CN110032018A - The full-solid electrochromic device of aluminium lithium alloy solid ionic conducting shell and preparation method thereof and the contained solid ionic conducting shell - Google Patents
The full-solid electrochromic device of aluminium lithium alloy solid ionic conducting shell and preparation method thereof and the contained solid ionic conducting shell Download PDFInfo
- Publication number
- CN110032018A CN110032018A CN201810031717.0A CN201810031717A CN110032018A CN 110032018 A CN110032018 A CN 110032018A CN 201810031717 A CN201810031717 A CN 201810031717A CN 110032018 A CN110032018 A CN 110032018A
- Authority
- CN
- China
- Prior art keywords
- solid
- conducting shell
- ionic conducting
- layer
- solid ionic
- 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.)
- Granted
Links
Classifications
-
- 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
- G02F1/1525—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 characterised by a particular ion transporting layer, e.g. electrolyte
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The present invention relates to the full-solid electrochromic devices of aluminium lithium alloy solid ionic conducting shell and preparation method thereof and the contained solid ionic conducting shell.The chemical composition of the solid ionic conducting shell is aluminium lithium alloy Al x Li, wherein 0 < x < 1.Solid ionic conducting shell of the invention is cheap and easy to get, can be used for the conducting lithium ions between the first photochromic layer and the second photochromic layer of electrochromic device and realizes electrochromism, improves ion in the conductivity and conduction of velocity of two discoloration interlayers.
Description
Technical field
The present invention relates to field of material technology, in particular to a kind of solid ion conducting layer material all solid state electricity corresponding to its
Mutagens color device and preparation method are mainly used for the application fields such as electrochomeric glass, moving body window and device.
Background technique
Ion conducting layer can be divided into solution-type, gel-type, solid-state version etc. according to the form of thin-film material.It is compared to packet
The problem of electrochromic device containing solution-type and gel-type is because of poor adhesive force, easily leakage, solid ionic conducting shell more possesses
Researching value.The electrochromic device that ion conducting layer and film containing solid-state form constitute all solids is known as total solids
Electrochromic device generally includes cathode, the first photochromic layer, ion conducting layer, the second photochromic layer, dielectric layer and anode.Such as
Shown in Fig. 1, previous total solids electrochomeric glass includes: substrate 100, the first conductive layer being set in turn on substrate 100
110, the first photochromic layer 120, ion conducting layer 130, the second photochromic layer 140, dielectric layer 150, the second conductive layer 160.
Solid ionic conduction layer material is prepared by radio-frequency power supply magnetron sputtering.And adequate thickness and dielectric layer are required to improve
Ionic conductivity.Such as: lithium tantalate, lanthanium titanate lithium, lithium metasilicate, lithium aluminate, lithium aluminosilicate, lithium chromate, sulfuric acid boron lithium, lithium vanadate or
Lithium tantalate etc..For usual this preparation method there are required preparation time is long, sputtering raste is low, and ion, which mutually spread, many ask such as is lost
Topic.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide one kind can also keep away even if under relatively small thickness
Exempt from the loss of the ion in photochromic layer caused by the counterdiffusion between cathode or anode material and photochromic layer, improves ion at two
The conductivity of interlayer that changes colour and the solid ionic conducting shell and preparation method thereof of conduction of velocity and contain the solid ionic conducting shell
Full-solid electrochromic device.
In a first aspect, the present invention provides a kind of solid ionic conducting shell, the chemical composition of the solid ionic conducting shell is
Aluminium lithium alloy AlxLi, wherein 0 < x < 1.
Solid ionic conducting shell of the invention is cheap and easy to get, can be used in the first photochromic layer of electrochromic device and second
Conducting lithium ions realize electrochromism between photochromic layer, improve ion in the conductivity and conduction of velocity of two discoloration interlayers, add
It the response time of fast electrochromic device, can avoid between cathode or anode material and photochromic layer under relatively small thickness
The loss of ion in photochromic layer caused by counterdiffusion, stability are high, can be used in automobile anti-glazing rearview mirror, automobile peak window with
And on side window, Energy-saving Building Glass, other moving body vehicle windows, display screen, Electronic Paper, it is stealthy camouflage etc. fields.
Preferably, the solid ionic conducting shell is transparent film layer, it is preferable that the transmitance of the solid ionic conducting shell
90% or more.
Preferably, the sheet resistivity of the solid ionic conducting shell is not less than 100k Ω/m2。
Preferably, the thickness of the solid ionic conducting shell is in 10~500nm, preferably 10~100nm.
