CN110095913A - A kind of preparation method of flexible self-supporting electrochomeric films - Google Patents
A kind of preparation method of flexible self-supporting electrochomeric films Download PDFInfo
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Abstract
A kind of preparation method of flexible self-supporting electrochomeric films, is related to a kind of preparation method of electrochomeric films.The present invention is to solve NiO material conductivity differences in existing Ni-based flexible electrochromic electrode and traditional flexible conducting substrate and electrode material to combine the technical issues of influencing on device performance.The present invention: one, encapsulated layer and conductive layer are cleaned；Two, nickel hydroxide dispersion liquid is prepared；Three, graphene oxide dispersion is prepared；Four, mixing and doping graphene oxide；Five, composite membrane is calcined；Six, PVA/KOH gel electrolyte is prepared；Seven, assembled compound film；Eight, it encapsulates.The present invention realizes electrochromism, and is assembled again using two-dimensional material and realize flexible self-supporting characteristic, overcomes electrode material resistance with conductive substrates ining conjunction with, and the electric conductivity for improving nickel oxide is adulterated in the modification for passing through graphene oxide.
Description
Technical field
The present invention relates to a kind of preparation methods of electrochomeric films.
Background technique
With social development, electrochemistry basic performance such as electrochromism optical property becomes the heat of scientists from all over the world's research
Point.Flexibility, lightweight, wearable intelligent electrochromism are constructed before smart window and intelligent display field have a wide range of applications
Scape.It is well known that electrode material is the key that determine flexible intelligent device, current flexibility electrochromism electrode of super capacitor one
As be using materials such as metal oxide, carbon material (carbon nanotube, graphene etc.), conducting polymers as transparency conducting layer, with
Inorganic off-color material (WO3、MoO3、TiO2、V2O, IrO, NiO etc.) or with metachrosis conducting polymer (polyaniline compound,
Poly- thiophene class, multi-metal polypyrrole etc.) it is active material layer, it is deposited on and is prepared on plastic substrate flexible.Nickel oxide therein
With preferable electrochromic property, the advantages such as cheap.
Published document prepares the combination that Ni-based flexible electrochromism is directed to electrode material and conductive substrates, passes through rotation
The modes such as coating, situ aggregation method, LBL self-assembly method, electrochemical polymerization method are by electrically conducting transparent substrate and the super electricity of electrochromism
Container electrode material combines.And combination has large effect to the performance of device, and some flexible substrates want environment
Ask higher.There is presently no the electrochromic relevant reports of Ni-based flexible self-supporting.
Summary of the invention
The present invention is to solve NiO material conductivity differences in existing Ni-based flexible electrochromic electrode and traditional soft
Property conductive substrates and electrode material combine the technical issues of influencing on device performance, and provide a kind of flexible self-supporting electrochromism
The preparation method of film.
The preparation method of flexible self-supporting electrochomeric films of the invention carries out according to the following steps:
One, encapsulated layer and conductive layer are cleaned: 60 DEG C~70 after PET film and PET-ITO film are cleaned by ultrasonic respectively
It is dried in vacuo under conditions of DEG C；The ultrasonic cleaning is successively each ultrasound 10min in deionized water, acetone and dehydrated alcohol
~12min；
Two, it prepares nickel hydroxide dispersion liquid: nickel nitrate, neopelex and hexa being mixed and are dissolved in
In deionized water, 1h~1.5h is stirred, is then transferred into polytetrafluoroethylene (PTFE) water heating kettle, is 95 DEG C~97 in hydrothermal temperature
