CN101726956A - Novel unit module for solar-powered self-driven electronic paper apparatus and method for preparing same - Google Patents
Novel unit module for solar-powered self-driven electronic paper apparatus and method for preparing same Download PDFInfo
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Abstract
The invention relates to the technical field of electronic paper apparatuses, in particular to a unit module for a self-driven organic-inorganic electro-chromic electronic paper apparatus. The unit module is characterized in that the unit module has the following structure: a lower conductive film of cathode conductive glass is provided with a square etching region; the lower conductive film outside the square etching region is provided with an energy storage film layer and a solar cell light anode in turn; the lower conductive film inside the square etching region is provided with an electro-chromic cathode; an encapsulating material is arranged in the etching region and around the lower conductive film; the anode conductive glass and cathode conductive glass are longitudinally symmetrically arranged on the encapsulating material so as to be solidified into zigzag inner and outer cavities; an electro-chromic capacitance layer and a large-grain TiO2 reflecting layer are arranged in turn below an upper conductive film of the inner cavity; a Pt film counter electrode is arranged below the upper conductive film of the outer cavity; and the inner and outer cavities are respectively provided with electro-chromic electrolyte and solar cell electrolyte. Compared with the prior art, the novel unit module has the advantages of simple technique and low cost.
Description
[technical field]
The present invention relates to Electronic Paper device technology field, particularly a kind of unit module of Electronic Paper device of self-driven organic and inorganic novel electrochromic.
[technical background]
On the one hand, fast development along with infotech, in the research of the flat-panel monitor of pursuing ultra-thin, low-power consumption, electrochromic display device (ECD) (ECD) has low driving voltage, super contrast clearly, broad visual angle and superior memory effect become the research focus of new display and e-book, electronic newspaper.On the other hand, also increasing to the demand of the energy along with the rapid increase of world population, sun power is as a kind of regenerative resource, have other energy incomparable advantage.The solar-energy photo-voltaic cell that 20 th century later grow up has been used for the power supply, advertisement of artificial satellite, signal lamp, field inspection website with fields such as power supply, photoelectricity water pump, family's electric power system, solar telephone/ship/aircraft, microwave communication relay station power supply, mobile phones, shows huge market application foreground.
Free time in the life, we need see that some books improve the mastery of oneself, expand the visual field of oneself, obviously it is impracticable carrying a large amount of conventional book, everybody most of the selection reaches this purpose with portable terminal at present, but eyes are stared at for a long time on the screen of LCD flicker can cause eyes dry and astringent, consequences such as visual deterioration, and be limited to the capacity problem of lithium ion battery at present, there are not enough electric weight to support the operation of long-time portable terminal.
Electrochromism (Electrochromic is called for short EC) phenomenon is meant that the optical property of material with extra electric field reversible variation takes place, and utilizes this character of material can be made into the adjustable electrochromic device of color and light penetration or reflectivity.Traditional electrochromic device is widely used in automobile Antiglaring rear mirror, controlled smart window etc.
Electrochromic material is divided into two big classes: a class is inorganic off-color material, also is the film material that traditional electrochromic device extensively adopts, and is most typical as MoO
3, V
2O
5, WO
3Deng, be injected into when making ion and electron synchrotron and realize variable color in the sull by the control external electrical field, because ion and electronics are inserted in the body mutually of sull, cause the variable color response time elongated, can't be applied in the demonstration field.In addition, the complex process of preparation well-crystallized's sull needs strict its crystal formation of control, and inorganic off-color material is difficult to as MATERIALS FOR DISPLAY.
Another kind of is the organic electrochromic material, the purpose that different change color realizes variable color takes place after getting betatopic by organic molecule, these organic molecules have: purpurine class, azophenlyene class, rare earth phthalocyanines, phenothiazines or the like, this organic off-color material is except having high colorant density and contrast, have more quicker response than inorganic off-color material, can reach femtosecond.In addition, can realize the demonstration of full color by the structure of chemical method control organic molecule.Organic photochromic molecule directly is adsorbed onto the conductive substrates surface,,, can't makes its practicability in the variable color device because colorant density is very low though the response time can reach a millisecond order of magnitude.