Second aspect, the present invention provide the preparation method of above-mentioned solid ionic conducting shell, using aluminium lithium alloy be target with
DC power supply magnetron sputtering preparation, wherein base vacuum is 1 × 10-4~5 × 10-2Pa, preferably 5 × 10-4~5 × 10-3Pa,
Base reservoir temperature is 0~200 DEG C, and preferably 20~70 DEG C, plated film time is 20s~1h, and operating air pressure is 0.5~5Pa, preferably
1Pa~3Pa, sputtering work atmosphere are argon gas, and Sputtering power density is 0.5~3.0W/cm2。
5th aspect, the present invention provide a kind of full-solid electrochromic device comprising substrate；And it is set in turn in institute
State the first conductive layer, the first photochromic layer, above-mentioned solid ionic conducting shell, the second photochromic layer, the second conductive layer on substrate.
Full-solid electrochromic device of the invention contains by aluminium lithium alloy AlxLi constitute transparent film layer as solid-state from
Ionic conductivity and ion conduction rate can be improved in sub- conducting shell, can avoid cathode or anode material under relatively small thickness
The loss of ion in photochromic layer caused by counterdiffusion between material and photochromic layer, stability is high, can be used in automobile anti-glazing backsight
Mirror, automobile peak window and side window, Energy-saving Building Glass, on other moving body vehicle windows, it is display screen, Electronic Paper, stealthy
The fields such as camouflage.
Preferably, also there is protective layer in the outside of second conductive layer.
Preferably, the protective layer is SiAlNxOyTransparent thin-film material, metal-oxide film material or transparent height
Molecular film material.
Preferably, first photochromic layer is nickel oxide.
Preferably, first photochromic layer with a thickness of 100~300nm.
Preferably, the sheet resistivity of first photochromic layer is not less than 100k Ω/m2。
Preferably, second photochromic layer is tungsten oxide.
Preferably, second photochromic layer with a thickness of 200~600nm.
Preferably, the sheet resistivity of second photochromic layer is not less than 100k Ω/m2。
Detailed description of the invention
Fig. 1 is the structural schematic diagram of previous full-solid electrochromic glass；
Fig. 2 is the structural schematic diagram of the full-solid electrochromic device of an embodiment of the present invention；
Fig. 3 is the transmitted light spectrogram of the solid ion conductive layer of an embodiment of the present invention；
Fig. 4 is the transmitted light spectrogram of the total solids electrochomeric glass of an embodiment of the present invention；
Fig. 5 is the reflectance spectrum figure of the total solids electrochomeric glass of an embodiment of the present invention；
Fig. 6 is the AC impedance spectroscopy of the total solids electrochomeric glass of an embodiment of the present invention；
Fig. 7 is the transmitance of the total solids electrochomeric glass of an embodiment of the present invention with voltage responsive variation diagram.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
Embodiment of the present invention provides a kind of solid-state electrolyte layer, full-solid electrochromic glass devices and its preparation side
Method can reduce cost, and simple process reduces preparation time, improves stability, improve ion in the conductivity of two discoloration interlayers
And conduction of velocity.
An embodiment of the present invention provides a kind of solid ionic conduction layer membrane materials.The solid ionic conducting shell is
Aluminium lithium alloy AlxLi.Wherein 0 < x < 1.
The solid ionic conducting shell is preferably transparent smooth film material, visible light transmittance can reach 90% with
On.
The solid ionic conducting shell can be unformed loose film, in order to which lithium ion quickly conducts, and then realize electricity
Mutagens colour response.
The thickness of the solid ionic conducting shell can be 10~500nm, preferably 10~100nm.Solid ionic of the invention
Conducting shell can avoid photochromic layer caused by the counterdiffusion between cathode or anode material and photochromic layer under relatively small thickness
In the loss of ion (can be anti-from the impedance spectra of the electrochromic device comprising the solid ionic conducting shell and electrochromism
It is known in answering).
The solid ionic conducting shell is preferably transparent non-conductive.Its sheet resistivity is preferably not less than 100k Ω/m2。
Aluminium lithium alloy target can be used to pass through DC power supply magnetron sputtering method, electron beam auxiliary law for ion conducting layer of the invention
Deng preparation.The aluminium lithium alloy target used can be AlxLi (0 < x < 1).Hereinafter, as an example, illustrating that the solid ionic passes
The preparation method of conducting shell.