It is reacted under conditions of DEG C for 24 hours, naturally cools to room temperature, obtain the nickel hydroxide of dodecyl intercalation, by dodecyl intercalation
Nickel hydroxide is respectively washed three times with deionized water and dehydrated alcohol respectively, is dried at room temperature for, with immersion method using formamide as removing
The nickel hydroxide of dodecyl intercalation after solvent removing is dry, after deionized water centrifuge washing, ultrasonic redisperse to water
In, obtain nickel hydroxide dispersion liquid；The concentration of nickel hydroxide is 3mg/mL~4mg/mL in the nickel hydroxide dispersion liquid；
Three, it prepares graphene oxide dispersion: preparing graphene oxide with improved Hummers method, then ultrasound point
It is scattered in water, obtains graphene oxide water solution；Diallyl dimethyl ammoniumchloride is distributed in deionized water, is gathered
Diallyldimethylammonium chloride aqueous solution；Graphene oxide water solution is added dropwise to diallyl dimethyl ammoniumchloride
In aqueous solution, 48h~50h is stirred, modified graphene oxide dispersion liquid is obtained；The concentration of the graphene oxide water solution is
1mg/mL~1.5mg/mL；The concentration of diallyl dimethyl ammoniumchloride aqueous solution is 0.02mg/mL~0.03mg/mL；Institute
The concentration of graphene oxide is 0.3mg/mL~0.5mg/mL in the modified graphene oxide dispersion liquid stated；
Four, mixing and doping graphene oxide: change what is prepared in the nickel hydroxide dispersion liquid of step 2 preparation and step 3
Property graphene oxide dispersion is mixed, and mixed liquor is obtained, with the method that vacuum filters by mixed liquor be prepared into nickel hydroxide/
Graphene oxide composite membrane；In the solute of the mixed liquor mass fraction of graphene oxide be 1%~10%, solute be by
Nickel hydroxide and graphene oxide composition；
Five, composite membrane is calcined: by the nickel hydroxide of step 4 preparation/graphene oxide composite membrane by freeze-drying, so
After remove suction filtration film, under 5 DEG C/min~7 DEG C/min heating rate from room temperature to 300~400 DEG C and 300~400
DEG C calcining 2h~3h, obtain flexible compound film；
Six, it prepares PVA/KOH gel electrolyte: PVA and deionized water being placed in three-necked flask, at 90 DEG C~95 DEG C
Under the conditions of stirring and dissolving, obtain PVA aqueous solution；60 DEG C~65 DEG C are cooled to after PVA dissolution completely, it is water-soluble that KOH is added dropwise
Liquid simultaneously stirs, and obtains PVA/KOH gel electrolyte；The concentration of PVA is 0.15g/mL~0.4g/mL in the PVA aqueous solution；
The concentration of KOH is 0.16g/mL~0.17g/mL in the KOH aqueous solution；KOH in the PVA/KOH gel electrolyte
Concentration is 1mol/L~1.2mol/L；
Seven, in the PET film after cleaning the resulting flexible compound film tiling of step 5 to step 1, in flexible compound film
Upper surface be added dropwise the resulting PVA/KOH gel electrolyte of one layer of step 6, at normal temperature solidify 10h~11h；
Eight, the PET-ITO film that step 1 is cleaned is covered into the upper of the PVA/KOH gel electrolyte after step 7 solidifies
Surface, and encapsulate, obtain flexible self-supporting electrochomeric films.
The present invention is by encapsulated layer (PET film), electrochromic layer (flexible compound film), PVA/KOH gel electrolyte and leads
Electric layer (flexible compound film) is packaged into device.It connects electrochromic layer and conductive layer carries out chemical property and optical property
Test, color becomes dark brown when device charges, and device orientation is transparent when electric discharge.
The present invention has the beneficial effect that:
The beneficial effects of the present invention are realizing electrochromism, and assembled again using two-dimensional material realize it is flexible from propping up
Characteristic is supportted, electrode material resistance in conjunction with conductive substrates is overcome, nickel oxide is improved by the modified doping of graphene oxide
Electric conductivity.
Flexible self-supporting electrochomeric films of the invention have the structure of layer upon layer, bending deformation may be implemented, thoroughly
The rate adjustable range of mistake is about 50%, coloration time 5s~6s, bleaching time 1s~2s.
