the electrochromic layer for tungstic acid, bismuth oxide, molybdenum trioxide or
At least one of nickel oxide composition.
In the solid-state electrochromic window, the ion storage is embedding lithium vanadic anhydride, embedding lithium titanium dioxide, embedding
At least one of lithium tungstic acid or embedding lithium nickel oxide composition.
The preparation method of the solid-state electrochromic window is sequentially deposited to form the first conductive layer, electroluminescent in substrate surface
Photochromic layer, electrolyte layer, ion storage and the second conductive layer deposit in reverse order.
The deposition method can choose existing conventional corresponding deposition method according to the material characteristic of each layer.
The preparation method of the solid-state electrochromic window, specifically includes following steps：
Step (1)：On substrate deposited oxide tin, zinc oxide, indium tin oxide target, indium gallium zinc complexes, fluorine doped tin oxide, mix
Aluminum zinc oxide or fluorine doped zinc oxide form the first conductive layer；The thickness of first conductive layer is 50-200 nm；
Step (2)：It is formed in the first conductive layer surface deposition tungstic acid, bismuth oxide, molybdenum trioxide or nickel oxide electroluminescent
Photochromic layer；The thickness of the electrochromic layer is 100-500 nm；
Step (3)：Li is deposited in electrochromism layer surfacexSiyRezSmOnForm electrolyte layer；The thickness of the electrolyte layer
For 200-800 nm；
Step (4)：Embedding lithium vanadic anhydride, embedding lithium titanium dioxide, embedding lithium tungstic acid are deposited in the electrolyte layer surface of formation
Or embedding lithium nickel oxide, form ion storage；The thickness of the ion storage is 100-500 nm；
Step (5)：It is compound in ion storage layer surface deposited oxide tin, zinc oxide, indium tin oxide target, the indium gallium zinc of formation
Object, fluorine doped tin oxide, Al-Doped ZnO or fluorine doped zinc oxide form the second conductive layer；The thickness of second conductive layer is 50-200
nm。
The substrate can be transparent high-molecular organic material or inorganic material.Preferably, substrate is glass.
The solid-state electrochromic window can be applied to building glass, aircraft and vehicle intelligent color-changing window, optical filter, decoration material
The application fields such as material, stealth material, color-changing solar glasses, presentation of information.
The present invention also provides a kind of solid-state electrochromic mirrors, are sequentially substrate, conductive reflective, the first conductive layer, electroluminescent
Photochromic layer, electrolyte layer, ion storage and the second conductive layer, the electrolyte layer are selected from the solid state electrolysis material
Material.
Preferably, in the solid-state electrochromic mirror, the Re in the electrolyte layer be selected from rare earth element y or
Sm。
In the solid-state electrochromic mirror, first conductive layer and the second conductive layer be it is transparent, preferably
In tin oxide, zinc oxide, indium tin oxide target, indium gallium zinc complexes, fluorine doped tin oxide, Al-Doped ZnO and fluorine doped zinc oxide
At least one is formed.
In the solid-state electrochromic mirror, the conductive reflective is formed for noble metal and precious metal alloys.
Preferably, the conductive reflective for silver layer, platinum layer or silver with gold, chromium, ruthenium, platinum, rhodium, lawrencium, palladium in extremely
A kind of few alloy-layer of formation.
In the solid-state electrochromic mirror, the electrochromic layer for tungsten oxide, bismuth oxide, molybdenum trioxide or
At least one of nickel oxide composition.
In the solid-state electrochromic mirror, the ion storage for embedding lithium vanadic anhydride, embedding lithium titanium dioxide,
At least one of embedding lithium tungstic acid or embedding lithium nickel oxide composition.
The preparation method of the solid-state electrochromic mirror, is sequentially deposited to form the first conductive layer, conduction in substrate surface
Reflecting layer, electrochromic layer, electrolyte layer, ion storage and the second conductive layer；Or first is sequentially depositing in substrate and is led
Electric layer, conductive reflective, ion storage, electrolyte layer, electrochromic layer and the second conductive layer.
The deposition method can choose existing conventional corresponding deposition method according to the material characteristic of each layer.