[summary of the invention]
The objective of the invention is to design a kind of organic-inorganic compoiste electrochromic device (ECD) module that drives by DSSC (DSSC), the electric current that produces by self dye sensitization light anode under the condition that does not need external voltage carries out self-powered, painted and fading time is that the response time was less than 1 second, the visual angle is near 180 ℃, the flicker free problem, utilize the self-powered Electronic Paper device of sun power, can realize energy consumption saving to a greater extent, easy to carry, and lower compared with current E-book reader cost, therefore have very big application potential.
For achieving the above object, design a kind of novel unit module for solar-powered self-driven electronic paper apparatus, it is characterized in that unit module is provided with following structure: the following conductive film that the lower glass substrate upper surface covers as cathode electrode constitutes the negative electrode electro-conductive glass, on following conductive film, be provided with the ring groove etch areas of " mouth " word structure, cover energy storage rete on the following conductive film outside " mouth " font, cover the electrochromism negative electrode on the following conductive film in " mouth " font, cover solar battery light anode on the energy storage rete, reach down in etch areas and be provided with encapsulating material around the conductive film upper surface; The last conductive film that the top glass substrate lower surface covers as anode electrode constitutes anode conducting glass, and anode conducting glass and negative electrode electro-conductive glass symmetry up and down are placed on the inside and outside chamber that solidifies formation " returning " font on the encapsulating material; With the corresponding inner cavity chamber of electrochromism negative electrode on the conductive film lower surface be provided with electrochromism capacitor layers and bulky grain TiO from top to bottom successively
2The reflection horizon, the conductive film lower surface covers the Pt film to electrode on outer chamber; The top of inside and outside chamber is respectively equipped with the encapsulated holes that runs through anode conducting glass, is packaged with electrochromism electrolytic solution and solar cell electrolytic solution in the inside and outside chamber respectively; On the solar battery light anode of the electrochromism negative electrode of inner cavity chamber, outer chamber, be respectively equipped with lead and draw outside the cavity, adopt gauge tap to be cascaded; Described solar battery light anode, electrochromism negative electrode all adopt nanocrystalline TiO
2Semiconductor porous film.
Described following conductive film as cathode electrode is to adopt among metal A g, Al, Cu, Cr or the Ni any, or conductive oxide ZnO:Al, ITO, FTO, SnO
2In the transparent conductive film that forms of any material preparation; Described last conductive film as anode electrode is to adopt ZnO:Al, ITO, FTO or SnO
2In the transparent conductive film that forms of any material preparation.
Described energy storage rete is WO
3Film.
Described nanocrystalline TiO
2Semiconductor porous film is to adopt nanoscale TiO
2Slurry serigraphy film forming, described nanoscale TiO
2Slurry is with the TiO of 4g-6g particle diameter at 25nm～30nm
2Powder places glass mortar, adding 6ml contains the terpinol of 3%-6% (weight) ethyl cellulose, and the 1.0ml diacetone grinds evenly, after the TiO2 powder is uniformly dispersed, add the terpinol dilution of 20ml 3%-6% (weight) ethyl cellulose again and continue grinding, front and back twice grinding step 2 hours altogether adds the 0.6mlOP emulsifying agent at last and forms.
Described bulky grain TiO
2The reflection horizon is to adopt bulky grain TiO
2Slurry serigraphy film forming, described bulky grain TiO
2Slurry is to be the TiO of 250nm with the 4g-6g particle diameter
2Powder places glass mortar, adding 6ml contains the terpinol of 3%-6% (weight) ethyl cellulose, and the 1.0ml diacetone grinds evenly, after the TiO2 powder is uniformly dispersed, add the terpinol dilution of 20ml 3%-6% (weight) ethyl cellulose again and continue grinding, front and back twice grinding step continues 2 hours altogether, adds the 0.6mlOP emulsifying agent at last and forms.
Described electrochromism capacitor layers adopts SnO
2: the Sb membraneous material.
Described solar cell electrolytic solution comprises 1mmol LiI, 0.05mmol I2,6mmolDMPII, 0.5mmol TBP and solvent 3-methoxypropionitrile; Described electrochromism electrolytic solution comprises 0.2M lithium perchlorate, 0.2M ferrocene and solvent 1,4-butyrolactone.
