CN107315298A - A kind of brown electrochromism charge storage electrode and preparation method - Google Patents

A kind of brown electrochromism charge storage electrode and preparation method Download PDF

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CN107315298A
CN107315298A CN201710549979.1A CN201710549979A CN107315298A CN 107315298 A CN107315298 A CN 107315298A CN 201710549979 A CN201710549979 A CN 201710549979A CN 107315298 A CN107315298 A CN 107315298A
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CN107315298B (en
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刘伟明
颜悦
韦友秀
陈牧
张晓锋
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AECC Beijing Institute of Aeronautical Materials
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

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Abstract

The present invention relates to electrochomeric films technical field, more particularly to a kind of brown electrochromism charge storage electrode and preparation method.The present invention deposits transparency conducting layer and LiFe (WO by way of vacuum vapor deposition in transparent substrates4)2Electrochromism charge storage layer, makes its crystallization after the annealing process, successfully prepares the electrochromic electrode with electric charge store function.LiFe(WO4)2Film, as electrode charge accumulation layer, is a kind of negative electrode off-color material.The electrode charge amount storage capacity is higher, without carrying out prelithiation processing, and oxidation state transmitance is high, with unique brown and transparent state adjusting function, and possesses good circulation performance, driving voltage is low, the advantages of environmental suitability is strong.

Description

A kind of brown electrochromism charge storage electrode and preparation method
Technical field
The present invention relates to electrochomeric films technical field, more particularly to a kind of brown electrochromism charge storage electrode And preparation method.
Background technology
Electrochromism refers to the optical properties (reflectivity, transmitance, absorptivity etc.) of material in the presence of extra electric field Occur the phenomenon of reversible color discoloration, the reversible change of color and transparency is shown as in appearance.With electrochromism The material of energy is referred to as electrochromic material, the Electrochromic device made with electrochromic material referred to as electrochromic device.In recent years The passenger plane porthole of Boeing 787 has further transferred exploitation upsurge using electrochomeric glass.With the further maturation of correlation technique With the reduction of production cost, electrochromism technology can obtain wider market application.
Electrochromic device is made up of transparency conducting layer, electrochromic layer, dielectric substrate, ion storage, wherein electroluminescent Photochromic layer and the material of ion storage are complementary type materials, can be divided into organic and inorganic two major class, wherein inorganic material is because having Stable environment weatherability and relatively low material cost and it is wide concerned.Material generally as ion storage is nickel oxide (NiOx), vanadic anhydride (V2O5), yttrium oxide (IrOx), cobalt oxide (CoOx), nickel-tungsten oxide (WNiOx), cerium oxide (CeOx), Prussian blue (PB) etc., the quantity of electric charge of these materials is relatively low, influences the effect of the colored state of device.Also there are some electric charges The higher materials application of amount of storage is in electrochromic device, for example：LiFePO 4 (LiFePO4), cobalt acid lithium (LiCoO2), Lithium vanadate (LiV2O5) etc., for the preparation method of these materials, it common are solution-deposition method, sol-gal process and cladding process Deng but these materials and the universal transmitance of preparation method are relatively low, and thickness prepares that uneven, discoloration is inconsistent, film attachment The more low FAQs of power, can influence the transmitance of device bleached state.
The content of the invention
The purpose of the present invention is to surround LiFe (WO4)2Core material, proposes a kind of electrochromism charge storage electrode.Success Preparing one kind has driving voltage low, and transmitance is high, and charge capacity is higher, and brown coloured state itself has lithium source as biography The charge storage electrode of transmission of electricity lotus, the preparation method is vacuum PVD, and electrode film prepared by this method has Adhesion of coating film is strong, the advantage such as discoloration uniformity.
The present invention is achieved through the following technical solutions
The composition of electrode includes：Transparent base layer, transparency conducting layer and the part of electrochromism charge storage layer three, from upper and Under be followed successively by electrochromism charge storage layer, transparency conducting layer, transparent base layer, electrochromism charge storage layer is by LiFe (WO4)2Composition；Electrically conducting transparent layer material used in electrode is tin indium oxide, the tin oxide of Fluorin doped, tin oxide, zinc oxide, Al mix One or more of Film laminateds in the ZnO of miscellaneous ZnO, Ga doping；Transparent substrates layer material used in electrode is unorganic glass, gathered Acid imide, polyethylene terephthalate or polycarbonate transparent base material.