The preparation method of the solid-state electrochromic mirror, specifically includes following steps：
Step (1)：Deposition of silver, platinum or the silver-colored alloy at least one with gold, chromium, ruthenium, platinum, rhodium, lawrencium, palladium on substrate, shape
Into conductive reflective；The thickness of the conductive reflective is 10-100 nm；
Step (2)：Deposited oxide tin, zinc oxide, indium tin oxide target, indium gallium zinc complexes, fluorine doped oxygen in conductive reflective
Change tin, Al-Doped ZnO or fluorine doped zinc oxide and form the first conductive layer；The thickness of first conductive layer is 50-200 nm；
Step (3)：At least one in the first conductive layer surface deposited oxide tungsten, bismuth oxide, molybdenum trioxide or nickel oxide
Kind forms electrochromic layer；The thickness of the electrochromic layer is 100-500 nm；
Step (4)：Li is deposited in electrochromic layerxSiyRezSmOnForm electrolyte layer；The thickness of the electrolyte layer is
200-800 nm；
Step (5)：Embedding lithium vanadic anhydride, embedding lithium titanium dioxide, embedding lithium tungstic acid are deposited in the electrolyte layer surface of formation
Or embedding lithium nickel oxide, form ion storage；The thickness of the ion storage is 100-500 nm；
Step (6)：It is compound in ion storage layer surface deposited oxide tin, zinc oxide, indium tin oxide target, the indium gallium zinc of formation
Object, fluorine doped tin oxide, Al-Doped ZnO or fluorine doped zinc oxide form the second conductive layer；The thickness of second conductive layer is
50-200 nm。
In the solid-state electrochromic mirror, the substrate can be high-molecular organic material, glass, ceramics, metal etc.
Material.Preferably, substrate is glass.
The solid-state electrochromic mirror can be applied to the application fields such as the anti-string mesh rearview mirror of automobile.
Compared with prior art, beneficial effects of the present invention are：
The present invention uses LixSiyRezSmOn（2≤x≤3,0.5≤y≤2,0.3≤z≤0.6, (x+4y+3z)/2.1≤m+n≤
(x+4y+3z)/1.8, Re is selected from rare earth element y, Gd, Gy or Sm）As the electrolyte layer in solid-state electrochromic device, lithium
Ionic conductivity is high, electron conductivity is low, electrochemical window mouth width and temperature tolerance are good, so as to significantly improve solid-state electrochromic device
Fade rates and cycle life.The solid-state electrochromic window of the present invention and the colored state of solid-state electrochromic mirror are with taking off
The transition response time between color state is less than 0.5 second.Voltage is alternately applied to electrochromic device（Forward and reverse voltage respectively stops
10 seconds）To realize that it is persistently converted between colored state and bleached state, after recycling 10000 times, solid-state electrochromic window
The difference of visible light transmittance and initial value is less than 4% under colored state, and the difference of visible light transmittance and initial value is small under bleached state
In 3%；After recycling 10000 times, the difference of visible reflectance and initial value is less than 4% under solid-state electrochromic mirror colored state,
The difference of visible reflectance and initial value is less than 4% under bleached state, shows splendid stability.
Specific embodiment：
The present invention is described in further detail below in conjunction with specific embodiment, it is necessary to be pointed out that the present embodiment is served only for pair
The present invention is further detailed, it is impossible to be interpreted as limiting the scope of the invention.
Embodiment 1
Structure for [glass substrate/conductive indium-tin oxide layer/embedding lithium vanadic anhydride ion storage/
Li2.4Si0.6Y0.4S2.4O0.8Electrolyte layer/tungstic acid electrochromic layer/conductive indium-tin oxide layer] electrochromic
Preparation method：With by 10 wt%SnO2With 90 wt%In2O3The ceramics sintered into are target, pass through radio-frequency magnetron sputter method
The conductive indium-tin oxide layer that plating a layer thickness is 150 nm on a glass substrate；Using vanadium metal as target, in argon gas and oxygen
Mixed gas（Flow-rate ratio is 1：9）Under, a layer thickness is plated as 200 nm on conductive indium-tin oxide layer by rf magnetron sputtering
Vanadic anhydride, then embedding lithium vanadic anhydride ion is made by vanadic anhydride by the thermal evaporation of lithium metal under vacuum and is deposited
Reservoir；With Li2.4Si0.6Y0.4S2.4O0.8For target, sunk in embedding lithium vanadic anhydride ion storage by rf magnetron sputtering
The electrolyte layer that product thickness is 600 nm；Using tungstic acid ceramics as target, sunk on the electrolyte layer by rf magnetron sputtering
The tungstic acid electrochromic layer that product thickness is 400 nm；Finally, by radio-frequency magnetron sputter method in tungstic acid electrochromism
The conductive indium-tin oxide layer that a layer thickness is 150 nm is plated on layer.