A kind of preparation method of novel unit module for solar-powered self-driven electronic paper apparatus, it is characterized in that adopting following technology to be prepared from: a, preparation cathode and anode electro-conductive glass by the described structure of claim 1, adopt conductive film under the chemical etching method etching then, make down the etch areas of conductive film centre formation " mouth " font groove structure, and distinguish encapsulated holes of pre-subdrilling in the part of the inside and outside chamber of anode conducting correspondence on glass; B, preparation unit module negative electrode: the WO that adopts constant voltage electrodeposition process preparation desired thickness on the extra-regional conductive film down of " mouth " font
3After film is stored rete as energy, again at WO
3While serigraphy nanocrystalline TiO on the thin layer and on the last conductive film in " mouth " font
2Semiconductor porous film forms the negative electrode of whole unit module respectively as electrochromism negative electrode and solar battery light anode; C, preparation unit module anode: the Pt film that the conductive film lower surface prepares desired thickness on outer chamber is to electrode, and the preparation of conductive film lower surface is as the nanoscale SnO of electrochromism capacitor layers in inner cavity chamber
2: the Sb thin layer prepares bulky grain TiO at electrochromism capacitor layers lower surface again
2The reflection horizon, the anode of formation whole unit module; D, the electrochromism organic molecule is synthetic: 4.5g～5.5g 4 ' 4-dipyridine and 15g～20g 2-bromoethyl phosphoric acid dihexyl are joined in the 60-80ml deionized water and mix, mixed solution 80-90 ℃ was refluxed 60～80 hours, natural cooling, adding 75～85ml concentration is 50% hydrochloric acid, 50-70 ℃ is continued down to reflux 24～30 hours, the mixed liquor that will continue the backflow cooling then revolves to steam and is concentrated into 50ml, dropwise add 200ml～350ml isopropyl alcohol, ice bath stirs simultaneously, obtains white opacity liquid, filter, get the white crystals thing, the white crystals thing with 0 ℃ of isopropyl alcohol flushing, obtains white crystal again, be organic photochromic molecule with phosphate group, white crystal is dissolved in deionized water, prepares 2-phosphoric acid ethyl-4, the 4 dipyridine solution of 0.2mM-0.5mM, the dark preservation, standby; E, with the unit module negative electrode that makes with 120 ℃ of oven dry 20min, the annealing that heats up stage by stage rises to 300 ℃ in promptly 60 minutes, be incubated 20 minutes, rise to 500 ℃ of sintering 30 minutes again, naturally cool to 100 ℃ of taking-ups, immerse in the D102 dye solution of 0.5mM, soaking at room temperature 15-20 hour, behind 80 ℃ of dry 6h, again negative electrode is immersed in 2-phosphoric acid ethyl-4, the 4 dipyridine solution of 0.2mM-0.5mM in the drying box, soaking at room temperature 24h takes out dry place and preserves; F, draw two leads respectively, be cascaded with external control switch at electrochromism negative electrode and solar battery light anode; G, etch areas and down on the conductive film around place the strip encapsulating material, and with the unit module anode be placed on the encapsulating material with unit module negative electrode symmetry after, be cured encapsulation in 40 minutes with 120 ℃ of heating, form have an interior outer chamber " return " font structure; H, Vacuum Package electrolytic solution: through encapsulated holes, encapsulate the solar cell electrolytic solution of outer chamber earlier, encapsulate the electrochromism electrolytic solution of inner cavity chamber again.