Preparing the method for inorganic brown electrochromism charge storage electrode is,
(1) transparent substrates are pre-processed
It is utilized respectively acetone, ethanol and pure water to be successively cleaned by ultrasonic transparent base layer, is placed in after nitrogen purging Drying process in baking oven, removes the greasy dirt and impurity on its surface；
(2) vacuum PVD prepares transparency conducting layer
Transparency conducting layer is prepared using magnetron sputtering mode or electron-beam evaporation mode, the resistance per square of transparency conducting layer is 5- 30Ω/□；
(3) vacuum PVD electrochromism charge storage layer and subsequent heat treatment crystallization
Charge storage layer is prepared using magnetron sputtering mode or electron-beam evaporation mode, the deposition atmosphere used is argon gas Or argon oxygen gas mixture, setting chamber deposition air pressure range 1 × 10-2~5Pa, prepares the charge storage layer with thickness, and electric charge is deposited 50~700nm of thickness range of reservoir, the progress heat treatment crystallization after deposition terminates, 200~500 DEG C of heat-treatment temperature range, Heat treatment time is 10~180 minutes, and heat-treating atmosphere is argon oxygen gas mixture or dry air.
The deposition atmosphere is argon gas or argon oxygen gas mixture, deposition pressure scope 1 × 10-1~2Pa.
100~600nm of thickness range of the charge storage layer.
Progress heat treatment crystallization, 250~450 DEG C of heat-treatment temperature range after the deposition terminates, heat treatment time is 20 ~100 minutes, heat-treating atmosphere was argon oxygen gas mixture or dry air.
The invention has the advantages that and beneficial effect：
The present invention deposits transparency conducting layer and LiFe (WO by way of vacuum vapor deposition in transparent substrates4)2It is electroluminescent Change colour charge storage layer, and its crystallization is made after the annealing process, the electrochromic electrode with high magnitude of the stored charge is successfully prepared. Compared with the ion storage electrode reported before, the electrode charge amount storage capacity is strong, without carrying out prelithiation processing, environment Strong adaptability, the transmitance of oxidation state is high, reducing condition coloring, and can match preparation electrochromism with anode off-color material electrode Device.
The present invention is with LiFe (WO4)2The mode of vacuum vapor deposition is utilized for core material, is deposited in transparent substrates transparent Conductive layer and LiFe (WO4)2Electrochromism charge storage layer, makes its crystallization after recycling the processing of ex situ ambient anneal, successfully makes It is standby go out the electrochromic electrode with high magnitude of the stored charge.LiFe(WO4)2Film is as electrode charge accumulation layer, while having one concurrently Determine degree colour change function.Experiment proves that the electrode is a kind of cathodic electrochromic electrode, can be adjusted between brown and leuco-state Color, and possess quantity of electric charge storage capacity by force, oxidation state transmitance is high, and driving voltage is low, the advantages of environmental suitability is strong.The electricity Pole is a kind of cathodic electrochromic electrode.Compared with the inorganic ion-storage layer electrode reported before, the electrode is pre- without carrying out Lithiumation processing, quantity of electric charge storage capacity is strong, and the transmitance of oxidation state is high, reducing condition coloring, and electrode preparation method letter It is single efficiently, homogeneity of product preferably, with the inorganic ions reported before deposit by the thickness of electrode and uniform component distribution prepared with this Reservoir electrode is compared, and the electrode can change colourless between brown state, itself have lithium source as transmission electric charge, without entering Row prelithiation processing, driving voltage is low, and quantity of electric charge storage capacity is strong, and the transmitance of oxidation state is high, can be with anode off-color material electricity Pole, which matches, prepares electrochromic device, and the electrode preparation method is simply efficient, can make full use of existing flat board or winding Plated film mode realizes preparation of industrialization.
Figure of description
Fig. 1 is transparent electrochromism charge storage electrode structural representation；
Fig. 2 is that three kinds of embodiment sample colored states absorb spectrogram；
Fig. 3 is that three kinds of embodiment sample bleached states absorb spectrogram；
Fig. 4 is three kinds of embodiment sample cyclic voltammetric datagrams；
Fig. 5 is three kinds of embodiment sample charge capacity datagrams.
Embodiment
The present invention is done below with reference to drawings and examples and is further described in detail：
The composition of electrode includes：Transparent base layer 101, transparency conducting layer 102 and electrochromism charge storage layer 103 3 Point, electrochromism charge storage layer 103, transparency conducting layer 102, transparent base layer 101, electrochromism electricity are followed successively by from top to bottom Lotus accumulation layer is by LiFe (WO4)2Composition；Electrically conducting transparent layer material used in electrode is tin indium oxide (ITO), the tin oxide of Fluorin doped (FTO), tin oxide (SnO2), zinc oxide (ZnO), the ZnO (AZO) of Al doping, the ZnO (GZO) of Ga doping is one or more of thin Film is combined；Transparent substrates layer material used in electrode is unorganic glass, polyimides (PI), polyethylene terephthalate Or the transparent base such as makrolon (PC) (PET).
