CN103918051B

CN103918051B - For the optoelectronic pole of DSSC and manufacture method thereof, the DSSC utilizing this optoelectronic pole

Info

Publication number: CN103918051B
Application number: CN201280053894.XA
Authority: CN
Inventors: 高敏宰; 李都权; 金奉帅; 金弘坤; 崔仁硕; 刘基天; 李真娥; 金庆坤
Original assignee: Korea Advanced Institute of Science and Technology KAIST
Current assignee: Korea Advanced Institute of Science and Technology KAIST
Priority date: 2011-09-06
Filing date: 2012-09-06
Publication date: 2016-11-30
Anticipated expiration: 2032-09-06

Abstract

The present invention relates to a kind of optoelectronic pole for DSSC and manufacture method thereof, utilize the DSSC of this optoelectronic pole.In more detail, relate to the perforated membrane (nanoparticulate metal oxide skin(coating)) including on a kind of electrically-conductive backing plate being made up of nanoparticulate metal oxide photosensitive material macromolecule layer, thus outside stimulus is had outstanding durability and mechanical strength, and the excellent optoelectronic pole for DSSC of electrical characteristics and manufacture method thereof.

Description

For DSSC optoelectronic pole and manufacture method thereof, utilize this light The DSSC of electrode

Technical field

The present invention relates to a kind of optoelectronic pole for DSSC and manufacture method thereof, utilize this optoelectronic pole DSSC, relate in more detail a kind of to outside stimulus (ultraviolet, chemical, heat and impact) tool There are outstanding durability and a mechanical strength, and the most excellent the comprising by metal oxide nanoparticles-photosensitive of electrical characteristics Property the optoelectronic pole for DSSC of perforated membrane that constitutes of material-macromolecule and manufacture method and utilization The DSSC of the method.

Background technology

Typical DSSC (dye-sensitized solar cell) be 1991 by the lattice of Switzerland The Photoelectrochemistry that Lan Zeer (Gratzel) etc. delivers, DSSC is typically by absorbing visible ray The photonasty dyestuff of line, there is the metal oxide nanoparticles of broad-band gap energy, play catalyst action by platinum (Pt) Electrode (counter electrode) and the electrolyte filled in-between are constituted.Including described photonasty dyestuff and gold The structure belonging to oxide nano-particles plays a role as semi-conducting electrode (that is, optoelectronic pole).

Described DSSC and conventional silicon solar cell or compound semiconductor solaode phase Cheaper than manufacturing expense, high with organic solar batteries phase specific efficiency, there is the feature of environmental protection and transparent advantage in addition.In order to The commercialization of this DSSC, need to outside stimulus (ultraviolet, chemical, heat and impact) there is length The stability of phase.

But, it is used for the semi-conducting electrode (that is, optoelectronic pole) of DSSC because of outside stimulus (ultraviolet in the past Line, chemical, heat, impact) there is following problem: the structural deterioration (ultraviolet, heat) of photosensitive material；Photosensitive material With the connection between metal nano oxide disconnects (chemical)；Or because of the interconnection between metal-oxide (interconnection) architectural characteristic, easily produces crack during by external force (impact).Additionally, conventional optoelectronic pole has Also result in electrode from problems such as strippable substrates.Therefore reality is a need for developing one not only to outside stimulus tool There is a durability of excellence, and the novel photoelectric pole that electrical characteristics are also excellent.

Summary of the invention

In order to solve the most conventional technical problem, it is an object of the invention to provide one for dye sensitization too The optoelectronic pole of sun energy battery and manufacture method thereof, utilize macromolecule to ensure that optoelectronic pole is to outside stimulus by simple operation There is the durability of excellence, and there are mechanical strength and the electrical characteristics of excellence.

It is a further object of the present invention to provide a kind of independently the most applicable on various substrates with the kind of substrate, use Optoelectronic pole and manufacture method thereof in DSSC.

It is a further object of the present invention to provide a kind of solaode, described optoelectronic pole is used as partly to lead by this solaode Body electrode, thus ensure durability and the mechanical strength of the semiconductor film layer of DSSC, and there is height Photoelectric efficiency.

Technical scheme

The present invention provides a kind of optoelectronic pole for DSSC, and it includes electrically-conductive backing plate and is formed at this Perforated membrane on electrically-conductive backing plate,

Described perforated membrane includes the metal oxide nanoparticles layer being adsorbed with photosensitive material and is formed at this metal oxygen Macromolecule layer on compound particle layer surface.

Described macromolecule layer can have the shape on the surface around the metal oxide nanoparticles being adsorbed with photosensitive material Shape.

The described optoelectronic pole for DSSC under following state, the slip of its photoelectric transformation efficiency Can be such that

It is 500W/m by intensity²Burdick lamp irradiate the slip (%) of the photoelectric transformation efficiency after 30 minutes for irradiating Less than 70% of starting efficiency before ultraviolet；

Subtracting of photoelectric transformation efficiency after impregnating in the alkaline solution that concentration is 0.1～80wt%, alcoholic solution or water Few rate (%) is impregnated in starting efficiency before chemical solution less than 70%；

The slip (%) of the photoelectric transformation efficiency after taking care of in 60～120 DEG C is less than the 70% of starting efficiency.

Described electrically-conductive backing plate can include being coated with the glass substrate of conducting film, flexible plastic substrates or metal basal board.Additionally, The most described electrically-conductive backing plate is flexible plastic substrates, it is possible to provide utilize the cylindrical bend of a diameter of below 10mm to test Machine carries out the light of slip (%) is starting efficiency less than 70% of the photoelectric transformation efficiency after 100～1000 bend tests Electrode.Described perforated membrane can have 30～the porosity of 80% and the thickness of 1～100um.

Additionally, the present invention provides the manufacture method of described optoelectronic pole, comprise the steps:

A) on electrically-conductive backing plate, formation includes the perforated membrane of metal oxide nanoparticles；

B) make on the surface of the metal oxide nanoparticles that photosensitive material is adsorbed in described perforated membrane；And

C) on the surface of the metal oxide nanoparticles of the perforated membrane being adsorbed with described photosensitive material, high score is applied Sub-solution is also dried, and includes macromolecule manufacturing the surface of metal oxide nanoparticles layer being adsorbed with photosensitive material The perforated membrane of layer.

Additionally, the present invention provides a kind of DSSC including described optoelectronic pole.

Below, the present invention is described in detail.

As it has been described above, the film durability that the manufacture method of conventional general semiconductor electrode has solaode declines Etc. problem.

In order to solve these problems, the applicant is it has been suggested that one mixes high score in nanoparticulate metal oxide skin(coating) Son and form the method (Korean Patent Publication No. 2010-0088310) of thin film.But, described method has the drawback that Follow-up for nanoparticulate metal oxide dye adsorption during, be available for dye adsorption position and accounted for by macromolecule According to, therefore reduce dye adsorption amount, and be coated on the surface of metal nanoparticle as the macromolecule of insulator, it is possible to harm Hinder electric transmission, thus the minimizing of current value can be caused.Additionally, described method relates to ensureing flexible dye-sensitized solar battery Problem to the durability of external impact.

Therefore, the present invention, as the invention of the described method of improvement, is characterized in that providing following method: make photosensitive material It is adsorbed under low temperature (temperature of less than 150 DEG C) or high temperature (temperature of more than 150 DEG C) Nanocrystalline metal oxide baked After Ceng, apply macromolecule and form the Nanocrystalline metal oxide layer-macromolecule layer by being adsorbed with photosensitive material and constitute Structure such that it is able to bring the photoelectric transformation efficiency of excellence, and conventional problem can be solved.That is, the present invention to provide a kind of Method can efficiently reduce the electrode problem from strippable substrate and outside stimulus (ultraviolet, chemical, heat, impact) cause Following problem: the structural deterioration (ultraviolet, heat) of photosensitive material；Or between photosensitive material and metal nano oxide Connection disconnect (chemical)；Or because of interconnection (interconnection) architectural characteristic between metal-oxide, it is subject to Crack is easily produced during external force (impact).Additionally, the present invention provides a kind of DSSC and manufacture method thereof, should Battery has the mechanical strength of excellence can bear outside strong mechanical shock.

Additionally, another feature of the present invention is to provide one independently can be applicable to any substrate such as glass with substrate type The manufacture method of the optoelectronic pole of substrate or flexible base board.

Below, it is described with reference to the preferred embodiments of the present invention so that one of skill in the art's energy of the present invention Enough easily enforcement.It should be pointed out that, for those skilled in the art, embodiment described later is used only to illustrate the present invention, Various ways is can be deformed in without departing from idea of the invention and scope.For same or similar part, use as far as possible Identical reference.