Performance characterization：Apply forward and reverse 1.5 V of voltage to above-mentioned electrochromic, visible light-transmissive under initial colored state
Rate is 15%, and color is navy blue；Visible light transmittance is 77% under initial bleached state, and color is light blue；Colored state with
Conversion time between bleached state is 0.3 second.Apply forward and reverse 1.5 V of voltage repeatedly to above-mentioned electrochromic（It is forward and reverse
Voltage respectively stops 10 seconds）Its persistent loop between bleached state and colored state is converted, after 10000 cycles, coloring
Visible light transmittance is 16% under state, and color is navy blue；Visible light transmittance is 75% under bleached state, and color is light blue
Color；Conversion time between colored state and bleached state is 0.3 second.
Embodiment 2
Structure for [glass substrate/Al-Doped ZnO conductive layer/embedding lithium tungstic acid ion storage/
Li2.4Si0.6Sm0.6S3.1O0.4Electrolyte layer/electro-allochromatic nickel oxide layer/Al-Doped ZnO conductive layer] electrochromic
Preparation method：With by (1-x) ZnO+xAl2O3（x = 2 wt%）The ceramics sintered into are target, are splashed by radio frequency magnetron
It penetrates method and plates the Al-Doped ZnO conductive layer that a layer thickness is 150 nm on a glass substrate；Using tungstic acid ceramics as target, lead to
It crosses rf magnetron sputtering and the tungstic acid that a layer thickness is 200 nm is plated on Al-Doped ZnO conductive layer, then by vacuum
Embedding lithium tungstic acid ion storage is made in the thermal evaporation of lower lithium metal；With Li2.4Si0.6Sm0.6S3.1O0.4For target, by penetrating
The electrolyte layer that frequency magnetron sputtering deposition thickness in embedding lithium tungsten ion accumulation layer is 400 nm；Using nickel oxide as target,
Pass through the rf magnetron sputtering electrochromic layer that deposition thickness is 400 nm on the electrolyte layer；Finally, it is splashed by radio frequency magnetron
It penetrates method and the Al-Doped ZnO conductive layer that a layer thickness is 150 nm is plated on electrochromic layer.
Performance characterization：Apply forward and reverse 1.8 V of voltage to above-mentioned electrochromic, visible light-transmissive under initial colored state
Rate is 12%, and color is navy blue；Visible light transmittance is 81% under initial bleached state, and color is transparent；Colored state is with taking off
Conversion time between color state is 0.2 second.Apply forward and reverse 1.8 V of voltage repeatedly to above-mentioned electrochromic（Forward and reverse electricity
Press each stop 10 seconds）Its persistent loop between colour fading and coloured state is converted, it, can under colored state after 10000 cycles
It is 13% to see light transmission rate, and color is navy blue；Visible light transmittance is 79% under bleached state, and color is transparent；Colored state
Conversion time between bleached state is 0.3 second.
Embodiment 3
Structure for [glass substrate/reflective silver layer/conductive indium-tin oxide layer/embedding lithium vanadic anhydride ion storage/
Li2SiY0.3S3.1O0.2Electrolyte layer/tungstic acid electrochromic layer/conductive indium-tin oxide layer] EC mirror
Preparation method：Using metallic silver as target, the silver that a layer thickness is 70 nm is plated on a glass substrate by rf magnetron sputtering
Reflecting layer；With by 10 wt%SnO2With 90 wt%In2O3The ceramics sintered into are target, by radio-frequency magnetron sputter method silver-colored anti-
The conductive indium-tin oxide layer for plating that a layer thickness is 150 nm is penetrated on layer；Using vanadium metal as target, in argon gas and the gaseous mixture of oxygen
Body（Flow-rate ratio is 1：9）Under, five oxygen that a layer thickness is 200 nm are plated on conductive indium-tin oxide layer by rf magnetron sputtering
Change two vanadium, then embedding lithium vanadic anhydride ion storage is made by vanadic anhydride by the thermal evaporation of lithium metal under vacuum；
With Li2SiY0.3S3.1O0.2For target, by rf magnetron sputtering, deposition thickness is in embedding lithium vanadic anhydride ion storage
The electrolyte layer of 400 nm；Using tungstic acid ceramics as target, by rf magnetron sputtering, deposition thickness is on the electrolyte layer
The tungstic acid electrochromic layer of 400 nm；Finally, by radio-frequency magnetron sputter method one is plated on tungstic acid electrochromic layer
Layer thickness is the conductive indium-tin oxide layer of 150 nm.