Detailed description of the invention
Fig. 1 is the SEM figure for testing the flexible compound film that step 5 obtains in one；
Fig. 2 is the picture in kind for testing the flexible compound film that step 5 obtains in one；
Fig. 3 is the Raman figure for testing the composite membrane in one before step 5 calcining；
Fig. 4 is the Raman figure for testing the flexible compound film obtained after step 5 calcining in one；
Fig. 5 is the transmitance figure for testing the flexible self-supporting electrochomeric films of a preparation；
Fig. 6 is the timing diagram for testing the flexible self-supporting electrochomeric films of a preparation.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of preparation method of flexible self-supporting electrochomeric films, specifically
It carries out according to the following steps:
One, encapsulated layer and conductive layer are cleaned: 60 DEG C~70 after PET film and PET-ITO film are cleaned by ultrasonic respectively
It is dried in vacuo under conditions of DEG C；The ultrasonic cleaning is successively each ultrasound 10min in deionized water, acetone and dehydrated alcohol
~12min；
Two, it prepares nickel hydroxide dispersion liquid: nickel nitrate, neopelex and hexa being mixed and are dissolved in
In deionized water, 1h~1.5h is stirred, is then transferred into polytetrafluoroethylene (PTFE) water heating kettle, is 95 DEG C~97 in hydrothermal temperature
It is reacted under conditions of DEG C for 24 hours, naturally cools to room temperature, obtain the nickel hydroxide of dodecyl intercalation, by dodecyl intercalation
Nickel hydroxide is respectively washed three times with deionized water and dehydrated alcohol respectively, is dried at room temperature for, with immersion method using formamide as removing
The nickel hydroxide of dodecyl intercalation after solvent removing is dry, after deionized water centrifuge washing, ultrasonic redisperse to water
In, obtain nickel hydroxide dispersion liquid；The concentration of nickel hydroxide is 3mg/mL~4mg/mL in the nickel hydroxide dispersion liquid；
Three, it prepares graphene oxide dispersion: preparing graphene oxide with improved Hummers method, then ultrasound point
It is scattered in water, obtains graphene oxide water solution；Diallyl dimethyl ammoniumchloride is distributed in deionized water, is gathered
Diallyldimethylammonium chloride aqueous solution；Graphene oxide water solution is added dropwise to diallyl dimethyl ammoniumchloride
In aqueous solution, 48h~50h is stirred, modified graphene oxide dispersion liquid is obtained；The concentration of the graphene oxide water solution is
1mg/mL~1.5mg/mL；The concentration of diallyl dimethyl ammoniumchloride aqueous solution is 0.02mg/mL~0.03mg/mL；Institute
The concentration of graphene oxide is 0.3mg/mL~0.5mg/mL in the modified graphene oxide dispersion liquid stated；
Four, mixing and doping graphene oxide: change what is prepared in the nickel hydroxide dispersion liquid of step 2 preparation and step 3
Property graphene oxide dispersion is mixed, and mixed liquor is obtained, with the method that vacuum filters by mixed liquor be prepared into nickel hydroxide/
Graphene oxide composite membrane；The mass fraction of graphene oxide is 1%~10% in the solute of the mixed liquor；
Five, composite membrane is calcined: by the nickel hydroxide of step 4 preparation/graphene oxide composite membrane by freeze-drying, so
After remove suction filtration film, under 5 DEG C/min~7 DEG C/min heating rate from room temperature to 300~400 DEG C and 300~400
DEG C calcining 2h~3h, obtain flexible compound film；
Six, it prepares PVA/KOH gel electrolyte: PVA and deionized water being placed in three-necked flask, at 90 DEG C~95 DEG C
Under the conditions of stirring and dissolving, obtain PVA aqueous solution；60 DEG C~65 DEG C are cooled to after PVA dissolution completely, it is water-soluble that KOH is added dropwise
Liquid simultaneously stirs, and obtains PVA/KOH gel electrolyte；The concentration of PVA is 0.15g/mL~0.4g/mL in the PVA aqueous solution；
The concentration of KOH is 0.16g/mL~0.17g/mL in the KOH aqueous solution；KOH in the PVA/KOH gel electrolyte
Concentration is 1mol/L~1.2mol/L；
Seven, in the PET film after cleaning the resulting flexible compound film tiling of step 5 to step 1, in flexible compound film
Upper surface be added dropwise the resulting PVA/KOH gel electrolyte of one layer of step 6, at normal temperature solidify 10h~11h；
Eight, the PET-ITO film that step 1 is cleaned is covered into the upper of the PVA/KOH gel electrolyte after step 7 solidifies