Additionally, the term used in the description " include " meaning by specific characteristic, field, integer, step, action, Key element and/or composition embody, it is not excluded that other characteristics, field, integer, step, action, key element and/or composition.

The term " nanometer " recorded in the description of the invention represents nanosized, it is possible to include units of micrometers.Additionally, The term " nanoparticle " recorded in the description includes having the particle of the form of ownership of nanosized.

First, example is realized according to the one of the present invention, it is provided that for the optoelectronic pole of DSSC, this optoelectronic pole Including electrically-conductive backing plate and be formed at the perforated membrane on this substrate, described perforated membrane includes the burning being adsorbed with photosensitive material Thing nanoparticle layers and the macromolecule layer being formed on this metal oxide nanoparticles layer surface.

The optoelectronic pole for DSSC of this present invention is coated with conducting film by transparency carrier 101 The electrically-conductive backing plate 103 of 102 and being formed on electrically-conductive backing plate, and include the metal oxide nano being adsorbed with photosensitive material The perforated membrane 107 of particle layer and macromolecule layer constitutes (Fig. 1).Fig. 1 is the generalized section of the dye-sensitized photoelectric pole of the present invention.

Especially, the optoelectronic pole of the present invention has a following feature: be 500W/m by intensity²Burdick lamp irradiate 30 minutes After the slip (%) of photoelectric transformation efficiency be less than 70% of the starting efficiency before irradiation ultraviolet radiation；It is 0.1 in concentration ～the slip (%) of the photoelectric transformation efficiency after impregnating in the alkaline solution of 80wt%, alcoholic solution or water is impregnated in Less than 70% of starting efficiency before solution；The slip (%) of the photoelectric transformation efficiency after taking care of in 60～120 DEG C For the starting efficiency before keeping in this temperature less than 70%.

It is further preferred that described optoelectronic pole is under following state, the slip of its photoelectric transformation efficiency can be such that with strong Degree is 500W/m²Burdick lamp irradiate before the slip (%) of the photoelectric transformation efficiency after 30 minutes is irradiation ultraviolet radiation The 1～70% of starting efficiency, more preferably 1～50%；The alkaline solution that concentration is 0.1～50wt%, alcoholic solution or In person's water the slip (%) of photoelectric transformation efficiency after dipping be impregnated in starting efficiency before chemical solution 1～ 70%, more preferably 1～50%；The slip (%) of the photoelectric transformation efficiency after taking care of in 60～120 DEG C is this temperature 1～70% of starting efficiency before middle keeping, more preferably 1～50%.

The optoelectronic pole of this present invention has following feature: perforated membrane includes being adsorbed with the burning of photosensitive material Thing nanoparticle layers and the macromolecule layer being formed on this metal oxide nanoparticles layer surface.Relate to i.e., in the present invention Perforated membrane can represent and use inorganic matter (metal oxide nanoparticles layer) and Organic substance (macromolecule layer) to have even simultaneously Connect the complex of relation.Additionally, the perforated membrane of the present invention can by nanoparticulate metal oxide-photosensitive material-macromolecule this Plant and be suitable for order composition.

In other words, conventional metal oxide nanoparticles and high molecular invention are utilized, although constitute burning Thing-high molecular complex, but owing to macromolecule is mixed in the fabrication process, therefore possess metal oxide nanoparticles and Macromolecule is the most entangled, and is adsorbed with the shape of dyestuff thereon.

But, the perforated membrane of the present invention, after metal oxide nanoparticles adsorbs photosensitive material, then it is being adsorbed with Apply macromolecular solution on the metal oxide nanoparticles of described photosensitive material and carry out heat treatment, so that perforated membrane can There is the shape including macromolecule layer on the surface of metal oxide nanoparticles layer being adsorbed with photosensitive material.Additionally, Can have the described macromolecule layer shape (Fig. 2) around the surface of the metal oxide nanoparticles being adsorbed with photosensitive material. Fig. 2 is the schematic diagram being coated with high molecular shape on the optoelectronic pole surface of the present invention.

That is, as in figure 2 it is shown, at the metal oxide nanoparticles layer including being adsorbed with photosensitive material of the present invention and height In the perforated membrane 107 of molecular layer, macromolecule layer 106 is received round the metal-oxide being adsorbed with photosensitive material (that is, dyestuff) The surface of rice corpuscles and formed, additionally, along with so forming macromolecule layer from the teeth outwards, in the portion not adsorbing photosensitive material Divide and also be able to be filled by described macromolecule layer, therefore, it is possible to improve electrical characteristics.

Therefore, the present invention is prevented from the minimizing of dye adsorption amount, and improves electric transmission effect such that it is able to improve electricity Characteristic.Additionally, in accordance with the invention it is possible to improve to outside stimulus (ultraviolet, chemical, heat, impact) durability and machine Tool intensity.Especially, even if under the outside stimulus that the present invention is under described rated condition, the durable of excellence also can be shown Property, therefore, it is possible to keep excellent electrical characteristics.

Additionally, the perforated membrane of the present invention is by coating process, part macromolecule is saturable to being adsorbed with photosensitive material Between metal oxide nanoparticles.Therefore, the present invention bonding force that can strengthen with substrate compared with the past.

The present invention be prevented from photosensitive material structure because of ultraviolet or heat destroyed.Additionally, in general, describedization Learn solution for disconnecting the combination between metal oxide nanoparticles and photosensitive material, even if but the optoelectronic pole of the present invention exist In described chemical solution after dipping, the connection between photosensitive material and metal oxide nanoparticles is not easy to fracture.This Outward, even if the present invention has interconnection structure (interconnection structure) characteristic between metal-oxide, due to Durability and excellent strength, therefore, it is possible to prevent crack, and the problem that can solve to peel off between substrate and electrode.

Now, the alkaline solution in described chemical solution can be the concentration comprising conventional alkaline metal be 1～80wt% Aqueous solution.Additionally, described alcoholic solution can be the aqueous solution of the ethanol comprising carbon number 1～6.Additionally, water (water) is Common water, it may include through ultra-pure water or the non-purified water of ion exchange resin.

It addition, the present invention has following feature: for the substrate being suitable in the present invention, as long as solaode On substrate can use, and transparent conductive substrate or flexible base board can use.The most described conduction Substrate can include being coated with the glass substrate of conducting film, flexible plastic substrates or metal basal board.

If in the present invention use transparent conductive substrate, it becomes possible to show the most excellent durability compared with the past, Mechanical strength and electrical characteristics.

If additionally, the present invention wants to improve further bending spy while improving durability, mechanical properties and mechanical property Property, then can use flexible plastic substrates.The DSSC being suitable for described flexible base board can be used in mobile phone, wearing The self-charging of power supply needed for the computer industry of future generation such as formula computer, or it is attached to clothes, medicated cap, vehicle glass or building etc. On, therefore receive much concern.Optoelectronic pole for the described structure of the present invention, it is possible to transparency conductive electrode is substituted by flexible base Plate such that it is able to while offer shows the flexural property of excellence, also has the light conversion interconversion rate of excellence and the resistance to of excellence The optoelectronic pole of property for a long time.

In the present invention, described electrically-conductive backing plate can be flexible plastic substrates, and described plastic base has flexibility, and includes institute State the perforated membrane of ad hoc structure.This optoelectronic pole utilizes a diameter of below 10mm, more preferably 5～the cylindrical bend of 10mm It can be the 70% of starting efficiency that testing machine carries out the slip (%) of the photoelectric transformation efficiency after 100～1000 bend tests Hereinafter, more preferably less than 50%.Therefore, described optoelectronic pole is even across bending several times, it may have excellent bending is special Property, therefore, it is possible to prevent durability from reducing because of external impact, but also excellent electrical characteristics can be kept.The most described bending Testing machine can use the bend test equipment of all routines, such as, can use the bending of the drum with described diameter range Testing machine.Additionally, can be by well known in the art curved to the bending method of optoelectronic pole when carrying out described bend test Qu Fangfa is carried out, and such as, is placed on by optoelectronic pole on the Apparatus for Bending at low-temp of circle, by mechanical means, the side of optoelectronic pole is solid Fixed, and opposite side is bent several times, or be repeated the both sides of described optoelectronic pole are bent simultaneously after the method stretched again.

Described plastic base can use selected from polyethylene terephthalate；PEN；Poly-carbonic acid Ester；Polypropylene；Polyimides；Triacetyl cellulose；Polyether sulfone；By selected from MTES, ethyl triethoxy It is three-dimensional netted that the hydrolysis of at least one the organic metal alkoxide in silane and propyl-triethoxysilicane and condensation reaction are formed The organically-modified esters of silicon acis of structure；The copolymer of above-mentioned substance；And at least one in the mixture of above-mentioned substance.Described metal Substrate can use any one in chosen from Fe, rustless steel, aluminum, titanium, nickel, copper and stannum.