The present invention compared with prior art, the modular design of Electronic Paper device utilizes the big characteristics of nano material specific surface area to adsorb organic photochromic molecule, significantly improved tinctorial yield, reached the visual angle broadness, low in energy consumption, response speed is quick, the high requirement of contrast as the display device indispensability, and and the light anode of DSSC has carried out integrated cleverly, become the self-powered Electronic Paper that breaks away from external power supply fully and show that these have paved road for compound type electrochromic device practicability;
Nanocrystalline TiO
2Because its suitable oxidation-reduction potential has very high transmitance in visible-range, the characteristics of higher reflection coefficient and nontoxic, fast light burn into cheapness are widely used in fields such as DSSC (DSSC), photocatalysis, automatically cleaning; DSSC material nano TiO
2Material utilizes TiO as the light anode
2The porous membrane adsorpting dye molecule, under radiation of visible light, dyestuff is excited, and electronics is injected into TiO
2Conduction band in finish carrier separation, it is reported that the present efficient of DSSC surpasses 11%;
Preparation technology of the present invention is simply many compared with current E-book reader, and cost is cheaper, this kind preparation of devices encapsulation flow process and current LCD streamline are identical substantially, need not the practicability that too big change can realize this device, the Electronic Paper device of making has that contrast height, visual angle are wide, low-power consumption, fast, the advantages of environment protection of response speed, is a kind of very promising e-book display technique.
[description of drawings]
Fig. 1 is a structural representation of the present invention.
Fig. 2 is the connection diagram on the lower glass substrate among the present invention.
Fig. 3 is the connection diagram under the top glass substrate among the present invention.
Appointment Fig. 1 is a Figure of abstract.
To Fig. 3,1 is lower glass substrate referring to accompanying drawing 1; 2 for following conductive film, as cathode electrode; 3 are the electrochromism negative electrode, adopt nanocrystalline TiO
2Semiconductor porous film; 4 is solar battery light anode; 5 are energy storage rete; 6 is etch areas, for being the groove of " mouth " font; 7 are the electrochromism capacitor layers; 8 is that the Pt film is to electrode; 9 is encapsulating material; 10 is outer chamber, is encapsulated into solar cell electrolytic solution; 11 is inner cavity chamber, is encapsulated into electrochromism electrolytic solution; 12 is bulky grain TiO
2The reflection horizon; 13 encapsulated holes are provided with 2, lay respectively on the upper glass of inside and outside chamber; 14 is top glass substrate; 21 is last conductive film, as anode electrode; 22 is lead.
[embodiment]
The invention will be further described below in conjunction with example.
Embodiment
The design display module is prepared two 4cm * 5cm glass substrates, reserves encapsulated holes, the radius 3mm of encapsulated holes, and concrete processing step is as follows:
One, preparation electro-conductive glass
1, the preparation of negative electrode electro-conductive glass:
Lower glass substrate 1 is prepared, and mainly comprises cutting, polishing and the cleaning of lower-glass;
Cathode electrode, promptly descend the preparation of conductive film 2: can adopt technology preparation conductive films 2 under preparation on the lower glass substrate 1 such as various one-tenth membrane meanses such as serigraphy, evaporation, magnetron sputtering, pulling film forming, spendable material comprises any in the metals such as Ag, Al, Cu, Cr or Ni, or ZnO:Al, ITO, FTO, SnO
2Deng in the conductive oxide any, adopt FTO in this example;
Cathode electrode is graphical: adopt the conventional chemical lithographic technique to make, etching " mouth " font groove formation etch areas 6 on the conductive film 2 down.
2, the preparation of anode conducting glass:
Anode electrode, the preparation of promptly going up conductive film 21: adopt conductive film in the thin film-forming method preparations such as vacuum moulding machine PVD or CVD or serigraphy at top glass substrate 14 lower surfaces, adoptable material: ZnO:Al, ITO, FTO or SnO
2In any.
3, with the cleaning of cathode and anode electro-conductive glass:
The cathode and anode electro-conductive glass is earlier with acetone ultrasonic cleaning 20 minutes, after soaked 2 hours in the 10%NaOH solution again, take out the back deionized water rinsing, last N
2Dry up, place aqueous isopropanol standby;
Two, preparation unit module negative electrode
1, adopts the WO of constant voltage electrodeposition process preparation as energy storage rete 5
3Film:
Adopt the constant voltage electrodeposition process to prepare the WO of desired thickness on the following conductive film outside " mouth " font
3Film is ring-type, and described constant voltage electrodeposition process is that 4.5g tungsten powder and 15ml hydrogen peroxide are reacted 20h-24h in ice bath, product is filtered, remove the bulky grain of generation and the tungsten powder aggregate of complete reaction not, filtrate at 50 ℃～60 ℃ backflow 10-12h, is obtained buff WO
3Colloidal sol is got 4mlWO
3Colloidal sol with mix with the volume absolute ethyl alcohol, be heated to 55 ℃-60 ℃ as electroplate liquid, adopt three-electrode system, working electrode is the FTO electro-conductive glass, auxiliary electrode is 5cm * 5cm Pt sheet, and contrast electrode is Ag/AgCl/3mol/L KCl, current potential-0.45V～-0.6V, constant potential was electroplated 30 minutes, obtained WO
3Film is used deionized water rinsing, 100 ℃～120 ℃ following thermal treatment 1h, and it is standby that room temperature is dried the sealing placement, can repeat above-mentioned technology, until reaching required WO
3Film thickness.