In an embodiment of the present invention, the solid ionic conducting shell uses aluminium lithium alloy AlxLi (0 x≤1 <) is target
Using DC current with aluminium lithium alloy AlxLi (0 < x < 1) is target with the preparation of DC power supply magnetron sputtering.Wherein, background is true
Sky can be 1 × 10-4~5 × 10-2Pa, preferably 5 × 10-4~5 × 10-3Pa.Base reservoir temperature can 0~200 DEG C, preferably 20~70
℃.Sputtering pressure can be 0.5~5Pa, preferably 1Pa~3Pa.Sputtering work atmosphere can be argon gas.Plated film time can for 20s~
1h.Sputtering power density can be 0.5~3.0W/cm2.By adjusting sputtering power and/or plated film time, solid ionic is adjusted
Conducting shell film thickness.
Above-mentioned preparation method is at low cost, simple process, it is possible to reduce preparation time is consolidated by prepared by above-mentioned preparation method
State ion conducting layer can accelerate the conducting lithium ions between the first photochromic layer and the second photochromic layer.The unformed loose knot
Structure, in order to quick, efficiently conducting lithium ions, and then realization electrochromic reaction.
The present invention also provides a kind of full-solid electrochromic glass.Fig. 2 shows all solid state electricity of an embodiment of the present invention
Cause the structural schematic diagram of photo chromic glass.As shown in Fig. 2, the full-solid electrochromic glass (also referred to as photo chromic glass in the present invention) can
To include: substrate 200, the first conductive layer 210, the first photochromic layer 220, ion conducting layer that are set in turn on substrate 200
230, the second photochromic layer 240, the second conductive layer 250, protective layer 260.
Substrate 200 can be the high molecule plastics such as common glass substrates, quartz glass substrate, PET or flexible base board and
Deng for bearing film layer.
The material of first conductive layer 210 can be transparent conductive material.The transparent conductive material can be saturating for metal oxide
Bright conductive material, blended metal oxide transparent conductive material (such as indium oxide, tin indium oxide, doped indium oxide, tin oxide,
Doped stannum oxide, zinc oxide, Al-Doped ZnO or aoxidized nail and their mixture), macromolecule transparent conductive material (example
Such as polyaniline, polythiophene, doping polyacetylene film) and flexible and transparent conductive material (such as mix the silver nanowires of ZnO
(AgNW), PET) etc..The thickness of first conductive layer 210 can be 100~800nm, preferably 100~200nm.First conductive layer
210 preparation method is not particularly limited, and may be, for example, magnetron sputtering method etc..
First photochromic layer 220 can contain the presence or absence of with good grounds lithium ion and discoloration (changing between coloured state and transparent state) occurs
Material for example, being transparent state when there is lithium ion be coloured state, preferably nickel oxide in no lithium ion.Wherein nickel oxide
Preparation method is simple and possesses preferable stability.First photochromic layer nickel oxide film 220, preferably porosity and looseness is unformed
State, surfacing are uniform.The thickness of first photochromic layer 220 can be 100~300nm.The sheet resistivity of first photochromic layer 220 is excellent
It is selected as not less than 100k Ω/m2.The preparation method of first photochromic layer 220 is not particularly limited, and may be, for example, physical vapour deposition (PVD)
Method can specifically enumerate magnetron sputtering method etc..In one example, prepared with nickel target material magnetic sputtering method, specific preparation condition can
Are as follows: base vacuum can be 1 × 10-4~5 × 10-2Pa.Base reservoir temperature can be 0~200 DEG C.Sputtering pressure can be 0.5~5Pa.It splashes
Penetrating work atmosphere can be oxygen argon mixture gas, and oxygen proportion is 10~30%.Plated film time can be 1~30min.Sputtering power is close
Degree can be 0.5~3.0W/cm2.In another example, obtained with the direct magnetron sputtering of nickel oxide target.Specific preparation condition can are as follows:
Base vacuum can be 1 × 10-4~5 × 10-2Pa.Base reservoir temperature can be 0~200 DEG C.Sputtering pressure can be 0.5~5Pa.Sputter work
Making atmosphere can be oxygen argon mixture gas, and oxygen proportion is 10~30%.Plated film time can be 20~60min.Sputtering power density
It can be 0.5~3.0W/cm2。
Above-mentioned solid ionic conducting shell (aluminium lithium alloy Al can be used in ion conducting layer 230xLi), details are not described herein.