Described conducting film can include SnO₂: F, ITO, average thickness be 1～1000nm metal electrode, metal nitride, Metal-oxide, carbon compound or electroconductive polymer, but it is not limited to described material, ability can be formed on the transparent substrate Well-known conventional conducting film in territory.

Described metal nitride can be the nitridation selected from the Group IVB metallic element including titanium (Ti), zirconium (Zr) and hafnium (Hf) Thing；Nitride including the VB race metallic element of niobium (Nb), tantalum (Ta) and vanadium (V)；Including chromium (Cr), molybdenum (Mo) and tungsten (W) The nitride of group vib metallic element；Aluminium nitride；Gallium nitride；Indium nitride；Silicon nitride；In the mixture of germanium nitride and these materials At least one.

Described metal-oxide can use selected from stannum (Sn) oxide；Stannum (Sn) doped with antimony (Sb), niobium (Nb) or fluorine Oxide；Indium (In) oxide；Indium (In) oxide doped with stannum；Zinc (Zn) oxide；Doped with aluminum (Al), boron (B), gallium (Ga), zinc (Zn) oxide of hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or stannum (Sn)；Magnesium (Mg) oxide；Cadmium (Cd) oxide；Magnesium zinc (MgZn) oxide；Indium zinc (InZn) oxide；Copper aluminum (CuAl) oxide；Silver (Ag) oxide；Gallium (Ga) oxide；Zinc tin oxide (ZNSNO)；Titanium oxide (TIO₂) and zinc indium stannum (ZIS) oxide；Nickel (Ni) oxide；Rhodium (Rh) oxide；Ruthenium (Ru) oxide；Iridium (Ir) oxide；Copper (Cu) oxide；Cobalt (Co) oxide；Tungsten (W) oxide；Titanium (Ti) at least one in the mixture of oxide and these materials.

Described carbon compound can use mixing selected from activated carbon, graphite, CNT, carbon black, Graphene or these materials At least one in compound.

Described electroconductive polymer can use selected from PEDOT (poly-(3,4-ethene dioxythiophene))-PSS (poly-(styrene Sulphonic acid ester)), polyaniline-camphorsulfonic acid, Benzo[b, polyacetylene, P3HT (poly-(3-hexyl thiophene)), polysiloxanes carbazole, polyphenyl Amine, poly(ethylene oxide), poly-(1-methoxyl group-4-(0-Red-1 200)-2,5-phenylene vinylene, polybenzazole, polycarbazole, poly-rattle away Piperazine, poly-different thia naphthalene, polyphenylene sulfide, polyvinyl pyridine, polythiophene, polyfluorene, polypyridine, polypyrrole, polysulfide nitrogen compound and this At least one in the copolymer of a little materials.

Macromolecule for described macromolecule layer can include selected from polyurethane, poly(ethylene oxide), polyvinylpyrrolidone, gather Expoxy propane, Polyethylene Glycol, chitosan, chitin, polyacrylamide, polyvinyl alcohol, polyacrylic acid, cellulose, ethyl cellulose, Poly hydroxy ethyl acrylate, polymethyl methacrylate, polysaccharide, polyamide, Merlon, polyethylene, polypropylene, polyphenyl second Alkene, polyethylene terephthalate, PEN, include dimethione containing polymeric silicon, isoamyl At least one macromolecule in diene, butadiene type rubber and derivant thereof.But polymer substance is not particularly limited, often The macromolecule of rule all can use.Additionally, the average thickness of described macromolecule layer can be 1～100nm, more preferably 150nm, It is preferably 1～20nm.

The metal oxide nanoparticles layer being adsorbed with photosensitive material described in additionally, can include aoxidizing selected from stannum (Sn) Thing；Stannum (Sn) oxide doped with antimony (Sb), niobium (Nb) or fluorine；Indium (In) oxide；Indium (In) oxide doped with stannum； Zinc (Zn) oxide；Doped with aluminum (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or stannum (Sn) zinc (Zn) oxide；Magnesium (Mg) oxide；Cadmium (Cd) oxide；Magnesium zinc (MgZn) oxide；Indium zinc (InZn) aoxidizes Thing；Copper aluminum (CuAl) oxide；Silver (Ag) oxide；Gallium (Ga) oxide；Zinc tin oxide (ZnSnO)；Titanium oxide (TiO₂) And zinc indium stannum (ZIS) oxide；Nickel (Ni) oxide；Rhodium (Rh) oxide；Ruthenium (Ru) oxide；Iridium (Ir) oxide；Copper (Cu) oxide；Cobalt (Co) oxide；Tungsten (W) oxide；Titanium (Ti) oxide；Zirconium (Zr) oxide；Strontium (Sr) oxide；Lanthanum (La) oxide；Vanadium (V) oxide；Molybdenum (Mo) oxide；Niobium (Nb) oxide；Aluminum (Al) oxide；Yttrium (Y) oxide；Scandium (Sc) oxide；Samarium (Sm) oxide；At least one burning in the mixture of strontium titanium (SrTi) oxide and these materials Thing nanoparticle.Preferably, described metal oxide nanoparticles can include titanium oxide nanoparticle.Described photosensitive material Can include that can absorb band gap (Band Gap) is the heliosensitivity organic substance of visible ray of 1 eV～3.1 eV, photosensitive inorganic Material, heliosensitivity organic-inorganic composition matter or the mixture of these materials.

In the present invention, described perforated membrane preferably include to be adsorbed with photosensitive material metal oxide nanoparticles layer and Polymethyl methacrylate macromolecule layer, the metal oxide nanoparticles layer being adsorbed with photosensitive material and polyvinylpyrrolidine Ketone macromolecule layer or be adsorbed with the metal oxide nanoparticles layer of photosensitive material and polymethyl methacrylate and poly-second Alkene pyrrolidone macromolecule layer.

Additionally, described perforated membrane can be to have 30～80% porosity and the perforated membrane of 1～100um thickness.

It addition, realize example according to another of the present invention to provide the manufacture method of a kind of described dye-sensitized photoelectric pole, including Following steps: (a) forms the perforated membrane including metal oxide nanoparticles on electrically-conductive backing plate；B () makes photosensitive material inhale On the surface of the metal oxide nanoparticles investing described perforated membrane；And (c) is in the porous being adsorbed with described photosensitive material Apply macromolecular solution on the surface of the metal oxide nanoparticles of film and be dried, being adsorbed with photosensitive material to manufacture The surface of metal oxide nanoparticles layer include the perforated membrane of macromolecule layer.

Additionally, according to the present invention, it is provided that a kind of DSSC including described optoelectronic pole.

The manufacture method of the dye-sensitized photoelectric pole of this present invention is preferably according to the method manufacture shown in Fig. 1.Fig. 3 is for using Manufacture method in the dye-sensitized photoelectric pole of the explanation present invention and include the DSSC of described optoelectronic pole The operation schematic diagram of manufacture method.Additionally, the sectional view of the DSSC that Fig. 4 is the present invention.

With reference to Fig. 3, in the present invention, prepare electrically-conductive backing plate 103, and formation includes metal oxide nano on the substrate The perforated membrane 104 (Fig. 3 (a)) of particle.Described electrically-conductive backing plate 103 is usable on transparency carrier 101 being coated with conducting film 102 Transparency conductive electrode (TCO:transparent conducting oxide), and the most desirable on behalf of described flexibility Substrate or metal basal board.

Afterwards, in the present invention, make photosensitive material adsorb on the surface of described perforated membrane 104, include inhaling to be formed With the perforated membrane 105 of the metal oxide nanoparticles of photosensitive material, manufacture the basic of optoelectronic pole by this technical process Structure (Fig. 3 (b)).

It follows that including being adsorbed with perforated membrane 105 upper of the metal oxide nanoparticles of described photosensitive material Topcoating applies macromolecular solution, and to manufacture the dye-sensitized photoelectric pole 110 including perforated membrane 107, this perforated membrane 107 includes being adsorbed with The metal oxide nanoparticles layer of photosensitive material and the macromolecule being formed on this metal oxide nanoparticles layer surface Layer (Fig. 3 (c)).Although there is no the structure of specifically depicted described perforated membrane 107 in Fig. 3 (c), but can have the structure of Fig. 2.