The preparation method of the inorganic brown electrochromism charge storage electrode is,
(1) transparent substrates are pre-processed
It is utilized respectively acetone, ethanol and pure water to be successively cleaned by ultrasonic transparent base layer, is placed in after nitrogen purging Drying process in baking oven, removes the greasy dirt and impurity on its surface；
(2) vacuum PVD prepares transparency conducting layer
Transparency conducting layer is prepared using magnetron sputtering mode or electron-beam evaporation mode, the resistance per square of transparency conducting layer is 5- 30Ω/□；
(3) vacuum PVD electrochromism charge storage layer and subsequent heat treatment crystallization
Charge storage layer is prepared using magnetron sputtering mode or electron-beam evaporation mode, the deposition atmosphere used is argon gas Or argon oxygen gas mixture, setting chamber deposition air pressure range 1 × 10-2~5Pa, prepares the charge storage layer with thickness, and electric charge is deposited 50~700nm of thickness range of reservoir, the progress heat treatment crystallization after deposition terminates, 200~500 DEG C of heat-treatment temperature range, Heat treatment time is 10~180 minutes, and heat-treating atmosphere is argon oxygen gas mixture or dry air.
The deposition atmosphere is argon gas or argon oxygen gas mixture, deposition pressure scope 1 × 10-1~2Pa.
100~600nm of thickness range of the charge storage layer.
Progress heat treatment crystallization, 250~450 DEG C of heat-treatment temperature range after the deposition terminates, heat treatment time is 20 ~100 minutes, heat-treating atmosphere was argon oxygen gas mixture or dry air.
The inorganic brown electrochromism charge storage electrode includes transparent base layer, transparency conducting layer and electrochromism electric charge The part of accumulation layer three, wherein electrochromism charge storage layer is by LiFe (WO4)2The step of film composition, method prepared by the electrode It is：
(1) transparent substrates are pre-processed, transparent substrates layer material used in electrode is unorganic glass, polyimides (PI), the transparent base such as polyethylene terephthalate (PET) or makrolon (PC).It is utilized respectively acetone, ethanol and pure Water purification is cleaned by ultrasonic to transparent base layer successively, is placed in drying process in baking oven after nitrogen purging, removes the oil on its surface Dirty and impurity；Then transparency conducting layer, transparency conducting layer material used are prepared using magnetron sputtering mode or electron-beam evaporation mode Expect for tin indium oxide (ITO), the tin oxide (FTO) of Fluorin doped, tin oxide (SnO2), zinc oxide (ZnO), the ZnO of Al doping (AZO), the one or more of Film laminateds of the ZnO (GZO) of Ga doping, the resistance per square of transparency conducting layer is 5-30 Ω/；
(2) LiFe (WO are prepared using magnetron sputtering mode or electron-beam evaporation mode4)2Charge storage layer, what is used is heavy Pneumatosis atmosphere is argon gas or argon oxygen gas mixture, setting chamber deposition air pressure range 1 × 10-2~5Pa, prepares 50~700nm thickness Charge storage layer, progress heat treatment crystallization, 200~500 DEG C of heat-treatment temperature range after deposition terminates, heat treatment time is 10 ~180 minutes, heat-treating atmosphere was argon oxygen gas mixture or dry air.