2, solar battery light anode and the pre-service of electrochromism negative electrode:
TiCl with 40mM～50mM
4Aqueous solution is carried out pre-service to the cathode and anode electro-conductive glass, and to improve the contact performance between conductive glass surface and the TiO2 porous membrane, 75 ℃ are incubated 30-40 minute in the vacuum drying chamber.
3, preparation TiO
2Slurry: with the TiO of 4g-6g particle diameter at 25nm～30nm
2Powder, this TiO
2Powder can adopt commercial P25, Degussa, 25% rutile phase, 75% anatase phase, place glass mortar, adding 6ml contains the terpinol of 3%-6% (weight) ethyl cellulose, and the grinding of 1.0ml diacetone evenly, after the TiO2 powder is uniformly dispersed, add the terpinol dilution of 20ml3%-6% (weight) ethyl cellulose again and continue grinding, the grinding of previous step is ground altogether with the continuation in one step of back and continued 2 hours, adds the 0.6mlOP emulsifying agent at last and forms, and is standby.
4, adopt the TiO of above-mentioned preparation
2Slurry is at WO
3Adopt silk screen print method to prepare nanocrystalline TiO on the film and on the following conductive film in " mouth " font
2Semiconductor porous film forms the negative electrode of whole unit module respectively as electrochromism negative electrode and solar battery light anode.
Three, preparation unit module anode
1, preparation bulky grain TiO
2Slurry: with the TiO of 4g～6g 250nm
2Powder places glass mortar, adds the terpinol that 6ml contains 3%～6% (weight) ethyl cellulose, and the grinding of 1.0ml diacetone evenly, works as TiO
2After powder is uniformly dispersed, adds the terpinol dilution of 20ml 3%～6% (weight) ethyl cellulose again and continue grinding, the grinding of previous step is ground altogether with the continuation in one step of back and continued 2 hours, adds the 0.6mlOP emulsifying agent at last and forms, and is standby.The purpose that adds the OP emulsifying agent is to promote colloid in on-chip even dispersion.
2, the Pt that the lower surface of conductive film 21 employing spin-coating method prepares desired thickness on outer chamber is to electrode 8, and method is as follows: with 5 * 10
-3Chloroplatinic acid-aqueous isopropanol of mol/L evenly is applied to FTO with desk-top sol evenning machine and goes up on the electro-conductive glass substrate, after the drying, 400 ℃ of sintering are 10～15 minutes in the muffle furnace, be cooled to about 100 ℃ and take out, when being cooled to 60 ℃, carry out the even glue second time, so repeat 3 times, the Pt that makes target thickness is to electrode; Conductive film 21 lower surfaces adopt nanoscale SnO in inner cavity chamber
2: the Sb slurry prepares SnO with the method for serigraphy
2: the Sb thin layer is as electrochromism capacitor layers 7, need to heat up stage by stage annealing in preparation electrochromism capacitor layers 7 processes, rise to 300 ℃ in promptly 60 minutes, be incubated 20 minutes, rise to 500 ℃ of sintering 30 minutes again, again at the bulky grain TiO of electrochromism capacitor layers 7 lower surfaces with preparation
2Slurry adopts silk screen print method to be prepared into bulky grain TiO
2Reflection horizon 12, the anode of formation whole unit module.