Finally, in the present invention, configuration to electrode 120 and makes itself and described dye-sensitized photoelectric pole 110 separate between regulation Every toward each other, inject electrolyte 130 afterwards and use polymer binder 140 to seal and manufacture DSSC (Fig. 3 (d)).Described can have structure well known in the art to electrode 120.As follows for an example to electrode: as Shown in Fig. 4, electrode can be included transparency carrier 101, the conducting film 102 being formed on described substrate 101 and catalyst layer 121. Through these steps, the present invention can complete the structure of the DSSC shown in Fig. 2.

Below, each step is more specifically illustrated.

Step (a)

According to the present invention, when forming perforated membrane 104 in step (a), can be according to comprising metal oxide nanoparticles Slurry preparation process in whether use binding agent to decide whether to be suitable for low temperature or high-temperature firing.And, in the present invention, root According to the applicable low temperature of the kind of described substrate or high-temperature firing.

That is, described perforated membrane 104 can will comprise the slurry coating of metal oxide nanoparticles in the one of electrically-conductive backing plate 103 On face and after carrying out heat treatment, fire under the conditions of low temperature (less than 150 DEG C) or high temperature (temperature of more than 150 DEG C) and formed.

Therefore, described (a) step forming perforated membrane can comprise the steps: that (i) will comprise metal oxide nano grain After the low-firing slurry coating of son and solvent is on electrically-conductive backing plate, at a temperature of 20～150 DEG C, carry out 1～2 little Time heat treatment；Or (ii) the high-temperature firing slurry of metal oxide nanoparticles, adhesive resin and solvent will be comprised Be coated in electrically-conductive backing plate above after, at a temperature of 450～500 DEG C, carry out the heat treatment of 1～2 hour.

Specifically, when being fired at low temperatures, the present invention can be by low-firing slurry coating at electrically-conductive backing plate After above, at a temperature of 20～150 DEG C, carry out the heat treatment of 1～2 hour, and below 150 DEG C, preferably 100～150 Fire in a low temperature of DEG C and form perforated membrane.In this case, the substrate described in electric conductivity preferably includes flexible base board. " low-firing " represents and carries out under the low temperature state relatively lower than high-temperature firing temperature more than 150 DEG C in the past in the present invention Fire.Additionally, " high-temperature firing " represents that firing temperature exceedes described 150 DEG C.

During additionally, be at high temperature fired, the present invention can be by high-temperature firing slurry coating on electrically-conductive backing plate After, at a temperature of 450～500 DEG C, carry out the heat treatment of 1～2 hour and form perforated membrane.In this case, described substrate Glass substrate etc. is preferably used.

The slurry fired under described low temperature and high temperature can be prepared by method well known in the art, therefore the method It is not particularly limited.

Such as, low-firing slurry can be prepared by the following method: metal oxide nanoparticles is mixed into solvent In, after preparing the colloid solution that the dispersed concentration of metal oxide nanoparticles reaches 10～50wt%, pass through distillator Remove solvent.Additionally, described metal oxide nanoparticles and the mixed proportion of solvent and kind are not particularly limited, can lead to Cross method selection well known in the art.Such as, described solvent can use ethanol, methanol, terpinol or lauric acid etc..With In prepare described slurry metal oxide nanoparticles be preferably sized to 10～100nm.

Additionally, high-temperature firing slurry can be prepared by the following method: metal oxide nanoparticles is mixed into solvent In, preparing and being dispersed with the viscosity of metal-oxide is 5 × 10⁴～5 × 10⁵After the colloid solution of cps, add adhesive resin Mix, and remove solvent by distillator.Additionally, described metal oxide nanoparticles, adhesive resin and solvent Mixed proportion and kind are not particularly limited, and can pass through method selection well known in the art.Such as, described bonding Agent resin can use Polyethylene Glycol, poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone or ethyl cellulose etc..Additionally, institute State solvent and can use ethanol, methanol, terpinol or lauric acid etc..

Metal oxygen well known in the art can be used for preparing the metal oxide nanoparticles of described perforated membrane Compound.Such as, metal-oxide as above can be used.

The coating method of described slurry can use the methods such as silk screen printing, but is not particularly limited, and scraper plate coating etc. is often The coating method of rule all can use.

Step (b)

The step adsorbing described photosensitive material at (b) of the present invention can include will be formed with including described metal-oxide The substrate of the perforated membrane 104 of nanoparticle impregnates the step of 1～24 hour in the solution containing photosensitive material, is consequently formed Perforated membrane 105 including the metal oxide nanoparticles being adsorbed with described photosensitive material.By this structure, shape of the present invention Become an optoelectronic pole.Second perforated membrane represents the metal oxide nanoparticles layer being adsorbed with photosensitive material.

Described photosensitive material can use the photosensitive material with as above band gap.As an example, described photosensitive material Can include selected from aluminum (Al), platinum (Pt), palladium (Pd), europium (Eu), lead (Pb), iridium (Ir), ruthenium (Ru), selenium (Se), tellurium (Te), sulfur (S) element and in the complex of these elements.

The preparation method of the solution containing described photosensitive material is not particularly limited, and can use many institute's weeks in this area The method known.

Step (c)

In the present invention, by step (c), the manufacture of the optoelectronic pole for DSSC is completed.I.e., originally Invention can apply macromolecular solution on the optoelectronic pole be adsorbed with described in preparing through step (b) photosensitive material and go forward side by side Row is dried, thus manufactures the secondary light electrode being formed with perforated membrane 107 of Fig. 2, and this perforated membrane 107 includes being adsorbed with heliosensitivity thing The metal oxide nanoparticles layer of matter and the macromolecule layer 106 being formed on this metal oxide nanoparticles layer surface.

In the present invention, utilize the conventional method of spin coated etc. to form macromolecule layer, and can be on 25 DEG C of left sides In a low temperature of the right side, described macromolecular solution is dried, therefore has and can provide quick for dyestuff by method easily Change the feature of the optoelectronic pole of solaode.

Specifically, the coating of described macromolecular solution can be come by spin coated, slit coating or dip coating method Carry out, spin coated is preferably used.Additionally, when carrying out the coating of described macromolecular solution, its thickness is not so limited, can It is 1～100nm.

Additionally, the present invention is when forming macromolecule layer, before carrying out spin coated, macromolecular solution can be dropped in absorption Have on the metal oxide nanoparticles layer of photosensitive material, make macromolecule be impregnated with in nanoparticulate metal oxide greatly afterwards About 1 minute～10 minutes.When through this process, the entrance of part macromolecule is adsorbed with the metal-oxide of photosensitive material and receives Between grain of rice sublayer, therefore can improve the cohesive with substrate further relative to the situation being directly coated with macromolecular solution.

After coating described macromolecular solution, can below 20～150 DEG C at a temperature of be dried 1 minute～30 minutes.Preferably Ground, described being dried can be carried out 1 minute～30 minutes in a low temperature of 20 DEG C～30 DEG C.Additionally, the most also can 100～ Rapid draing about 1 minute at a temperature of 150 DEG C.

Described macromolecular solution colloid solution during preferably macromolecule is scattered in solvent, molten relative to whole macromolecule Liquid, the macromolecule of 0.01～50wt% is scattered in solvent.Described macromolecular solution can pass through side well known in the art Prepared by method, therefore the method is not particularly limited.Such as, described macromolecule can be mixed in solvent, and by uniform Stirring, makes the high molecular colloid solution state being uniformly dispersed 0.01～50wt%, more preferably 0.01～10wt%. Additionally, the blending ratio of described macromolecule and solvent can vary depending on, it is preferable to employ above-mentioned ratio.

Now, the invention is characterized in that different from the concept preparing the binding agent used in conventional slurry in the past, described height Molecule final residue is on electrode.The kind of this polymer substance is not particularly limited, and can use many institute's weeks in this area The material known.

Described macromolecule can include selected from polyurethane (Polyurethane), poly(ethylene oxide) (Polyethylenoxide, PEO), poly(propylene oxide) (Polypropyleneoxide), polyvinylpyrrolidone (Polyvinylpyrrolidone), poly-second Glycol (Polyethyleneglycol, PEG), chitosan (Chitosan), chitin (Chitin), polyacrylamide (Polyacrylamide), polyvinyl alcohol, polyacrylic acid (Polyacrylic Acid), ethyl cellulose (Ethyl Cellulose), poly hydroxy ethyl acrylate (Polyhydroxyethylmethacrylicacid, PHEMA), poly-methyl-prop E pioic acid methyl ester (Polymethylmethacrylate), cellulose (Cellulose), polysaccharide (Polysaccharide), polyamides Amine (Polyamide), Merlon (Polycarbonate), polyethylene (Polyethylene), polypropylene (Polypropylene), polystyrene (Polystyrene), polyethylene terephthalate (PET), poly-naphthalenedicarboxylic acid second Diol ester (PEN), include polydimethylsiloxane (PDMS) containing polymeric silicon, isoprene, butadiene type rubber and spread out At least one macromolecular compound in biology, more preferably can include two or more macromolecules.Additionally, in the present invention In, macromolecule can use polymethyl methacrylate (Polymethylmethacrylate, PMMA), polyvinylpyrrolidone (Polyvinylpyrrolidone, PVP) or poly(ethylene oxide) (Polyethylenoxide, PEO), and at these macromolecules In can use one or be used in mixed way two or more.Now, in the present invention, according to high molecular kind, can protect further Card UV stable and chemical stability.Such as, to ensure UV stable, PVP or PMMA-PVP can be used contour Molecule.Additionally, to ensure chemical stability, the macromolecules such as PMMA or PMMA-PVP can be used.