Second photochromic layer 240 can contain the presence or absence of with good grounds lithium ion and discoloration (changing between coloured state and transparent state) occurs
Material, for example, when there is lithium ion be coloured state transparent state, in no lithium ion be transparent state.Second photochromic layer is oxidation
Tungsten.The thickness of second photochromic layer 240 can be 200~600nm.The sheet resistivity of second photochromic layer 240 is preferably not less than 100k
Ω/m2.Second photochromic layer 240 (such as tungsten oxide film) can be the unformed state of porosity and looseness, and surfacing is uniform.Second
The preparation method of photochromic layer 240 is not particularly limited, and may be, for example, physical vaporous deposition, can specifically enumerate magnetron sputtering method
Deng.In one example, it is prepared with tungsten target material magnetic sputtering method.Specific preparation condition can are as follows: base vacuum can be 1
×10-4~5 × 10-2Pa.Base reservoir temperature can be 0~200 DEG C.Sputtering pressure can be 0.5~5Pa.Sputtering work atmosphere can be oxygen argon
Mixed gas, oxygen proportion are 2~20%.Plated film time can be 20~60min.Sputtering power density can be 0.5~3.0W/
cm2.In another example, obtained with the direct magnetron sputtering of oxidation tungsten target material.Specific preparation condition can are as follows: base vacuum can for 1 ×
10-4~5 × 10-2Pa.Base reservoir temperature can be 0~200 DEG C.Sputtering pressure can be 0.5~5Pa.Sputtering work atmosphere can be straight argon
Gas.Plated film time can be 10~60min.Sputtering power density can be 0.5~3.0W/cm2。
The material of second conductive layer 250 can be transparent conductive material.The transparent conductive material can be saturating for metal oxide
Bright conductive material, blended metal oxide transparent conductive material (such as indium oxide, tin indium oxide, doped indium oxide, tin oxide,
Doped stannum oxide, zinc oxide, Al-Doped ZnO or aoxidized nail and their mixture), macromolecule transparent conductive material (example
Such as polyaniline, polythiophene, doping polyacetylene film) and flexible and transparent conductive material (such as mix the silver nanowires of ZnO
(AgNW), PET) etc..The thickness of second conductive layer 250 can be 100~800nm, preferably 100~200nm.Second conductive layer
250 preparation method is not particularly limited, and may be, for example, magnetron sputtering method etc..
Protective layer 260 is transparent non-conductive material, to avoid full-solid electrochromic glass in practical applications by it is moist,
The influence of the external environments such as oxidation.The transmitance of protective layer can be 80% or more, preferably 90% or more.The thickness of protective layer can
In 50~500nm, preferably 150~300nm.Protective layer can be SiAlNxOy(0≤x≤2,2≤y≤5) thin transparent membrane material
Material, metal-oxide film or transparent polymer thin-film material etc..The preparation method of protective layer is not particularly limited, such as
Magnetron sputtering technology or electron beam ion source ancillary technique etc. can be used.With SiAlNxOyFor the preparation of transparent membrane,
With silico-aluminum (SiAlx, 0≤x≤1) and target, it is obtained by reaction magnetocontrol sputtering technology of preparing, sputtering atmosphere can be argon gas:
Oxygen: three kinds of mixed-gas atmospheres of nitrogen, wherein argon gas: oxygen: the volume ratio of nitrogen can be (30~60): (20~30):
(10~20), such as 40:5:5.Sputtering power can be 50~200W.Sputtering pressure can be in 0.3~5.0Pa range.Sputter temperature
It can be 0~200 DEG C.
In full-solid electrochromic glass, ion conducting layer is solid-state, in the first photochromic layer 220 and the second photochromic layer
Ion is conducted between 240.First photochromic layer 220 and the second photochromic layer 240 are used to that electroluminescent change to occur with ion under electric field action
Colour response.For example, when the second conductive layer 250 applies forward voltage, lithium ion is located at the first photochromic layer 220 and (such as aoxidizes
Nickel), the first photochromic layer 220 (such as nickel oxide layer) shows as transparent state, the second photochromic layer 240 of no lithium ion (such as aoxidize
Tungsten layer) pale yellow transparent state is shown as, the light in environment can penetrate each layer, and electrochomeric glass is with higher to light
Penetrate rate；When the first conductive layer 210 applies backward voltage, when lithium ion is located at second photochromic layer 240 (such as tungsten oxide layer),
Second photochromic layer 240 (such as tungsten oxide) is coloured state, shows as blue, and first photochromic layer 220 (such as nickel oxide layer) nothing
Lithium ion shows as brown color, has lower transmissivity to light.The side of the voltage of electrochomeric glass is applied to by controlling
To and voltage application time, control lithium ion the first photochromic layer 220 (such as nickel oxide layer) and the second photochromic layer 240 (such as
Tungsten oxide) between migrate, the reflectivity of dynamic regulation electrochomeric glass.In full-solid electrochromic glass of the invention, nothing
It needs dielectric layer also and can have high ionic conductivity.