Embodiment 1
(1) it is utilized respectively acetone, ethanol and pure water unorganic glass to be carried out being cleaned by ultrasonic 15 minutes successively, nitrogen purging After be placed in drying process in baking oven, remove the greasy dirt and impurity on its surface, the glass substrate for cleaning dry be placed in vacuum chamber Interior, depositional mode is Deposited By Dc Magnetron Sputtering, and target is ITO targets, and target-substrate distance is 9cm, and Chamber vacuum is dropped using vavuum pump To 1 × 10-3Pa, regulation argon gas and oxygen gas flowmeter make chamber pressure be maintained at 1.0Pa, and wherein argon oxygen ratio is 30/1, base Plate temperature is room temperature, and deposition power is 100W, and sedimentation rate is 50nm/min, and deposit thickness is 300nm；
(2) glass substrate for having deposited transparency conducting layer is placed in vacuum annealing furnace, 250 DEG C under 1Pa argon atmospheres Annealing 30 minutes, cools to room temperature with the furnace；
(3) sample after will be annealed above is placed in vacuum chamber, and depositional mode is r. f. magnetron sputtering, and target is LiFe(WO4)2Target, target-substrate distance is 9cm, Chamber vacuum is down to 1 × 10 using vavuum pump-3Pa, regulation argon gas and oxygen gas Flowmeter makes chamber pressure be maintained at 0.05Pa, and wherein argon oxygen ratio is 3/1, and substrate temperature is room temperature, and deposition power is 100W, is sunk Product speed is 30nm/min, and deposit thickness is 70nm；
(4) ITO layer and LiFe (WO are coated with by more than4)2The glass substrate of layer is placed in vacuum annealing furnace, in 1Pa argon oxygen (argon oxygen is than 3/1) atmosphere is enclosed lower 220 DEG C and annealed 180 minutes, cools to room temperature with the furnace；
Electrochromism charge storage electrode coloring made above/colour fading absorbs spectrogram, and cyclic voltammetry curve holds with electric charge Amount curve is shown in accompanying drawing：Fig. 2~Fig. 5 (Sample 1).
Embodiment 2
(1) it is utilized respectively acetone, ethanol and pure water unorganic glass to be carried out being cleaned by ultrasonic 15 minutes successively, nitrogen purging After be placed in drying process in baking oven, remove the greasy dirt and impurity on its surface, the glass substrate for cleaning dry be placed in vacuum chamber Interior, depositional mode is Deposited By Dc Magnetron Sputtering, and target is ZnO (AZO) target that Al adulterates, and target-substrate distance is 9cm, utilizes vavuum pump Chamber vacuum is set to be down to 1 × 10-3Pa, regulation argon gas and oxygen gas flowmeter make chamber pressure be maintained at 0.8Pa, wherein argon oxygen Than for 25/1, substrate temperature is room temperature, and deposition power is 100W, and sedimentation rate is 40nm/min, and deposit thickness is 100nm；After Continuous to deposit the transparency conducting layers of ITO second with ITO targets, target-substrate distance is 9cm, Chamber vacuum is down to 1 × 10 using vavuum pump-3Pa, Regulation argon gas and oxygen gas flowmeter make chamber pressure be maintained at 1.0Pa, and wherein argon oxygen ratio is 30/1, and substrate temperature is room Temperature, deposition power is 100W, and sedimentation rate is 50nm/min, and deposit thickness is 200nm；
(2) glass substrate for having deposited transparency conducting layer is placed in vacuum annealing furnace, 250 DEG C under 1Pa argon atmospheres Annealing 30 minutes, cools to room temperature with the furnace；
(3) sample after will be annealed above is placed in vacuum chamber, and depositional mode is r. f. magnetron sputtering, and target is LiFe(WO4)2Target, target-substrate distance is 9cm, Chamber vacuum is down to 1 × 10 using vavuum pump-3Pa, regulation argon gas and oxygen gas Flowmeter makes chamber pressure be maintained at 1.0Pa, and wherein argon oxygen ratio is 3/1, and substrate temperature is room temperature, and deposition power is 100W, is sunk Product speed is 20nm/min, and deposit thickness is 400nm；
(4) AZO/ITO layers and LiFe (WO are coated with by more than4)2The glass substrate of layer is placed in vacuum annealing furnace, dry in 1Pa Dry lower 300 DEG C of air atmosphere is annealed 60 minutes, cools to room temperature with the furnace；
Electrochromism charge storage electrode coloring made above/colour fading absorbs spectrogram, and cyclic voltammetry curve holds with electric charge Amount curve is shown in accompanying drawing：Fig. 2~Fig. 5 (Sample 2).