The solvent species used when preparing described macromolecular solution is also not limited, and such as, solvent can be ethanol, first Alcohol, terpinol, lauric acid, ethyl acetate, hexane or toluene etc., as long as macromolecule can be dissolved fully, it is possible to uses and appoints What solvent.

Step (d)

In the present invention, the structure of DSSC can obtain by performing the step (d) of Fig. 2.Described Electrode, electrolyte etc., in addition to the optoelectronic pole of the configuration present invention, can be carried out by step (d) by conventional method utilizing.

Therefore, the present invention be can configure electrode and makes it electric for dye sensitization of solar with prepared by said method It is relative to each other that pond optoelectronic pole separates predetermined distance, and at described optoelectronic pole with to the space filling electrolyte between electrode, passes through Polymer binder seals described optoelectronic pole and to electrode, thus manufactures solaode.

This solaode, as shown in Fig. 3 (d) and Fig. 4, including optoelectronic pole 110, including transparency carrier 101, is coated on Conducting film 102 on described substrate and the perforated membrane 107 being formed on conducting film, this perforated membrane 107 includes being adsorbed with heliosensitivity The metal oxide nanoparticles layer of material and the macromolecule layer 106 being formed on this metal oxide nanoparticles layer surface； To electrode 120, the conducting film 102 including transparency carrier 101, being coated on described substrate and be formed at urging on described conducting film Agent layer 121；Electrolyte 130, be filled in described optoelectronic pole and to electrode between；And high molecular bonding oxidant layer 140, it is used for sealing Described optoelectronic pole and to electrode.

Described in electrode 120, catalyst layer can be formed by conventional method, for instance it can be possible that refer to utilize the shapes such as Pt Become nanoparticulate metal thin film, to form the part of structure paired electrode.This catalyst layer can include selected from platinum (Pt), activated carbon (activated carbon), graphite (graphite), CNT, carbon black, p-type quasiconductor, PEDOT (poly-(3,4-ethylene Dioxy thiophene)-PSS (poly-(styrene sulfonate)), polyaniline-CSA, Benzo[b, polyacetylene, P3HT (poly-(3-hexyl thiophene), Polysiloxanes carbazole, polyaniline, poly(ethylene oxide), (poly-(1-methoxyl group-4-(0-Red-1 200)-2,5-phenylene vinylene), Polybenzazole, polycarbazole, poly-pyridazine, poly-different thia naphthalene, polyphenylene sulfide, polyvinyl pyridine, polythiophene, polyfluorene, polypyridine, poly-pyrrole Cough up, polysulfide nitrogen compound and the derivant of these materials, the copolymer of these materials, the complex of these materials and these materials Mixture at least one.

Additionally, form the substrate phase that the described substrate 101 to electrode 120 can use and use when manufacturing described optoelectronic pole With transparency conductive electrode, transparent plastic substrate or such as the metal basal board such as rustless steel, Ti.

Additionally, in the present invention, described the substrate of electrode and the thickness of catalyst layer are not particularly limited, it may include Structure well known in the art.

For convenience of description, Fig. 1 and Fig. 2 illustrate state simply that fill up described electrolyte 130, but actually At optoelectronic pole 110 with in the space between electrode 120, described electrolyte 130 may be uniformly dispersed in the interior of perforated membrane 107 Portion.

Described electrolyte can be selected from oxidation-reduction derivant, containing macromolecule or inorganic particulate high-molecular gel electricity One in Xie Zhi, organic hole conductor (HCM, spiro-OMeTAD) and P-type semiconductor (CuSCN).

That is, described electrolyte includes oxidation-reduction derivant, and this oxidation-reduction derivant plays anti-by oxidation-reduction From electrode being received electronics and the effect of the electronics received should be transmitted to the dyestuff of optoelectronic pole, as long as can be used in the dye of routine Material sensitization solar battery, is just not particularly limited this.Specifically, oxidation-reduction derivant is preferably selected from containing iodine (I) at least one in the electrolyte of class, bromine (Br) class, cobalt (Co) class, sulfur cyanogen (SCN-) class and selenium cyanogen (SeCN-) class.Additionally, Described can be containing selected from polyvinylidene fluoride-co-polyhexafluoropropylene, polypropylene containing high molecular polymer gel electrolyte At least one macromolecule in nitrile, poly(ethylene oxide) and polyalkyl acrylate.Additionally, the described macromolecule containing inorganic particulate Gel electrolyte can be containing selected from silicon dioxide and TiO₂At least one inorganic particulate in nanoparticle.Additionally, described electrolysis Matter can include organic hole conductor (HCM, spiro-OMeTAD) and P-type semiconductor (CuSCN).

Additionally, described solaode can farther include for sealing described semi-conducting electrode and the thermal welding to electrode Macromolecule membrane 140 or the binding agent as slurry.At this moment the binding agent used can use the binding agent of routine, and its kind is not subject to Particularly limit.

Invention effect

In accordance with the invention it is possible to easily manufactured under low temperature (about 25 DEG C) by rotary coating method, there is perforated membrane Optoelectronic pole, this perforated membrane includes nanoparticulate metal oxide skin(coating) and the macromolecule layer being adsorbed with photosensitive material.This method Dye adsorption amount is high compared with the conventional high molecular method of mixing, therefore, it is possible to expect the rising of current value.And, such shape The electrode become with conventional only compared with the electrode that inorganic matter is constituted, for result from outside stimulus (ultraviolet, chemical, Heat, impact), the structural deterioration (ultraviolet, heat) of photosensitive material；Company between photosensitive material and metal nano oxide Connect disconnection (chemical)；Or because of interconnection (interconnection) architectural characteristic between metal-oxide, by external force Easily produce the problems such as crack time (impact), and electrode is from the problem of strippable substrate, it is possible to effectively produce and there is excellence The DSSC of durability.

Accompanying drawing explanation

Fig. 1 is the generalized section of the dye-sensitized photoelectric pole of the present invention.

Fig. 2 is the schematic diagram being coated with high molecular shape on the surface of the optoelectronic pole of the present invention.

Fig. 3 is for illustrating the manufacture method of the dye-sensitized photoelectric pole of the present invention and including the dye sensitization of described optoelectronic pole The operation schematic diagram of the manufacture method of solaode.

Fig. 4 is the sectional view of the DSSC of the present invention.

Fig. 5 is for observing the macromolecule degree of distribution in the metal oxide nanoparticles of embodiment 1 and comparative example 1 Carbon probe-microanalyser (electron probe micro-analyser) result.

Fig. 6 is the macromolecule coating for observing on the metal oxide nanoparticles surface of embodiment 1 and comparative example 1 Transmission electron microscope (the transmission electron microscope) result of state.

Fig. 7 is by embodiments of the invention 1～3 and after comparative example 1 impregnates 10 minutes in NaOH solution, compares heliosensitivity The desorption of material whether photo.

Fig. 8 be by embodiments of the invention 1～3 and comparative example 1 in high temperature (100 DEG C), after keeping, compare dye sensitization The chart of the efficiency change in solaode produced high temperature in time.

Fig. 9 be to using the embodiment 4 of flexible base board and comparative example 2 to carry out outer bend test after, compare dye sensitization The chart that solar battery efficiency reduces.

Figure 10 is the outer bend test according to embodiments of the invention 4 and comparative example 2, compares dye sensitization of solar electricity The voltage in pond and the chart of charge rate curve.

Description of reference numerals

110: optoelectronic pole

101: substrate

102: conducting film

103: electrically-conductive backing plate

104: include the perforated membrane of metal oxide nanoparticles

105: include the perforated membrane being adsorbed with the metal oxide nanoparticles of photosensitive material

106: macromolecule layer

107: include the metal oxide nanoparticles layer being adsorbed with photosensitive material and be formed at this metal-oxide and receive The perforated membrane of the macromolecule layer in grain of rice sub-layer surface

121: catalyst layer

120: to electrode

130: electrolyte

140: high molecular bonding oxidant layer

Detailed description of the invention

It is below embodiments of the invention, it is provided that the following example is intended merely to contribute to understanding the present invention, the present invention's Interest field is not limited to these embodiments.