The present invention also provides a kind of full-solid electrochromic devices.The full-solid electrochromic device includes all solid state
Electrochomeric glass and voltage-operated device.Wherein, full-solid electrochromic glass can be as described above.Voltage-operated device electricity
First conductive layer and second conductive layer are connected, for providing supply voltage to the full-solid electrochromic glass.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Test method:
Transmitance: U-4100 photometer)
AC impedance: CS electrochemical workstation (Electrochemical Workstation)
Sheet resistivity: multimeter.
Embodiment 1
Cleaning glass substrate is put into magnetron sputtering apparatus, and sputtering forms transparent conductive material: target selects ITO target, sputtering electricity
Source uses radio-frequency power supply, power density 1.5w/cm2, atmosphere pure argon, pressure 0.5Pa room temperature sputtering time 60 minutes, obtains
The ITO conductive film of surfacing is obtained, thickness 100-200nm, measurement sheet resistivity, sheet resistivity is less than 50 Ω.
Embodiment 2
At room temperature using Magnetron reactive sputtering prepare it is transparent lead nickel oxide film, substrate is put into magnetron sputtering cavity, target
Nickel target is selected, shielding power supply uses DC power supply, power density 1.5w/cm2, atmosphere is that oxygen is argon-mixed, wherein carrier of oxygen
Product room temperature sputtering time 30 minutes, obtains the nickel oxide film of surfacing, thickness 100- than being 15%, pressure 1.5Pa
200nm, measurement sheet resistivity, sheet resistivity are not less than 100k Ω.
Embodiment 3
Aluminium lithium alloy solid ionic is formed on nickel oxide film and conducts layer film: transparent aluminium is prepared using Magnetron reactive sputtering
Substrate is put into magnetron sputtering cavity, target aluminium lithium target AlLi (ratio 1:1) by lithium alloy film, and shielding power supply is adopted
With DC power supply, power density 1.5w/cm2, atmosphere is pure argon, and pressure 2.5Pa room temperature sputtering time 20 minutes, is obtained
The aluminium lithium alloy film of surfacing measures sheet resistivity with a thickness of 30nm, and sheet resistivity is not less than 100k Ω.Fig. 3
Resulting solid ionic conduction layer film transmitted light spectrogram is shown.As it can be seen that the solid ion conductive layer is to visible light transmittance
Range can be used for building intelligence window, automobile rearview mirror etc. up to 90% or more.
Embodiment 4
Tungsten oxide film is formed on aluminium lithium solid ionic conduction layer film: the second photochromic layer is prepared using Magnetron reactive sputtering
Glass substrate is put into magnetron sputtering cavity by tungsten oxide transparent membrane, and target selects metal tungsten target material, and shielding power supply uses direct current
Power supply, power density 1.5w/cm2, atmosphere is that oxygen is argon-mixed, and wherein oxygen volume ratio is 10%, and pressure 2.5Pa, room temperature is splashed
It penetrates the time 30 minutes, obtains the tungsten oxide film of surfacing, thickness 300nm, measurement sheet resistivity, sheet resistivity is not small
In 100k Ω.
Embodiment 5
The second conductive layer is formed on second photochromic layer: electrically conducting transparent body thin film being prepared using magnetron sputtering method at room temperature, by glass
Substrate is put into magnetron sputtering cavity, and target selects ITO target, and shielding power supply uses radio-frequency power supply, power density 1.5w/cm2, gas
Atmosphere pure argon, pressure 0.5Pa room temperature sputtering time 60 minutes, obtain the ITO conductive film of surfacing, thickness 100-
200nm, measures sheet resistivity, and sheet resistivity is less than 50 Ω.
Embodiment 6
Protective layer is formed on the second conductive layer: using SiAlx(x=1) alloy target material, in argon gas: oxygen: nitrogen ratios 40:
SiAlN is obtained by reactive magnetron sputtering method in the mixed atmosphere of 5:5xOyCompound.The sputtering power of supply is 100W, sputtering
Pressure is prepared in 2Pa, room temperature reaction sputtering.Gained film thickness is 300nm, and transmitance is 80% or more, sheet resistivity
For not less than 100k Ω.Thus full-solid electrochromic glass is obtained.