Surface, and encapsulate, obtain flexible self-supporting electrochomeric films.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: water is used described in step 2
Bath method with formamide be remove solvent removing it is dry after the nickel hydroxide of dodecyl intercalation carry out according to the following steps: will
The nickel hydroxide of dodecyl intercalation after drying is added in formamide, 40 DEG C of water-bath 96h；Dodecane after the drying
The quality of the nickel hydroxide of base intercalation and the volume ratio of formamide are 5mg:4mL.Other are same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: described in step 3
Graphene oxide is prepared with improved Hummers method to carry out according to the following steps: the concentrated sulfuric acid of 8mL being added to triangle and is burnt
In bottle, be heated to 80 DEG C, 1.7g potassium peroxydisulfate be added and 1.7g phosphorus pentoxide is dissolved, be added the powdered graphite of 2g and
80 DEG C of the reaction was continued 4.5h are cooled to the deionized water that 100mL is added after room temperature, stand 12h, filtering and washing, drying at room temperature；It will
Product after drying is added in beaker, and the concentrated sulfuric acid of 50mL and stirring is added, and 12g potassium permanganate is added simultaneously under condition of ice bath
Continue to stir 2h under condition of ice bath, be heated to 35 DEG C, stops heating and continue to stir 2h, the deionized water that 100mL is added continues
2h is stirred, the deionized water of 400mL is continuously added, instills the aqueous hydrogen peroxide solution of 5mL and stir 0.5h, stands 2d, prepares 1L
Mass fraction be 5% aqueous hydrochloric acid solution centrifuge washing, then neutrality is washed with deionized, obtains graphene oxide；Institute
The mass fraction for the concentrated sulfuric acid stated is 70%；The mass fraction of the aqueous hydrogen peroxide solution is 30%.Other and specific implementation
Mode one or two is identical.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: in step 7
Ambient temperature curing 10h.Other are identical as one of specific embodiment one to three.
Specific embodiment 5: present embodiment is unlike specific embodiment four: encapsulation described in step 8
Be to be packaged using uv-curable glue.Other are identical as specific embodiment four.
The present invention is verified with following tests:
Test one: this test is a kind of preparation method of flexible self-supporting electrochomeric films, specifically according to the following steps
It carries out:
One, encapsulated layer and conductive layer are cleaned: in 60 DEG C of item after PET film and PET-ITO film are cleaned by ultrasonic respectively
It is dried in vacuo under part；The ultrasonic cleaning is successively each ultrasound 10min in deionized water, acetone and dehydrated alcohol；
Two, nickel hydroxide dispersion liquid is prepared: by the six of the nickel nitrate of 0.5g, the neopelex of 1.4g and 1.6g
Methenamine mixing is dissolved in the deionized water of 50mL, is stirred 1h, is then transferred into polytetrafluoroethylene (PTFE) water heating kettle, in hydro-thermal
Reaction temperature is reacted for 24 hours under conditions of being 95 DEG C, is naturally cooled to room temperature, is obtained the nickel hydroxide of dodecyl intercalation, by ten
The nickel hydroxide of dialkyl group intercalation is respectively washed three times with deionized water and dehydrated alcohol respectively, is dried at room temperature for, with immersion method with
Formamide is the nickel hydroxide for removing the dodecyl intercalation after solvent removing drying, super after deionized water centrifuge washing
Sound redisperse obtains nickel hydroxide dispersion liquid into water；The concentration of nickel hydroxide is 3mg/ in the nickel hydroxide dispersion liquid
mL；
Three, it prepares graphene oxide dispersion: preparing graphene oxide with improved Hummers method, then ultrasound point
It is scattered in water, obtains graphene oxide water solution；Diallyl dimethyl ammoniumchloride is distributed in deionized water, is gathered
Diallyldimethylammonium chloride aqueous solution；Graphene oxide water solution is added dropwise to diallyl dimethyl ammoniumchloride
In aqueous solution, 48h is stirred, modified graphene oxide dispersion liquid is obtained；Stone is aoxidized in the modified graphene oxide dispersion liquid
The concentration of black alkene is 0.5mg/mL；The concentration of the graphene oxide water solution is 1mg/mL；Diallyl dimethyl chlorine