[embodiment 1]

(manufacture of optoelectronic pole)

Glass substrate (Philkington company, the material: conduction glass with electric conductivity is prepared as optoelectronic pole substrate Glass (FTO), the substrate including 101 and 102 of thickness 2.2cm, 8 Ω/sq, Fig. 3).

Afterwards, the binding agent use of the TiOx nano particle (mean diameter: 20nm) of 18.5wt%, 0.05wt% will be comprised The metal oxide nanoparticles slurry coating of the solvent (Terpineol) of macromolecule (ethyl cellulose) and surplus is at described glass After (utilizing scraper plate (doctor blade) coating process) on glass substrate, substrate is carried out the heat of 30 minutes at a temperature of 500 DEG C Process, thus form the perforated membrane (thickness: 10 μm) including metal oxide nanoparticles.It follows that by described combination electrode It is immersed in ruthenium (Ru) class sensitising dye N719 (double (tetrabutylammoniums)-cis-(double (the 4-carboxylic of dithiocyano-N, N'-containing 0.5mM Acidic group-4'-carboxylic acid-2,2'-bis-pyridine) ruthenium (II), bis (tetrabutylammonium)-cis-(dithiocyanato-N, N'-bis (4-carboxylato-4'-carboxylic acid-2,2'-bipyridine) ruthenium (II)) ethanol In solution, and impregnate one hour under conditions of 50 DEG C, so that sensitising dye is adsorbed in porous metal oxide layer In nanoparticle surface.

Afterwards, by polymethyl methacrylate (PMMA) macromolecule dissolution in ethyl acetate (EA), macromolecule is prepared Solution (colloid solution of the PMMA containing 5wt%).The macromolecular solution of preparation is dropped in the metal-oxide being adsorbed with dyestuff After on nanoparticle layers, give about 1 minute～the time of 10 minutes, enable macromolecule to be impregnated into nanoparticulate metal oxidation Thing, carries out spin coated with the speed of 2000rpm afterwards and is dried 10 minutes at a temperature of 25 DEG C.By these processes, will Macromolecule layer is formed on the surface of the oxide porous film of nanoparticulate metal being adsorbed with dyestuff, thus manufactures optoelectronic pole.

(manufacture to electrode)

About the manufacture to electrode, prepare to be formed with the transparent glass substrate of fluorine doped tin oxide including transparent conducting oxide layer. On the including transparent conducting oxide layer of described substrate, drippage is dissolved with chloroplatinic acid (H₂PtCl₆) 2-propanol solution after, 400 Carry out the heat treatment of 20 minutes at DEG C and form platinum layer, thus manufacture anode electrode.

(injection of electrolyte and sealing)

The optoelectronic pole above manufactured and to the space between electrode in inject comprise PMII (1-methyl-3-propyl group iodate Imidazoles (1-methyl-3-propylimidazolium iodide), 0.7M) and I₂(0.03M) acetonitrile (acetonitrile) electrolyte and seal and manufacture DSSC.

[embodiment 2]

(manufacture of optoelectronic pole)

Glass substrate (Philkington company, material FTO, the thickness with electric conductivity is prepared as optoelectronic pole substrate The substrate including 101 and 102 of 2.2cm, 8 Ω/sq, Fig. 3).

Afterwards, the binding agent use of the TiOx nano particle (mean diameter: 20nm) of 18.5wt%, 0.05wt% will be comprised The metal oxide nanoparticles slurry coating of the solvent (Terpineol) of macromolecule (ethyl cellulose) and surplus is at described glass After (utilizing scraper plate coating process) on glass substrate, substrate is carried out at a temperature of 500 DEG C the heat treatment of 30 minutes, thus forms bag Include the perforated membrane (thickness: 10 μm) of metal oxide nanoparticles.It follows that described combination electrode is immersed in containing 0.5mM Ruthenium (Ru) class sensitising dye N719 (double (tetrabutylammoniums)-cis-(and dithiocyano-N, N'-double (4-carboxylic acid group-4'-carboxylic acid-2, 2'-bis-pyridine) ruthenium (II), bis (tetrabutylammonium)-cis-(dithiocyanato-N, N'-bis (4- Carboxylato-4'-carboxylic acid-2,2'-bipyridine) ruthenium (II)) ethanol solution in, and And impregnate one hour under conditions of 50 DEG C, so that sensitising dye is adsorbed in the nanoparticle sublist of porous metal oxide layer On face.

Afterwards, by polyvinylpyrrolidone (PVP) macromolecule dissolution in 2-propanol (2-propanol), high score is prepared Sub-solution (colloid solution of the PVP containing 5wt%).The macromolecular solution of preparation is dropped in the metal-oxide being adsorbed with dyestuff After on nanoparticle layers, give about 1 minute～the time of 10 minutes, enable macromolecule to be impregnated into nanoparticulate metal oxidation Thing, carries out spin coated with the speed of 2000rpm afterwards and is dried 10 minutes at a temperature of 25 DEG C.By these processes, will Macromolecule layer is formed on the surface of the oxide porous film of nanoparticulate metal being adsorbed with dyestuff, thus manufactures optoelectronic pole.

(manufacture to electrode)

About the manufacture to electrode, prepare to be formed with the clear glass base of fluorine doped tin oxide transparent conductive oxides layer Plate.On the transparent conductive oxides layer of described substrate, drippage is dissolved with chloroplatinic acid (H₂PtCl₆) 2-propanol solution after, At 400 DEG C, carry out the heat treatment of 20 minutes and form platinum layer, thus manufacture anode electrode.

(injection of electrolyte and sealing)

The optoelectronic pole above manufactured and to the space between electrode in inject comprise PMII (1-methyl-3- Propylimidazolium iodide, 0.7M) and I₂(0.03M) acetonitrile (acetonitrile) electrolyte also seals and makes Make DSSC.

[embodiment 3]

(manufacture of optoelectronic pole)

Afterwards, the binding agent use of the TiOx nano particle (mean diameter: 20nm) of 18.5wt%, 0.05wt% will be comprised The metal oxide nanoparticles slurry coating of the solvent (Terpineol) of macromolecule (ethyl cellulose) and surplus is at described glass After (utilizing scraper plate coating process) on glass substrate, at a temperature of 500 DEG C, substrate is carried out the heat treatment of 30 minutes, thus forms bag Include the perforated membrane (thickness: 10 μm) of metal oxide nanoparticles.It follows that described combination electrode is immersed in containing 0.5mM Ruthenium (Ru) class sensitising dye N719 (double (tetrabutylammoniums)-cis-(and dithiocyano-N, N'-double (4-carboxylic acid group-4'-carboxylic acid-2, 2'-bis-pyridine) ruthenium (II), bis (tetrabutylammonium)-cis-(dithiocyanato-N, N'-bis (4- Carboxylato-4'-carboxylic acid-2,2'-bipyridine) ruthenium (II)) ethanol solution in, and And impregnate one hour under conditions of 50 DEG C, so that sensitising dye is adsorbed in the nanoparticle sublist of porous metal oxide layer On face.

Afterwards, by polymethyl methacrylate (PMMA) macromolecule dissolution in ethyl acetate (EA), macromolecule is prepared Solution (colloid solution of the PMMA containing 5wt%).The macromolecular solution of preparation is dropped in the metal-oxide being adsorbed with dyestuff After on nanoparticle layers, give about 1 minute～the time of 10 minutes, enable macromolecule to be impregnated into nanoparticulate metal oxidation Thing, carries out spin coated with the speed of 2000rpm afterwards and is dried 10 minutes at a temperature of 25 DEG C.Afterwards, by polyethylene pyrrole Pyrrolidone (PVP) macromolecule dissolution in 2-propanol (2-propanol), prepare macromolecular solution (PVP's containing 5wt% Colloid solution).The macromolecular solution of preparation is dropped in after being adsorbed with on the metal oxide nanoparticles layer of dyestuff, give about 1 minute～10 minutes, enable macromolecule to be impregnated into nanoparticulate metal oxide, enter with the speed of 2000rpm afterwards Row spin coated is also dried 10 minutes at a temperature of 25 DEG C.By these processes, macromolecule layer is formed at and is adsorbed with dyestuff The oxide porous film of nanoparticulate metal surface on, thus manufacture optoelectronic pole.

(manufacture to electrode)

(injection of electrolyte and sealing)

PMII (1-methyl-3-is comprised at the optoelectronic pole above manufactured with to the space injection between electrode Propylimidazolium iodide, 0.7M) and I₂(0.03M) acetonitrile (acetonitrile) electrolyte also seals and makes Make DSSC.