Fig. 4 is the transmitted light spectrogram of resulting full-solid electrochromic glass.As it can be seen that the total solids electrochomeric glass exists
To the maximum modulation range of visible light transmittance up to 80% or so when transparent state and absorbing state (also referred to as coloured state).
Fig. 5 is the reflectance spectrum figure of resulting total solids electrochomeric glass.As it can be seen that coloured state and transparent state reflectivity tune
Wider range processed, and containing compared with multimodal.It is multi-layer film structure that wherein more peak value, which represents electrochromic device,；And it is larger
Peak value represent in film comprising pure metal simple substance, while further demonstrating that ion conducting layer prepared by the present invention is simple
Aluminium lithium alloy film.
Fig. 6 is the AC impedance spectroscopy of resulting total solids electrochomeric glass.As it can be seen that the friendship under certain cycle frequency
Flow impedance spectrogram has the tendency that gradually regularity becomes larger, and represent solid-state aluminium lithium alloy film is that good, stable ion passes
It leads and the electrochromic device comprising this aluminium lithium alloy solid ionic conducting shell has preferable stability.
Fig. 7 is the transmitance of resulting total solids electrochomeric glass with voltage responsive variation diagram.As it can be seen that total solids is electroluminescent
Photo chromic glass can be with the variation of voltage in the transmissivity of coloured state and dynamic changes and the faster response time.Total solids is electroluminescent
The device that photo chromic glass is prepared into can control its transmission by controlling the voltage being applied on the total solids electrochomeric glass
Rate.
Full-solid electrochromic glass of the invention, full-solid electrochromic device can be applied to smart windows in building,
It with energy-conserving action, is also used as interior and dazzles mirror, be applied to interior decoration.
First conductive layer or the second conductive layer can be transparency conducting layer, and then the reflection-type full-solid electrochromic formed
Device can be used as automobile rearview mirror, in extraneous light intensity, can control rearview mirror from high reflection state and becomes low reflection state, reduce
Influence of the glare to driver guarantees driving safety.
It should be noted that for simple description, therefore, it is stated as a systems for each embodiment of the method above-mentioned
The combination of actions of column, but those skilled in the art should understand that, the present invention is not limited by the sequence of acts described, because
For according to the present invention, certain some step can be performed in other orders or simultaneously.Secondly, those skilled in the art also should
Know, the embodiments described in the specification are all preferred embodiments, related actions and modules not necessarily this hair
Necessary to bright.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, is not described in some embodiment
Part, reference can be made to the related descriptions of other embodiments.
Claims (8)
1. a kind of solid ionic conducting shell, which is characterized in that the chemical composition of the solid ionic conducting shell is aluminium lithium alloy
Al x Li, wherein 0 < x < 1.
2. solid ionic conducting shell according to claim 1, which is characterized in that the transmitance of the solid ionic conducting shell
90% or more.
3. solid ionic conducting shell according to claim 1 or 2, which is characterized in that the table of the solid ionic conducting shell
Face sheet resistance is not less than 100k Ω/m2；The thickness of the solid ionic conducting shell is in 10~500nm, preferably 10~100nm.
4. the preparation method of solid ionic conducting shell described in a kind of any one of claims 1 to 3, which is characterized in that use
Aluminium lithium alloy is target with the preparation of DC power supply magnetron sputtering, wherein base vacuum is 1 × 10-4~5 × 10-2Pa, substrate temperature
Degree is 0~200 DEG C, and plated film time is 20s~1h, and operating air pressure is 0.5~5Pa, and sputtering work atmosphere is argon gas, sputtering power
Density is 0.5~3.0W/cm2。
5. a kind of full-solid electrochromic device, which is characterized in that including substrate；And be set in turn on the substrate
One conductive layer, the first photochromic layer, solid ionic conducting shell, the second photochromic layer, second described in any one of claims 1 to 3
Conductive layer.