The concentration for changing aqueous ammonium is 0.02mg/mL；
Four, mixing and doping graphene oxide: change what is prepared in the nickel hydroxide dispersion liquid of step 2 preparation and step 3
Property graphene oxide dispersion is mixed, and mixed liquor is obtained, with the method that vacuum filters by mixed liquor be prepared into nickel hydroxide/
Graphene oxide composite membrane；The mass fraction of graphene oxide is 5% in the solute of the mixed liquor；
Five, composite membrane is calcined: by the nickel hydroxide of step 4 preparation/graphene oxide composite membrane by freeze-drying, so
After remove suction filtration film, under the heating rate of 5 DEG C/min from room temperature to 300 and in 300 DEG C of calcining 2h, obtain flexible compound
Film；
Six, it prepares PVA/KOH gel electrolyte: the deionized water of the PVA of 3g and 20mL being placed in three-necked flask, 90
Stirring and dissolving under conditions of DEG C obtains PVA aqueous solution；60 DEG C are cooled to after PVA dissolution completely, the KOH of 10mL is added dropwise
Aqueous solution simultaneously stirs, and obtains PVA/KOH gel electrolyte；The concentration of KOH is 0.168g/mL in the KOH aqueous solution；It is described
PVA/KOH gel electrolyte in the concentration of KOH be 1mol/L；
Seven, in the PET film after cleaning the resulting flexible compound film tiling of step 5 to step 1, in flexible compound film
Upper surface be added dropwise the resulting PVA/KOH gel electrolyte of one layer of step 6, solidify 10h at normal temperature；
Eight, the PET-ITO film that step 1 is cleaned is covered into the upper of the PVA/KOH gel electrolyte after step 7 solidifies
Surface, and encapsulate, obtain flexible self-supporting electrochomeric films；
Described in step 2 with immersion method with formamide be remove solvent removing it is dry after dodecyl intercalation hydrogen
Nickel oxide carries out according to the following steps: the nickel hydroxide of the dodecyl intercalation after drying being added in formamide, 40 DEG C
Water-bath 96h；The quality of the nickel hydroxide of dodecyl intercalation after the drying and the volume ratio of formamide are 5mg:4mL；
It prepares graphene oxide with improved Hummers method described in step 3 to carry out according to the following steps: will
The concentrated sulfuric acid of 8mL is added in conical flask, is heated to 80 DEG C, and 1.7g potassium peroxydisulfate is added and the progress of 1.7g phosphorus pentoxide is molten
The powdered graphite of 2g is added and the reaction was continued at 80 DEG C 4.5h in solution, is cooled to the deionized water that 100mL is added after room temperature, stands
12h, filtering and washing, drying at room temperature；Product after drying is added in beaker, the concentrated sulfuric acid of 50mL and stirring is added, in ice
12g potassium permanganate is added under the conditions of bath and continues to stir 2h under condition of ice bath, is heated to 35 DEG C, stops heating and continues to stir
2h, the deionized water that 100mL is added continue to stir 2h, continuously add the deionized water of 400mL, the hydrogen peroxide for instilling 5mL is water-soluble
Liquid simultaneously stirs 0.5h, stands 2d, and the mass fraction for preparing 1L is 5% aqueous hydrochloric acid solution centrifuge washing, then is washed with deionized water
Neutrality is washed, graphene oxide is obtained；The mass fraction of the concentrated sulfuric acid is 70%；The quality of the aqueous hydrogen peroxide solution
Score is 30%.
Encapsulation described in step 8 is packaged using uv-curable glue, encapsulated layer (PET film) and electroluminescent change
Chromatograph (flexible compound film) sticks together, and PVA/KOH gel electrolyte and conductive layer (flexible compound film) stick together.
Fig. 1 is the SEM figure for testing the flexible compound film that step 5 obtains in one, it can be seen that flexible compound film is nanometer sheet
Layer upon layer structure.
Fig. 2 is to test the picture in kind of flexible compound film that step 5 obtains in one, it can be seen that flexible compound film can be with
Bending.
Fig. 3 is the Raman figure for testing the composite membrane in one before step 5 calcining, it can be seen that has an apparent D, the peak G can be with
Find out and is mixed with graphene oxide.
Fig. 4 is the Raman figure for testing the flexible compound film obtained after step 5 calcining in one, it can be seen that after calcining
Sample is converted into nickel oxide.