Performance characterization：Apply forward and reverse 1.5 V of voltage to above-mentioned EC mirror, visible reflectance under initial colored state
Rate is 11%, and visible reflectance is 63% under initial bleached state, and the conversion time between colored state and bleached state is 0.3
Second.Apply forward and reverse 1.5 V of voltage repeatedly to above-mentioned EC mirror（Forward and reverse voltage respectively stops 10 seconds）Make its fade and
Persistent loop is converted between coloured state, and after 10000 cycles, visible reflectance is 13% under colored state, under bleached state
Visible reflectance is 60%, and the conversion time between colored state and bleached state is 0.3 second.
Claims (7)
1. a kind of solid electrolyte material of full-solid electrochromic device, which is characterized in that there is following chemical expression：
LixSiyRezSmOn, wherein 2≤x≤3,0.5≤y≤2,0.3≤z≤0.6, (x+4y+3z)/2.1≤m+n≤(x+4y+3z)/
1.8, Re selected from least one of rare earth element y, Gd, Gy or Sm.
2. a kind of solid-state electrochromic window is followed successively by substrate, the first conductive layer, electrochromic layer, electrolyte layer, ion storage
With the second conductive layer；It is characterized in that, the electrolyte layer uses solid electrolyte material described in claim 1.
3. solid-state electrochromic window according to claim 2, which is characterized in that first conductive layer and the second conduction
Layer is tin oxide, zinc oxide, tin indium oxide, indium gallium zinc complexes, fluorine doped tin oxide, Al-Doped ZnO and fluorine doped oxygen alone
Change at least one of zinc composition；
The electrochromic layer is at least one of tungsten oxide, bismuth oxide, molybdenum trioxide or nickel oxide composition；
The ion storage is in embedding lithium vanadic anhydride, embedding lithium titanium dioxide, embedding lithium tungstic acid or embedding lithium nickel oxide
At least one form.
4. a kind of preparation method of claim 2-3 any one of them solid-state electrochromic window, which is characterized in that in substrate table
Face is sequentially deposited to form the first conductive layer, electrochromic layer, electrolyte layer, ion storage and the second conductive layer or according to phase
Reverse-order deposits.
5. a kind of solid-state electrochromic mirror is sequentially substrate, conductive reflective, the first conductive layer, electrochromic layer, electrolyte
Layer, ion storage and the second conductive layer, which is characterized in that the electrolyte layer is using solid-state described in claim 1 electricity
Solve material.
6. solid-state electrochromic mirror according to claim 5, which is characterized in that first conductive layer and the second conduction
Layer is tin oxide, zinc oxide, tin indium oxide, indium gallium zinc complexes, fluorine doped tin oxide, Al-Doped ZnO and fluorine doped oxygen alone
Change at least one of zinc composition；
The conductive reflective is formed for noble metal or precious metal alloys；
The electrochromic layer is at least one of tungsten oxide, bismuth oxide, molybdenum trioxide or nickel oxide composition；
The ion storage is in embedding lithium vanadic anhydride, embedding lithium titanium dioxide, embedding lithium tungstic acid or embedding lithium nickel oxide
At least one form.
7. according to the preparation method of claim 5-6 any one of them solid-state electrochromic mirrors, which is characterized in that in substrate table
Face is sequentially deposited to form conductive reflective, the first conductive layer, electrochromic layer, electrolyte layer, ion storage and the second conduction
Layer is deposited according to reverse order.
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| CN109683418A (en) * | 2019-01-10 | 2019-04-26 | 五邑大学 | A kind of smart window and its manufacturing method |
| CN111142304A (en) * | 2019-12-25 | 2020-05-12 | 宁波祢若电子科技有限公司 | All-solid-state electrochromic device and manufacturing method thereof |
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