Four, the electrochromism organic molecule is synthetic
4.5g～5.5g 4 ' 4-dipyridine and 15g～20g 2-bromoethyl phosphoric acid dihexyl joins in 60～80ml deionized water, with mixed solution 80-90 ℃ backflow 60-80 hour, natural cooling, adding concentration is 50% hydrochloric acid 75-85ml, 50-70 ℃ is continued backflow 24-30 hour down, in order to obtain reaction product, the mixed liquor that cools off refluxing revolves to steam and is concentrated into 50ml, dropwise adds the 200ml-350ml isopropyl alcohol, and ice bath stirs simultaneously, obtain white opacity liquid, filter, get the white crystals thing, the white crystals thing is again with 0 ℃ of isopropyl alcohol flushing, obtain white crystal and be organic photochromic molecule of using among the present invention with phosphate group, white crystal is dissolved in deionized water, prepares 2-phosphoric acid ethyl-4, the 4 dipyridine solution of 0.2mM-0.5mM, the dark preservation, standby.
Five; the unit module negative electrode of above-mentioned preparation is dried 20min with 120 ℃; annealing stage by stage heats up; rise to 300 ℃ in promptly 60 minutes; be incubated 20 minutes; rise to 500 ℃ of sintering again and naturally cooled to 100 ℃ of taking-ups in 30 minutes; immerse in the D102 dye solution of 0.5mM; soaking at room temperature 15-20 hour; notice that simultaneously the electrochromism negative electrode in the middle of the protection is not dipped into by the D102 dyestuff; the method that adopts four limits to soak respectively; after taking out in drying box 80 ℃ of dry 6h; again the electrochromism negative electrode is immersed the 2-phosphoric acid ethyl-4 of 0.2mM-0.5mM; in 4 ' the dipyridine solution, soaking at room temperature 24h, endless belt shape solar battery light anode is not by 2-phosphoric acid ethyl-4 around noting simultaneously protecting; 4 ' dipyridine solution is dipped into; adopt dropper separately with 2-phosphoric acid ethyl-4,4 ' dipyridine solution drips to the method for electrochromism negative electrode, takes out dry place, back and preserves standby.
Six, draw two leads respectively at electrochromism negative electrode and solar battery light anode, be cascaded with external control switch.
Seven, around " mouth " font etch areas 6 and following conductive film upper surface, place strip Surlyn encapsulating material 9, and the unit module anode is placed on the encapsulating material 9 is fixed with unit module negative electrode symmetry, encapsulated in 40 minutes with 120 ℃ of heating, form the unit module of " returning " font structure with inside and outside chamber 10,11;
Eight, Vacuum Package electrolytic solution:
Solar cell electrolytic solution comprises 1mmol LiI, 0.05mmol I
2, 6mmol DMPH, 0.5mmol TBP and solvent 3-methoxypropionitrile; Electrochromism electrolytic solution comprises 0.2M lithium perchlorate, 0.2M ferrocene and solvent 1,4-butyrolactone;
Unit module with " returning " font structure, after being with the encapsulated holes of sealing in the inner cavity chamber with envelope earlier, immerse in the sun power electrolysis liquid, make sun power electrolysis liquid enter outer chamber, place vacuum drying chamber, vacuumize, open the vacuum drying chamber valve after 30 minutes, electrolytic solution is full of outer chamber under the external air pressure effect, reciprocation cycle 2-3 time, no obvious bubble in cavity, the encapsulated holes 13 of sealing 3mm with encapsulating material Surlyn and square little glass sheet;
Take down the envelope band in the inner cavity chamber then, the encapsulated holes in the inner cavity chamber is immersed in the electrochromism electrolytic solution, encapsulate, be full of inner cavity chamber fully as the electrochromism cavity until electrochromism electrolytic solution with above-mentioned same method.
In this example DSSC and Structures of Electrochromic Devices have been carried out effective integratedly, prepared a kind of self-powered practicability electrochromic device.
The inorganic material that relates in this example is nanocrystalline TiO
2Semiconductor porous film by optimizing thin film preparation process and prescription, has been prepared the porous nano film; The organic material that relates to is the smart class organic molecule of purple sieve, and 4, the relevant group of grafting is realized on 4 '-dipyridine molecule, and accurately grasps at the nanocrystalline TiO of preparation by chemical organic synthesis
2The proportioning of each component in the semiconductor porous film material has realized high photoelectric transformation efficiency.