[comparative example 1]

(manufacture of optoelectronic pole)

(manufacture to electrode)

(injection of electrolyte and sealing)

[embodiment 4 and comparative example 2]

In order to carry out outer bend test, manufacture solaode on flexible substrates.To this end, at embodiment 1 and ratio In the relatively test method of example 1 as substrate employ plastic base (peccell company, material: peccell, thickness 2.2cm, 15 Ω/sq)。

Additionally, as metal oxide paste, the TiO to 8g₂Nanoparticle (mean diameter 20nm) is scattered in 200ml's Solution in ethanol, uses machine mixer to be stirred (40 minutes/450rpm) and prepare uniform colloid solution.In order to Improve the viscosity of colloid solution, by distillation and concentration device (rotary evaporator, rotary evaporator) the temperature of 50 DEG C Under prepare slurry so that the speed of 170rpm carries out distilling.By scraper plate coating method in the upper painting of plastic base (ITO/PEN) Apply after described slurry, at a temperature of 100 DEG C, carry out the heat treatment of 2 hours to remove solvent, thus producing thickness is 6 μm Electrode.

Afterwards, the high molecular method of coating carried out is same as in Example 1.

Additionally, for the substrate of electrode being employed thin film (the Pei Saier science and technology applied by platinum/titanium alloy with 30nm thickness Co., Ltd. (Peccell Technologies), material: PEN, thickness 188 μm, 5 Ω/sq).

Through these processes, produce the solaode of embodiment 4.

Additionally, comparative example 2 is in addition to making substrate into plastic base, the method for comparative example 1 is carried out as described above.

[experimental example 1]

In order to observe the macromolecule degree of distribution within metal oxide nanoparticles, by carbon probe-microanalyser (electron probe micro-analyser) have detected the light of the DSSC of embodiment 1 and comparative example 1 The macromolecule degree of distribution of electrode.Its result represents in Figure 5.

As shown in Figure 5, it is known that the carbon density showing no sign of comprising the comparative example 1 of macromolecule (PMMA) is low and not distribution Macromolecule.On the contrary, in the case of being coated with the solution comprising 5wt% macromolecule (PMMA) such as embodiment 1, it is known that carbon density Rise and be evenly distributed macromolecule.

[experimental example 2]

Use the photoelectricity of the DSSC of transmission electron microscopy embodiment 1 and comparative example 1 Pole, this transmission electron microscope is for observing the polymeric coating layer on metal oxide nanoparticles surface.Its result represents In figure 6.

As shown in Figure 6, the metal oxide surface of the comparative example 1 showing no sign of comprising macromolecule (PMMA) looks sky nothing One thing.

On the contrary, in the case of being coated with the solution comprising 5wt% macromolecule (PMMA) such as embodiment 1, by micro- Mirror confirms and is coated with macromolecule on the surface of metal-oxide.

If additionally, understand the specific perforated membrane using the present invention when manufacturing optoelectronic pole, then the battery that can bring excellence is special Property, and inefficiency decline.

[experimental example 3]

To each DSSC manufactured in embodiment 1 to 3 and comparative example 1, detected by following method Open-circuit voltage, density of photocurrent, energy conversion efficiency (energy conversion efficiency) and fill factor, curve factor (FF, fill factor), its result is shown in Table 1 below.

(1) open-circuit voltage (V) and density of photocurrent (mA/cm²)

The detection of open-circuit voltage and density of photocurrent make use of Keithley (Keithley) SMU2400.

(2) energy conversion efficiency (%) and fill factor, curve factor (%)

The detection of energy conversion efficiency make use of 1.5AM100mW/cm²Solar simulator (by xenon lamp, [1600W, under mountain Denso], AM1.5 optical filter and Keithley SMU2400 constitute), fill factor, curve factor calculates and make use of conversion efficiency obtained above And below equation.

[formula]

In above-mentioned formula, J is the Y-axis value of conversion efficiency curve, and V is the X-axis value of conversion efficiency curve, and short circuit current is close Degree (Jsc) and the values of intercept that open-circuit voltage (Voc) is each axle.

[table 1]

As shown in Table 1, it is known that the DSSC of embodiment 1～3 has high with conventional not use The efficiency of the DSSC same level of the comparative example 1 of molecule.

[experimental example 4]

In order to investigate the UV stable of the optoelectronic pole of DSSC, by intensity 500W/m²Purple Outside line lamp to embodiment 1～3 and the optoelectronic pole of comparative example 1 irradiate 30 minutes after manufactured battery, and detect energy conversion efficiency (energy conversion efficiency).Result after ultraviolet irradiates is shown in Table 2 below.

[table 2]

As above shown in table 2, it is known that the efficiency rate of descent of the comparative example 1 after irradiation ultraviolet radiation is about 76%.Therefore, comparative example The battery of 1 has the problem that battery behavior is remarkably decreased.

But, the efficiency rate of descent of embodiment 1 to 3 is 62%, 40% and 22%, it is known that ultraviolet compared with comparative example 1 Have excellent photostability.

[experimental example 5]

In order to investigate the chemical stability of the optoelectronic pole of DSSC, by embodiment 1～3 and comparative example 1 Optoelectronic pole in the NaOH solution of 1M, impregnate 10 minutes after manufactured battery, and detect energy conversion efficiency (energy conversion efficiency).Its result is shown in Table 3 below.Fig. 7 be by embodiments of the invention 1～3 and comparative example 1 exist The NaOH solution of 1M impregnated after 10 minutes, compares the desorption whether photo of photosensitive material.

[table 3]

As above, shown in table 3, in NaOH solution after dipping, the efficiency rate of descent of comparative example 1 is about about 98%, it is known that several Not work.

But, the efficiency rate of descent of embodiment 1 to 3 is 29%, 98% and 24%, it is known that chemistry is steady compared with comparative example 1 Qualitative excellence.

Additionally, by the result of Fig. 7, it is known that embodiment 1 to 3 is compared with comparative example 1, even if being immersed in alkaline solution, There is no the desorption of dyestuff yet.

Knowable to result above, different according to high molecular weight species, ultraviolet and chemical stability.To ensure ultraviolet Line stabilization, uses PVP, PMMA-PVP macromolecule to ensure stability, to ensure chemical stability, use PMMA, PMMA-PVP macromolecule ensures chemical stability.

[experimental example 6]

In order to investigate the heat stability of the optoelectronic pole of DSSC, by embodiment 1 to 2 and comparative example 1 Battery is keeping in the baking box of 100 DEG C, and detects energy conversion efficiency (energy conversion efficiency).Its knot Fruit represents in fig. 8.

As shown in Figure 8, in order to investigate the heat stability of the optoelectronic pole of the DSSC of embodiment 1 to 2, will The DSSC keeping of embodiment 1 to 2 and comparative example 1 is in the baking box of 100 DEG C, and detects energy conversion efficiency (energy conversion efficiency).In the baking box of 100 DEG C after keeping, the battery of comparative example 1 is over time Passage, efficiency rate of descent is about about 90%, almost without work.But the efficiency rate of descent of the battery of embodiment 1 and 2 is 40% With 20%, it is known that excellent heat stability compared with comparative example 1.

[experimental example 7]

In order to investigate the mechanical stability of the optoelectronic pole of DSSC, embodiment 4 and comparative example 2 are manufactured Battery, and detect the energy conversion efficiency (energy conversion efficiency) according to bend test.Bending examination Test and make use of the cylindrical bend testing machine being illustrated in a diameter of 7mm on the left of Fig. 9, and by conventional method to each optoelectronic pole Its result is tested and detected to the physical bend having carried out 100～1000 times.Its result represents in fig .9.

As Fig. 9 represents, knowable to the outer bend result of the test of embodiment 4 and comparative example 2, manufacturing flexible light electrode Time, use the situation (embodiment 4) that macromolecular solution is coated on the metal oxide nanoparticles layer be adsorbed with dyestuff With without the result under the situation (comparative example 2) of this process, there is the biggest difference.That is, the battery (cell) to embodiment 4 Characteristic and the result of comparative example 2 compare and understand, when carrying out 200 bendings, do not add high molecular comparative example 2 Efficiency is 0%, does not the most work.On the contrary, the battery table of embodiment 4 reveals the efficiency of about 80%.Therefore, the present invention is not only In the case of being applicable to described glass substrate, and it is being applicable to the flexible dye-sensitized solar battery feelings of flexible base board Under condition, it is also possible to realize ensureing the stability of semiconductor film layer and there is the solaode of high photoelectric efficiency.