Embodiment 3
(1) it is utilized respectively acetone, ethanol and pure water unorganic glass to be carried out being cleaned by ultrasonic 15 minutes successively, nitrogen purging After be placed in drying process in baking oven, remove the greasy dirt and impurity on its surface, the glass substrate for cleaning dry be placed in vacuum chamber Interior, depositional mode is Deposited By Dc Magnetron Sputtering, and target is ZnO (AZO) target that Al adulterates, and target-substrate distance is 9cm, utilizes vavuum pump Chamber vacuum is set to be down to 1 × 10-3Pa, regulation argon gas and oxygen gas flowmeter make chamber pressure be maintained at 0.8Pa, wherein argon oxygen Than for 25/1, substrate temperature is room temperature, and deposition power is 100W, and sedimentation rate is 40nm/min, and deposit thickness is 80nm；Utilize GZO targets, target-substrate distance is 9cm, Chamber vacuum is down to 1 × 10 using vavuum pump-3Pa, regulation argon gas and oxygen gas flowmeter make Chamber pressure is maintained at 0.5Pa, and wherein argon oxygen ratio is 20/1, and substrate temperature is room temperature, and deposition power is 120W, and sedimentation rate is 55nm/min, deposit thickness is 100nm；Continue to deposit ITO conductive layer with ITO targets, target-substrate distance is 9cm, makes chamber using vavuum pump Room vacuum is down to 1 × 10-3Pa, regulation argon gas and oxygen gas flowmeter make chamber pressure be maintained at 1.0Pa, and wherein argon oxygen ratio is 30/1, substrate temperature is room temperature, and deposition power is 100W, and sedimentation rate is 50nm/min, and deposit thickness is 120nm；
(2) glass substrate for having deposited transparency conducting layer is placed in vacuum annealing furnace, 250 DEG C under 1Pa argon atmospheres Annealing 30 minutes, cools to room temperature with the furnace；
(3) sample after will be annealed above is placed in vacuum chamber, and depositional mode is electron-beam evaporation, and target is LiFe(WO4)2Target, target-substrate distance is 15cm, Chamber vacuum is down to 1 × 10 using vavuum pump-3Substrate temperature in Pa, deposition process For room temperature, electron gun line is 7mA, and voltage is 6.5kV, and sedimentation rate is 76nm/min, and deposit thickness is 700nm；
(4) AZO/GZO/ITO layers and LiFe (WO are coated with by more than4)2The glass substrate of layer is placed in vacuum annealing furnace, Lower 400 DEG C of 1Pa dry air atmosphere is annealed 20 minutes, cools to room temperature with the furnace；
Electrochromism charge storage electrode coloring made above/colour fading absorbs spectrogram, and cyclic voltammetry curve holds with electric charge Amount curve is shown in accompanying drawing：Fig. 2~Fig. 5 (Sample 3).

Claims (5)

1. a kind of inorganic brown electrochromism charge storage electrode, it is characterised in that：
The composition of electrode includes：Transparent base layer (101), transparency conducting layer (102) and electrochromism charge storage layer (103) three Part, is followed successively by electrochromism charge storage layer, transparency conducting layer, transparent base layer, the storage of electrochromism electric charge from top to bottom Layer is by LiFe (WO4)2Composition；Electrically conducting transparent layer material used in electrode is tin indium oxide, the tin oxide of Fluorin doped, tin oxide, oxidation One or more of Film laminateds in zinc, the ZnO of ZnO, Ga doping of Al doping；Transparent substrates layer material used in electrode is inorganic Glass, polyimides, polyethylene terephthalate or polycarbonate transparent base material.
2. a kind of method of the inorganic brown electrochromism charge storage electrode prepared described in claim 1, it is characterized in that,
(1) transparent substrates are pre-processed
It is utilized respectively acetone, ethanol and pure water to be successively cleaned by ultrasonic transparent base layer, baking oven is placed in after nitrogen purging Interior drying process, removes the greasy dirt and impurity on its surface；
(2) vacuum PVD prepares transparency conducting layer
Transparency conducting layer is prepared using magnetron sputtering mode or electron-beam evaporation mode, the resistance per square of transparency conducting layer is 5-30 Ω/□；
(3) vacuum PVD electrochromism charge storage layer and subsequent heat treatment crystallization
Charge storage layer is prepared using magnetron sputtering mode or electron-beam evaporation mode, the deposition atmosphere used is argon gas or argon Oxygen gas mixture, setting chamber deposition air pressure range 1 × 10-2~5Pa, prepares the charge storage layer with thickness, charge storage layer 50~700nm of thickness range, after deposition terminates carry out heat treatment crystallization, 200~500 DEG C of heat-treatment temperature range, heat at The reason time is 10~180 minutes, and heat-treating atmosphere is argon oxygen gas mixture or dry air.
3. the method for inorganic brown electrochromism charge storage electrode according to claim 2, it is characterized in that, the deposition Atmosphere is argon gas or argon oxygen gas mixture, deposition pressure scope 1 × 10-1~2Pa.
4. the method for inorganic brown electrochromism charge storage electrode according to claim 2, it is characterized in that, the electric charge 100~600nm of thickness range of accumulation layer.
5. the method for inorganic brown electrochromism charge storage electrode according to claim 2, it is characterized in that, the deposition Heat treatment crystallization, 250~450 DEG C of heat-treatment temperature range are carried out after end, heat treatment time is 20~100 minutes, heat treatment Atmosphere is argon oxygen gas mixture or dry air.
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