Electrochromism test is carried out to the film of synthesis:
Fig. 5 is the transmitance figure for testing the flexible self-supporting electrochomeric films of a preparation, and curve 1 is colour fading state, curve 2
For coloured state, it can be seen that the optics adjustable range of composite membrane is 50% at 550nm.
Fig. 6 is the timing diagram for testing the flexible self-supporting electrochomeric films of a preparation, and can calculate coloration time is
5s~6s, bleaching time are 1s~2s.
Claims (11)
1. a kind of preparation method of flexible self-supporting electrochomeric films, it is characterised in that flexible self-supporting electrochomeric films
Preparation method carries out according to the following steps:
One, encapsulated layer and conductive layer are cleaned: at 60 DEG C~70 DEG C after PET film and PET-ITO film are cleaned by ultrasonic respectively
Under the conditions of be dried in vacuo；The ultrasonic cleaning be successively in deionized water, acetone and dehydrated alcohol each ultrasound 10min~
12min；
Two, prepare nickel hydroxide dispersion liquid: by nickel nitrate, neopelex and hexa mix be dissolved in from
In sub- water, 1h~1.5h is stirred, is then transferred into polytetrafluoroethylene (PTFE) water heating kettle, is 95 DEG C~97 DEG C in hydrothermal temperature
Under the conditions of react for 24 hours, naturally cool to room temperature, obtain the nickel hydroxide of dodecyl intercalation, by the hydrogen-oxygen of dodecyl intercalation
Change nickel respectively washed three times with deionized water and dehydrated alcohol respectively, be dried at room temperature for, with immersion method with formamide be removing solvent
The nickel hydroxide of dodecyl intercalation after removing is dry, after deionized water centrifuge washing, ultrasonic redisperse is obtained into water
To nickel hydroxide dispersion liquid；The concentration of nickel hydroxide is 3mg/mL~4mg/mL in the nickel hydroxide dispersion liquid；
Three, it prepares graphene oxide dispersion: preparing graphene oxide with improved Hummers method, then ultrasonic disperse arrives
In water, graphene oxide water solution is obtained；Diallyl dimethyl ammoniumchloride is distributed in deionized water, polydiene is obtained
Diallyidimethylammonium chloride aqueous solution；It is water-soluble that graphene oxide water solution is added dropwise to diallyl dimethyl ammoniumchloride
In liquid, 48h~50h is stirred, modified graphene oxide dispersion liquid is obtained；The concentration of the graphene oxide water solution is 1mg/
ML~1.5mg/mL；The concentration of diallyl dimethyl ammoniumchloride aqueous solution is 0.02mg/mL~0.03mg/mL；Described
The concentration of graphene oxide is 0.3mg/mL~0.5mg/mL in modified graphene oxide dispersion liquid；
Four, mixing and doping graphene oxide: the modification oxygen that will be prepared in the nickel hydroxide dispersion liquid of step 2 preparation and step 3
Graphite alkene dispersion liquid is mixed, and mixed liquor is obtained, and mixed liquor is prepared into nickel hydroxide/oxidation with the method that vacuum filters
Graphene composite film；The mass fraction of graphene oxide is 1%~10% in the solute of the mixed liquor；
Five, it calcines composite membrane: by the nickel hydroxide of step 4 preparation/graphene oxide composite membrane by freeze-drying, then going
Fall to filter film, to forge from room temperature to 300~400 DEG C under 5 DEG C/min~7 DEG C/min heating rate and at 300~400 DEG C
2h~3h is burnt, flexible compound film is obtained；
Six, it prepares PVA/KOH gel electrolyte: PVA and deionized water being placed in three-necked flask, in 90 DEG C~95 DEG C of condition
Lower stirring and dissolving, obtains PVA aqueous solution；60 DEG C~65 DEG C are cooled to after PVA dissolution completely, KOH aqueous solution is added dropwise simultaneously
Stirring, obtains PVA/KOH gel electrolyte；The concentration of PVA is 0.15g/mL~0.4g/mL in the PVA aqueous solution；It is described
KOH aqueous solution in the concentration of KOH be 0.16g/mL~0.17g/mL；The concentration of KOH in the PVA/KOH gel electrolyte
It is 1mol/L~1.2mol/L；
Seven, in the PET film after cleaning the resulting flexible compound film tiling of step 5 to step 1, in the upper of flexible compound film
The resulting PVA/KOH gel electrolyte of one layer of step 6 is added dropwise in surface, solidifies 10h~11h at normal temperature；
Eight, the PET-ITO film that step 1 is cleaned is covered to the upper table of the PVA/KOH gel electrolyte after step 7 solidifies
Face, and encapsulate, obtain flexible self-supporting electrochomeric films.
2. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
It is dried in vacuo under conditions of 60 DEG C after being cleaned by ultrasonic PET film and PET-ITO film respectively in one.
3. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
Nickel nitrate, neopelex and hexa are mixed in two and are dissolved in deionized water, 1h is stirred, then shifts
Into polytetrafluoroethylene (PTFE) water heating kettle, is reacted for 24 hours under conditions of hydrothermal temperature is 95 DEG C, naturally cool to room temperature, obtain
The nickel hydroxide of dodecyl intercalation.
4. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
The concentration of nickel hydroxide is 3mg/mL in nickel hydroxide dispersion liquid described in two.
5. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
Described in two with immersion method with formamide be remove solvent removing it is dry after dodecyl intercalation nickel hydroxide be by with
What lower step carried out: the nickel hydroxide of the dodecyl intercalation after drying being added in formamide, 40 DEG C of water-bath 96h；It is described
Drying after dodecyl intercalation nickel hydroxide quality and formamide volume ratio be 5mg:4mL.
6. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
Graphene oxide is prepared with improved Hummers method described in three to carry out according to the following steps: the concentrated sulfuric acid of 8mL is added
Enter into conical flask, be heated to 80 DEG C, 1.7g potassium peroxydisulfate is added and 1.7g phosphorus pentoxide is dissolved, the stone of 2g is added
Ink powder end and the reaction was continued at 80 DEG C 4.5h are cooled to the deionized water that 100mL is added after room temperature, stand 12h, filtering and washing,
Drying at room temperature；Product after drying is added in beaker, the concentrated sulfuric acid of 50mL and stirring is added, is added under condition of ice bath
12g potassium permanganate simultaneously continues to stir 2h under condition of ice bath, is heated to 35 DEG C, stops heating and continues to stir 2h, is added 100mL's
Deionized water continues to stir 2h, continuously adds the deionized water of 400mL, instills the aqueous hydrogen peroxide solution of 5mL and stir 0.5h, quiet
2d is set, the mass fraction for preparing 1L is 5% aqueous hydrochloric acid solution centrifuge washing, then neutrality is washed with deionized, and obtains oxygen
Graphite alkene；The mass fraction of the concentrated sulfuric acid is 70%；The mass fraction of the aqueous hydrogen peroxide solution is 30%.
7. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
The mass fraction of graphene oxide is 5% in the solute of mixed liquor described in four.
8. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
In five under the heating rate of 5 DEG C/min from room temperature to 300 and in 300 DEG C of calcining 2h, obtain flexible compound film.
9. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
60 DEG C are cooled to after PVA dissolution completely in six, the KOH aqueous solution of 0.168g/mL is added dropwise and stirs, obtains PVA/KOH
Gel electrolyte.
10. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
Solidify 10h in seven at normal temperature.
11. a kind of preparation method of flexible self-supporting electrochomeric films according to claim 1, it is characterised in that step
Encapsulation described in eight is packaged using uv-curable glue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430295.9A CN110095913B (en) | 2019-05-22 | 2019-05-22 | Preparation method of flexible self-supporting electrochromic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910430295.9A CN110095913B (en) | 2019-05-22 | 2019-05-22 | Preparation method of flexible self-supporting electrochromic film |
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| CN115061321A (en) * | 2022-07-14 | 2022-09-16 | 西北工业大学 | Electrochromic device comprising two-dimensional flexible material and preparation method thereof |
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| CN115061321A (en) * | 2022-07-14 | 2022-09-16 | 西北工业大学 | Electrochromic device comprising two-dimensional flexible material and preparation method thereof |
| CN115061321B (en) * | 2022-07-14 | 2023-10-03 | 西北工业大学 | Electrochromic device comprising two-dimensional flexible material and preparation method thereof |
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