[experimental example 8]

To embodiment 4 and comparative example 2, have detected according to acquisition under the conditions of AM1.5G, 1Sun (one times of sun light intensity) The open-circuit voltage of bend test and fill factor, curve factor (fill factor).Its result represents in Fig. 10.Additionally, with experimental example 7 phase With, bend test make use of the cylindrical bend testing machine of a diameter of 7mm.

The outer bend result of the test of Figure 10 understands, when manufacturing flexible light electrode, uses macromolecular solution inhaling Situation with the situation (embodiment 2) being coated on the metal oxide nanoparticles layer of dyestuff with without this process (compares Relatively example 2) under result there is the biggest difference.The i.e. characteristic of battery (cell) and the result of comparative example 2 to embodiment 4 is carried out Relatively understanding, when carrying out 200 bendings, the efficiency not applying high molecular comparative example 2 is 0%, does not the most work.Phase Instead, the battery of embodiment 4 shows the highest efficiency according to high molecular content.Therefore, the present invention is manufacturing flexible dyestuff It also is able to during sensitization solar battery realize ensureing the stability of semiconductor film layer and there is the solar-electricity of high photoelectric efficiency Pond.

In a word, according to the present invention, can be easily manufactured by including being adsorbed with photosensitive material by rotary coating method Metal oxide nanoparticles layer and be formed at the macromolecule layer on this metal oxide nanoparticles layer surface or include The optoelectronic pole of nanoparticulate metal oxide-polymer composite.The conventional electrode being only made up of inorganic matter is because of outside stimulus (ultraviolet, chemical, heat, impact), so the structure of photosensitive material by destroy (ultraviolet, heat), photosensitive material With the connection between metal nano oxide can disconnect (chemical), or because of the interconnection between metal-oxide (interconnection) architectural characteristic, easily produces crack during by external force (impact), and electrode is from strippable substrate, with This electrode as formed above comparing the present invention can produce has the dye sensitization of excellent durability and mechanical strength too Sun can battery.

Claims

1. for an optoelectronic pole for DSSC, including:

Electrically-conductive backing plate；And

It is formed at the perforated membrane on this electrically-conductive backing plate,

Described perforated membrane includes the metal oxide nanoparticles layer being adsorbed with photosensitive material and is formed at this metal-oxide Macromolecule layer on nanoparticle layers surface,

Wherein, described perforated membrane has the porosity of 30～80%,

Wherein, the average thickness of described macromolecule layer is 1nm to 20nm,

Wherein, described macromolecule layer has the shape on the surface around the metal oxide nanoparticles being adsorbed with photosensitive material Shape.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

It is 500W/m by intensity²Burdick lamp irradiate the slip of the photoelectric transformation efficiency after 30 minutes be irradiation ultraviolet radiation it Less than the 70% of front starting efficiency；

The minimizing of the photoelectric transformation efficiency after impregnating in the alkaline solution that concentration is 0.1～80wt%, alcoholic solution or water Rate is to impregnated in less than 70% of the starting efficiency before chemical solution；

The slip of the photoelectric transformation efficiency after taking care of in 60～120 DEG C is the starting efficiency in this described temperature before keeping Less than 70%.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

Described electrically-conductive backing plate includes being coated with the glass substrate of conducting film, flexible plastic substrates or metal basal board.

Optoelectronic pole for DSSC the most according to claim 3, wherein,

Described electrically-conductive backing plate is flexible plastic substrates, and utilizes the cylindrical bend testing machine of a diameter of below 10mm to carry out 100 ～slip is starting efficiency less than 70% of the photoelectric transformation efficiency after 1000 bend tests.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

Described perforated membrane has the thickness of 1～100um.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

Macromolecule for described macromolecule layer includes selected from polyurethane, poly(ethylene oxide), polyvinylpyrrolidone, polycyclic oxygen third Alkane, Polyethylene Glycol, chitosan, chitin, polyacrylamide, polyvinyl alcohol, polyacrylic acid, cellulose, ethyl cellulose, poly-methyl 2-(Acryloyloxy)ethanol, polymethyl methacrylate, polysaccharide, polyamide, Merlon, polyethylene, polypropylene, polystyrene, poly- Ethylene glycol terephthalate, PEN, include dimethione containing polymeric silicon, isoprene, At least one macromolecule in butadiene type rubber and derivant thereof.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

The described metal oxide nanoparticles layer being adsorbed with photosensitive material includes selected from tin-oxide；Doped with antimony, niobium or The tin-oxide of fluorine；Indium oxide；Indium oxide doped with stannum；Zinc oxide；Doped with aluminum, boron, gallium, hydrogen, indium, yttrium, titanium, Silicon or the zinc oxide of stannum；Magnesium oxide；Cadmium oxide；Magnesium-zinc oxide；Indium-zinc oxide；Copper aluminum oxide；Silver oxide； Gallium oxide；Zinc tin oxide；Titanium oxide and zinc indium tin oxide；Nickel oxide；Rhodium oxide；Ru oxide；Iridium oxide； Cu oxide；Cobalt/cobalt oxide；Tungsten oxide；Titanium oxide；Zirconium oxide；Strontium oxide；Lanthanum-oxides；Barium oxide；Molybdenum oxygen Compound；Niobium oxide；Aluminum oxide；Yttrium oxide；Scandium oxide；Samarium oxide；Strontium titanium oxide and the mixing of these materials At least one metal oxide nanoparticles in thing.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

Described photosensitive material includes absorbing the heliosensitivity organic substance of the visible ray that band gap is 1eV～3.1eV, heliosensitivity Inorganic substances, heliosensitivity organic-inorganic composition matter or the mixture of these materials.

Optoelectronic pole for DSSC the most according to claim 1, wherein,

Described perforated membrane includes: the metal oxide nanoparticles layer and the polymethyl methacrylate that are adsorbed with photosensitive material are high Molecular layer；It is adsorbed with metal oxide nanoparticles layer and the polyvinylpyrrolidonemacromolecule macromolecule layer of photosensitive material；Or inhale With the metal oxide nanoparticles layer of photosensitive material and polymethyl methacrylate and polyvinylpyrrolidonemacromolecule macromolecule Layer.

10. a manufacture method for the optoelectronic pole for DSSC described in claim 1, including:

C) on the surface of the metal oxide nanoparticles of the perforated membrane being adsorbed with described photosensitive material, macromolecule is applied molten Liquid is also dried, and includes macromolecule layer manufacturing the surface of metal oxide nanoparticles layer being adsorbed with photosensitive material Perforated membrane,

Wherein, described macromolecular solution is the colloid solution that macromolecule is scattered in solvent, relative to whole macromolecular solution, The macromolecule of 0.01～50wt% is scattered in solvent.

The manufacture method of 11. optoelectronic poles for DSSC according to claim 10, wherein,

Described macromolecular solution includes selected from polyurethane, poly(ethylene oxide), polyvinylpyrrolidone, poly(propylene oxide), poly-second two Alcohol, chitosan, chitin, polyacrylamide, polyvinyl alcohol, polyacrylic acid, cellulose, ethyl cellulose, polymethylacrylic acid hydroxyl Ethyl ester, polymethyl methacrylate, polysaccharide, polyamide, Merlon, polyethylene, polypropylene, polystyrene, poly-terephthaldehyde Acid glycol ester, PEN, include dimethione containing polymeric silicon, isoprene, butadiene type At least one macromolecule in rubber and derivant thereof.

The manufacture method of 12. optoelectronic poles for DSSC according to claim 10, wherein,

Described solvent selected from ethanol, methanol, terpinol, lauric acid, ethyl acetate, hexane and toluene.

The manufacture method of 13. optoelectronic poles for DSSC according to claim 10, wherein,

Dry in described c) step is to carry out 1～30 minute at a temperature of 20 DEG C～150 DEG C.

The manufacture method of 14. optoelectronic poles for DSSC according to claim 10, wherein,

Described step a) forming perforated membrane, including:

By comprise the slurry coating of metal oxide nanoparticles and solvent in electrically-conductive backing plate above after, at 20～150 DEG C At a temperature of carry out the heat treatment of 1～2 hour；Or,

By comprise the slurry coating of metal oxide nanoparticles, adhesive resin and solvent in electrically-conductive backing plate above after, The heat treatment of 1～2 hour is carried out at a temperature of 450～500 DEG C.

The manufacture method of 15. optoelectronic poles for DSSC according to claim 14, wherein,

Described solvent is at least one in ethanol, methanol, terpinol and lauric acid,

Described adhesive resin is selected from Polyethylene Glycol, poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone and ethyl cellulose At least one in element.

The DSSC of 16. 1 kinds of optoelectronic poles included described in claim 1.