Adopt the surface plating to mix the glass (FTO) of tin indium oxide (ITO) conductive film of F in this example, face resistance is 15/.
Claims (8)
1. novel unit module for solar-powered self-driven electronic paper apparatus, it is characterized in that unit module is provided with following structure: the following conductive film (2) that lower glass substrate (1) upper surface covers as cathode electrode constitutes the negative electrode electro-conductive glass, on following conductive film (2), be provided with the ring groove etch areas (6) of " mouth " word structure, cover energy storage rete (5) on the following conductive film outside " mouth " font, cover electrochromism negative electrode (3) on the following conductive film in " mouth " font, cover solar battery light anode (4) on the energy storage rete (5), reach down in etch areas (6) and be provided with encapsulating material (9) around conductive film (2) upper surface; The last conductive film (21) that top glass substrate (14) lower surface covers as anode electrode constitutes anode conducting glass, and anode conducting glass and negative electrode electro-conductive glass symmetry up and down are placed on inner cavity chamber (11) and the outer chamber (10) that encapsulating material (9) is gone up curing formation " returning " font; Be provided with electrochromism capacitor layers (7) and bulky grain TiO from top to bottom successively at last conductive film lower surface with the corresponding inner cavity chamber of electrochromism negative electrode (3)
2Reflection horizon (12), the conductive film lower surface covers the Pt film to electrode (8) on outer chamber; The top of inside and outside chamber is respectively equipped with the encapsulated holes (13) that runs through anode conducting glass, is packaged with electrochromism electrolytic solution and solar cell electrolytic solution in the inside and outside chamber respectively; On the solar battery light anode of the electrochromism negative electrode of inner cavity chamber, outer chamber, be respectively equipped with lead (22) and draw outside the cavity, adopt gauge tap to be cascaded; Described solar battery light anode (4), electrochromism negative electrode (3) all adopt nanocrystalline TiO
2Semiconductor porous film.
2. novel unit module for solar-powered self-driven electronic paper apparatus as claimed in claim 1 is characterized in that: described following conductive film (2) as cathode electrode is any or conductive oxide ZnO:Al, ITO, FTO, the SnO that adopts among metal A g, Al, Cu, Cr or the Ni
2In the transparent conductive film that forms of any material preparation; Described last conductive film (21) as anode electrode is to adopt ZnO:Al, ITO, FTO or SnO
2In the transparent conductive film that forms of any material preparation.
3. novel unit module for solar-powered self-driven electronic paper apparatus as claimed in claim 1 is characterized in that: described energy storage rete (5) is WO
3Film.
4. novel unit module for solar-powered self-driven electronic paper apparatus as claimed in claim 1 is characterized in that: described nanocrystalline TiO
2Semiconductor porous film is to adopt nanoscale TiO
2Slurry serigraphy film forming, described nanoscale TiO
2Slurry is with the TiO of 4g-6g particle diameter at 25nm～30nm
2Powder places glass mortar, adding 6ml contains the terpinol of 3%-6% (weight) ethyl cellulose, and the 1.0ml diacetone grinds evenly, after the TiO2 powder is uniformly dispersed, add the terpinol dilution of 20ml 3%-6% (weight) ethyl cellulose again and continue grinding, front and back twice grinding step 2 hours altogether adds the 0.6mlOP emulsifying agent at last and forms.
5. novel unit module for solar-powered self-driven electronic paper apparatus as claimed in claim 1 is characterized in that: described bulky grain TiO
2Reflection horizon (12) is to adopt bulky grain TiO
2Slurry serigraphy film forming, described bulky grain TiO
2Slurry is to be the TiO of 250nm with the 4g-6g particle diameter
2Powder places glass mortar, adding 6ml contains the terpinol of 3%-6% (weight) ethyl cellulose, and the 1.0ml diacetone grinds evenly, after the TiO2 powder is uniformly dispersed, add the terpinol dilution of 20ml 3%-6% (weight) ethyl cellulose again and continue grinding, front and back twice grinding step continues 2 hours altogether, adds the 0.6mlOP emulsifying agent at last and forms.