6. full-solid electrochromic device according to claim 5, which is characterized in that first photochromic layer is oxidation
Nickel；Preferably, first photochromic layer with a thickness of 100~300nm；Preferably, the sheet resistivity of first photochromic layer is not
Less than 100k Ω/m2。
7. full-solid electrochromic device according to claim 5 or 6, which is characterized in that second photochromic layer is oxygen
Change tungsten；Preferably, second photochromic layer with a thickness of 200~600nm；Preferably, the sheet resistivity of second photochromic layer
Not less than 100k Ω/m2。
8. full-solid electrochromic device according to any one of claims 5 to 7, which is characterized in that described second
The outside of conductive layer also has protective layer, it is preferable that the protective layer is SiAlN x O y Transparent thin-film material, metal oxide are thin
Membrane material or transparent polymer thin-film material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810031717.0A CN110032018B (en) | 2018-01-12 | 2018-01-12 | Aluminum-lithium alloy solid ion conducting layer, preparation method thereof and electrochromic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810031717.0A CN110032018B (en) | 2018-01-12 | 2018-01-12 | Aluminum-lithium alloy solid ion conducting layer, preparation method thereof and electrochromic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110032018A true CN110032018A (en) | 2019-07-19 |
| CN110032018B CN110032018B (en) | 2020-11-24 |
Family
ID=67234927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810031717.0A Active CN110032018B (en) | 2018-01-12 | 2018-01-12 | Aluminum-lithium alloy solid ion conducting layer, preparation method thereof and electrochromic device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110032018B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110908208A (en) * | 2019-12-17 | 2020-03-24 | 深圳市光羿科技有限公司 | Electrochromic device and preparation method and application thereof |
| CN112285982A (en) * | 2020-11-06 | 2021-01-29 | 哈尔滨工业大学 | All-solid-state electrochromic device with lithium aluminum silicate as electrolyte layer and preparation method thereof |
| CN112666769A (en) * | 2019-10-16 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Quick response electrochromic intelligence window |
| CN114326241A (en) * | 2021-12-27 | 2022-04-12 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of ion transport layer and component composite film system for inorganic electrochromism |
| CN115128877A (en) * | 2021-03-25 | 2022-09-30 | 中国科学院上海硅酸盐研究所 | Electrochromic device based on nitride lithium ion conducting layer and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59216183A (en) * | 1983-05-24 | 1984-12-06 | 松下電器産業株式会社 | Electrochromic display element |
| US4889659A (en) * | 1985-09-30 | 1989-12-26 | Commissariat A L'energie Atomique | Nitrogenized electronic conductive polymers, their preparation processes, electrochromic display cell and electrochemical generator using these polymers |
| US7646526B1 (en) * | 2008-09-30 | 2010-01-12 | Soladigm, Inc. | Durable reflection-controllable electrochromic thin film material |
| US20100079845A1 (en) * | 2008-10-01 | 2010-04-01 | Zhongchun Wang | Reflection-Controllable Electrochromic Device Using A Base Metal As A Transparent Conductor |
| JP2010217367A (en) * | 2009-03-16 | 2010-09-30 | Toppan Forms Co Ltd | All-solid-state electrochromic element |
| CN102298241A (en) * | 2010-06-22 | 2011-12-28 | 河南师范大学 | Full thin film electrochromic intelligent window |
| CN105759469A (en) * | 2014-12-18 | 2016-07-13 | 汉朗科技(北京)有限责任公司 | Multifunctional smart glass and manufacturing method thereof |
| CN107015412A (en) * | 2017-04-13 | 2017-08-04 | 吉晟光电（深圳）有限公司 | A kind of structure and preparation method of the full film electrochromic device of solid-state |
| CN107045241A (en) * | 2017-05-19 | 2017-08-15 | 浙江大学 | One kind is based on Al3+Full-solid electrochromic device of ion and preparation method thereof |
| CN107085339A (en) * | 2017-03-01 | 2017-08-22 | 江苏繁华玻璃股份有限公司 | A kind of preparation method of full-solid electrochromic device |
-
2018
- 2018-01-12 CN CN201810031717.0A patent/CN110032018B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59216183A (en) * | 1983-05-24 | 1984-12-06 | 松下電器産業株式会社 | Electrochromic display element |
| US4889659A (en) * | 1985-09-30 | 1989-12-26 | Commissariat A L'energie Atomique | Nitrogenized electronic conductive polymers, their preparation processes, electrochromic display cell and electrochemical generator using these polymers |
| US7646526B1 (en) * | 2008-09-30 | 2010-01-12 | Soladigm, Inc. | Durable reflection-controllable electrochromic thin film material |
| US20100079845A1 (en) * | 2008-10-01 | 2010-04-01 | Zhongchun Wang | Reflection-Controllable Electrochromic Device Using A Base Metal As A Transparent Conductor |
| JP2010217367A (en) * | 2009-03-16 | 2010-09-30 | Toppan Forms Co Ltd | All-solid-state electrochromic element |
| CN102298241A (en) * | 2010-06-22 | 2011-12-28 | 河南师范大学 | Full thin film electrochromic intelligent window |