6. novel unit module for solar-powered self-driven electronic paper apparatus as claimed in claim 1 is characterized in that: described electrochromism capacitor layers (7) adopts nanoscale SnO
2: the Sb membraneous material.
7. novel unit module for solar-powered self-driven electronic paper apparatus as claimed in claim 1 is characterized in that: described solar cell electrolytic solution comprises 1mmol LiI, 0.05mmol I
2, 6mmol DMPII, 0.5mmol TBP and solvent 3-methoxypropionitrile; Described electrochromism electrolytic solution comprises 0.2M lithium perchlorate, 0.2M ferrocene and solvent 1,4-butyrolactone.
8. the preparation method of a novel unit module for solar-powered self-driven electronic paper apparatus, it is characterized in that adopting following technology to be prepared from: a, preparation cathode and anode electro-conductive glass by the described structure of claim 1, adopt conductive film under the chemical etching method etching (2) then, make down the etch areas (6) of conductive film (2) centre formation " mouth " font groove structure, and distinguish an encapsulated holes of pre-subdrilling (13) in the part of the inside and outside chamber of anode conducting correspondence on glass; B, preparation unit module negative electrode: the WO that adopts constant voltage electrodeposition process preparation desired thickness on the extra-regional conductive film down of " mouth " font
3After film is stored rete (5) as energy, again at WO
3While serigraphy nanocrystalline TiO on the thin layer and on the last conductive film in " mouth " font
2Semiconductor porous film forms the negative electrode of whole unit module respectively as electrochromism negative electrode (3) and solar battery light anode (4); C, preparation unit module anode: the Pt film that the conductive film lower surface prepares desired thickness on outer chamber is to electrode (8), and the preparation of conductive film lower surface is as the nanoscale SnO of electrochromism capacitor layers (7) in inner cavity chamber
2: the Sb thin layer prepares bulky grain TiO at electrochromism capacitor layers (7) lower surface again
2Reflection horizon (12), the anode of formation whole unit module; D, the electrochromism organic molecule is synthetic: 4.5g～5.5g 4 ' 4-dipyridine and 15g～20g 2-bromoethyl phosphoric acid dihexyl are joined in the 60-80ml deionized water and mix, mixed solution 80-90 ℃ was refluxed 60～80 hours, natural cooling, adding 75～85ml concentration is 50% hydrochloric acid, 50-70 ℃ is continued down to reflux 24～30 hours, the mixed liquor that will continue the backflow cooling then revolves to steam and is concentrated into 50ml, dropwise add 200ml～350ml isopropyl alcohol, ice bath stirs simultaneously, obtains white opacity liquid, filter, get the white crystals thing, the white crystals thing with 0 ℃ of isopropyl alcohol flushing, obtains white crystal again, be organic photochromic molecule with phosphate group, white crystal is dissolved in deionized water, prepares 2-phosphoric acid ethyl-4, the 4 dipyridine solution of 0.2mM-0.5mM, the dark preservation, standby; E, with the unit module negative electrode that makes with 120 ℃ of oven dry 20min, the annealing that heats up stage by stage rises to 300 ℃ in promptly 60 minutes, be incubated 20 minutes, rise to 500 ℃ of sintering 30 minutes again, naturally cool to 100 ℃ of taking-ups, immerse in the D102 dye solution of 0.5mM, soaking at room temperature 15-20 hour, behind 80 ℃ of dry 6h, again negative electrode is immersed in 2-phosphoric acid ethyl-4, the 4 dipyridine solution of 0.2mM-0.5mM in the drying box, soaking at room temperature 24h takes out dry place and preserves; F, draw two leads respectively, be cascaded with external control switch at electrochromism negative electrode and solar battery light anode; G, etch areas (6) and down on the conductive film around place strip encapsulating material (9), and the unit module anode is placed on that encapsulating material (9) is gone up and unit module negative electrode symmetry after, be cured encapsulation in 40 minutes with 120 ℃ of heating, form have an interior outer chamber " return " font structure; H, Vacuum Package electrolytic solution: through encapsulated holes (13), encapsulate the solar cell electrolytic solution of outer chamber earlier, encapsulate the electrochromism electrolytic solution of inner cavity chamber again.
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