| CN105759469A (en) * | 2014-12-18 | 2016-07-13 | 汉朗科技(北京)有限责任公司 | Multifunctional smart glass and manufacturing method thereof |
| CN107085339A (en) * | 2017-03-01 | 2017-08-22 | 江苏繁华玻璃股份有限公司 | A kind of preparation method of full-solid electrochromic device |
| CN107015412A (en) * | 2017-04-13 | 2017-08-04 | 吉晟光电（深圳）有限公司 | A kind of structure and preparation method of the full film electrochromic device of solid-state |
| CN107045241A (en) * | 2017-05-19 | 2017-08-15 | 浙江大学 | One kind is based on Al3+Full-solid electrochromic device of ion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨海刚: "全薄膜电致变色元件的制备及其光学性能研究", 《人工晶体学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112666769A (en) * | 2019-10-16 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Quick response electrochromic intelligence window |
| CN110908208A (en) * | 2019-12-17 | 2020-03-24 | 深圳市光羿科技有限公司 | Electrochromic device and preparation method and application thereof |
| CN110908208B (en) * | 2019-12-17 | 2021-11-09 | 深圳市光羿科技有限公司 | Electrochromic device and preparation method and application thereof |
| CN112285982A (en) * | 2020-11-06 | 2021-01-29 | 哈尔滨工业大学 | All-solid-state electrochromic device with lithium aluminum silicate as electrolyte layer and preparation method thereof |
| CN115128877A (en) * | 2021-03-25 | 2022-09-30 | 中国科学院上海硅酸盐研究所 | Electrochromic device based on nitride lithium ion conducting layer and preparation method thereof |
| CN115128877B (en) * | 2021-03-25 | 2023-09-08 | 中国科学院上海硅酸盐研究所 | Electrochromic device based on lithium nitride ion conducting layer and preparation method thereof |
| CN114326241A (en) * | 2021-12-27 | 2022-04-12 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of ion transport layer and component composite film system for inorganic electrochromism |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110032018B (en) | 2020-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110032018A (en) | The full-solid electrochromic device of aluminium lithium alloy solid ionic conducting shell and preparation method thereof and the contained solid ionic conducting shell | |
| CN110045558A (en) | Lithium aluminate solid ionic conducting shell and preparation method thereof and the full-solid electrochromic device containing the solid ionic conducting shell | |
| CN111025812B (en) | Metal electrodeposition-based variable emissivity device and preparation method thereof | |
| JP4320564B2 (en) | Transparent conductive film forming composition, transparent conductive film forming solution, and transparent conductive film forming method | |
| US20140340729A1 (en) | Reflective dimming electrochromic element with non-water based hydrogen ion conductive electrolyte layer inserted therein, and dimming element using the same | |
| JPH07504514A (en) | Electrochromic device with refractive index matching structure and its operation and manufacturing method | |
| KR102149672B1 (en) | Electrochromic device | |
| WO2021139330A1 (en) | Flexible electrochromic-based variable-emissivity device and preparation method therefor | |
| CN106959566A (en) | A kind of preparation method of quasi- solid-state electrochromic device | |
| CN104178731A (en) | Controllable preparation method of electrochromic WO3 film | |
| Ito et al. | Electrochromic properties of iridium oxide thin films prepared by reactive sputtering in O2 or H2O atmosphere | |
| WO2019228303A1 (en) | Solid-state ionic conduction layer and solid-state electrochromic device having solid-state ionic conduction layer | |
| CN112456813A (en) | Nickel oxide electrochromic film and preparation method and application thereof | |
| TWI604254B (en) | Method for fabricating electrochromic device | |
| CN108089388B (en) | Method for selectively controlling working voltage of electric dimming device | |
| JPH0215243A (en) | Electrochromium type variable transmitting glass plate | |
| CN105807525A (en) | Polyacid based electrochromic film capable of efficiently discoloring in nonaqueous neutral electrolyte | |
| CN107315299A (en) | A kind of inorganic electrochromic charge storage electrode and preparation method thereof | |
| CN109270761A (en) | A kind of flexibility hot melt glue type all-solid-state flexible electrochromic device | |
| CN110376817A (en) | A kind of flexible full-solid electrochromic device and its control method based on amberplex | |
| KR102101151B1 (en) | An Electrochromic Device | |
| KR102010754B1 (en) | An Electrochromic Device | |
| CN111057257B (en) | Transparent polymer film capable of conducting Li + ions as well as preparation method and application thereof | |
| US11500257B2 (en) | Inorganic solid-state electrochromic module containing inorganic transparent conductive film | |
| CN208580285U (en) | Shell, electronic equipment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230731 Address after: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: Jiangsu Institute of advanced inorganic materials Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |