CN101609750A - DSSC and method for making thereof - Google Patents
DSSC and method for making thereof Download PDFInfo
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- CN101609750A CN101609750A CNA2009101600454A CN200910160045A CN101609750A CN 101609750 A CN101609750 A CN 101609750A CN A2009101600454 A CNA2009101600454 A CN A2009101600454A CN 200910160045 A CN200910160045 A CN 200910160045A CN 101609750 A CN101609750 A CN 101609750A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention is relevant a kind of DSSC and method for making thereof.Described DSSC comprises one first electrode, a dielectric substrate and one second electrode.Wherein, described dielectric substrate comprises the electrolyte of illiquidity; Described second electrode comprises an electric conducting material, and its restrictive condition is not for comprising substrate; And described dielectric substrate and described second electrode are to be formed at first electrode top in regular turn.DSSC of the present invention is only used single substrate, can significantly reduce manufacturing cost, and the manufacture method of DSSC of the present invention is to finish the preparation of each assembly in regular turn with overlapped way, so but continued operation has more economic benefit.
Description
Technical field
The present invention relates to a kind of solar cell and method for making thereof; Especially about a kind of DSSC and method for making thereof of only using single substrate.
Background technology
Along with science and technology and rapid economy development, the demand of the energy also significantly increases.The storage of raw materials such as the oil of use amount maximum, natural gas, coal constantly reduces now, therefore must be dependent on the energy demand that other emerging energy satisfies to be increased day by day.Solar energy is because of having low contaminative and advantage such as obtain easily, for being expected most at present and one of most important emerging energy source.
In the twentieth century, at first develop a kind of silicon solar cell by U.S.'s Bell Laboratory, its operation principle is to be to utilize semi-conductive photovoltaic effect.Though at present the electricity conversion of silicon solar cell is better than other form person, because shortcoming, therefore still restriction to some extent on the commercialization volume production such as manufacturing process complexity, cost height, material requirements be harsh.
In recent years, (Dye-Sensitized Solar Cell DSSC) is considered to have development potentiality owing to having cheap advantage to DSSC, is expected to replace the traditional silicon solar cell, becomes the research emphasis of solar cell.
Generally speaking, DSSC be comprise electrically-conductive backing plate that the electric current flow passage is provided, as the conductor oxidate of electron transfer layer (as TiO
2), the electrolyte and the encapsulating material in sensitizing dyestuff, transmission electronic and hole.DSSC utilizes the semiconductor nano epitaxial that is formed on the electrically-conductive backing plate, behind its surface adsorption one sensitizing dyestuff, forms the work electrode of DSSC.After sensitizing dyestuff absorbed sunlight, its electron transition was to excitation state and be transferred to the semiconductor nano epitaxial rapidly, and electronics diffuses to electrically-conductive backing plate subsequently and is transferred to electrode through external circuit.Because of the sensitizing dyestuff that loses electronics and become oxidation state then reduces by electrolyte, the electrolyte after the oxidation is then accepted the electronics of electrode is reduced into ground state, thereby finishes the whole transmission course of electronics.
Say it for example, the M. of Switzerland
A kind of DSSC of team development, it is with TiO
2Nano-crystal grains coat the electrically-conductive backing plate fluorine-doped tin oxide (fluorine-doped tin oxide, FTO) on glass, and utilize TiO
2The pore structure of nanoparticle perforated membrane, absorption ruthenium complex (Ru-complexes is as N3, N719) sensitizing dyestuff, subsequently with the electro-conductive glass that plates platinum (Pt) as to electrode.Wherein, be to utilize iodide ion (I
3 -/ I
-) solution is as electrolyte, and DSSC is provided required oxidation-reduction reaction.The structure of N3 and N719 is as follows respectively:
Tradition is made the method for DSSC, comprises two electrically-conductive backing plates being made the work electrode of DSSC respectively and to electrode, with described two electrodes applying, encapsulation, injecting electrolyte subsequently, and last sealing of hole is finished operations such as DSSC.Particular words it, be earlier an electrically-conductive backing plate coating layer of semiconductor nanometer layer, and through a sintering program with after solidifying described semiconductor nano layer, the described electrically-conductive backing plate that is covered with the semiconductor nano layer is inserted in the sensitizing dyestuff solution, make sensitizing dyestuff be adsorbed on the semiconductor and form work electrode; Another piece electrically-conductive backing plate then forms one deck conductive materials (as platinum, carbon black) thereon by appropriate means under vacuum or antivacuum state, as to electrode; Subsequently again with work electrode with electrode is fitted, operation such as encapsulation, electrolyte and inlet sealed at last reinjects.
Tradition is made the method for DSSC, must be with two substrate separate processes, and this will cause discontinuous on the manufacture process.Not only very inconvenience when making large tracts of land DSSC also can be subject to the shape and the size of substrate, and also can inconvenience be arranged because of the material behavior of two substrates when follow-up encapsulation is fitted.Moreover, being subjected to limit in manufacturing process, the traditional method for making of this kind must be used two substrates, and the substrate cost reaches half of total cost approximately, and the consumption that therefore reduces substrate certainly will be able to more improve the commercial value of DSSC.
In addition, for ease of electrolyte being injected work electrode that encapsulation finishes and to electrode and guarantee to fill up fully the space, classical production process generally is to use liquid electrolyte.Liquid electrolyte commonly used at present is with the I based on halogen
3 -/ I
-Oxidation-reduction pair (oxidation-reduction pair) be scattered in solvent (as: nitrile, ester class, oxolane (tetrahydrofuran), dimethyl formamide (dimethylformamide, DMF), reach N-methyl 2-pyrrolidone N-(N-methyl-2-pyrrolidone, NMP)) after in, add some additive that is used for modifying semiconductor oxide (as TiO2) (as: tributyl pyridine (4-tert-butylpyridine, TBP), N-tolimidazole (N-methylbenzimidazole, NMBI), LiI, NaI) and obtaining.This kind liquid electrolyte because of the high activity of halogen and the high volatile volatile of solvent itself, causes liquid electrolyte to be penetrated into outside batteries easily, causes the pollution of DSSC inefficacy and environment.
This shows that above-mentioned existing DSSC and method for making thereof obviously still have inconvenience and defective, and demand urgently further being improved in product structure, manufacture method and use.In order to solve the problem of above-mentioned existence, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and common product and method do not have appropriate structure and method to address the above problem, and this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of new DSSC and method for making thereof, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.
Summary of the invention
The objective of the invention is to, overcome the defective that existing DSSC and method for making thereof exist, and provide a kind of new DSSC and method for making thereof, technical problem to be solved is to make DSSC only use single substrate, it can utilize overlapped way that each assembly is assembled in regular turn, makes that cost is low and can produce continuously.
The object of the invention to solve the technical problems realizes by the following technical solutions.According to a kind of DSSC that the present invention proposes, it comprises: one first electrode comprises: a substrate, a conductive layer, semi-conductor layer and a sensitizing dyestuff; One dielectric substrate comprises the electrolyte of illiquidity; And one second electrode, comprising an electric conducting material, its restrictive condition is not for comprising substrate, and wherein said dielectric substrate and described second electrode are the tops that is formed at first electrode in regular turn.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid DSSC, the electrolyte of wherein said illiquidity comprise a colloidal electrolyte, a solid electrolyte or its combination.
Aforesaid DSSC, wherein said electrolytical electrical conductivity is 10
-2S/cm to 10
-6S/cm.
Aforesaid DSSC, wherein said colloidal electrolyte comprises the additive that an oxidation-reduction pair and is selected from following group: specific area is 30m at least
2The filler of/g, molecular weight 1,000 to 5,000,000 macromolecule and combination thereof, and the content of described additive is at least 3 weight % with the total restatement of described electrolyte.
Aforesaid DSSC, wherein said additive are to be selected from following group: the about 30m of specific area
2/ g is to about 160m
2The filler of/g, molecular weight 500,000 to 5,000,000 macromolecule and combination thereof, and the content of described additive is 3 weight % to 10 weight % with the total restatement of described electrolyte.
Aforesaid DSSC, wherein said solid electrolyte comprises the additive that an oxidation-reduction pair and is selected from following group: specific area is 30m at least
2The filler of/g, molecular weight 500 to 4,000,000 macromolecule and combination thereof, and the content of described additive is with the total restatement at least 50 weight % of described electrolyte.
Aforesaid DSSC, wherein said additive are molecular weight 500 to 4,000, and 000 macromolecule and its content are 60 weight % to 95 weight % with the total restatement of described electrolyte.
Aforesaid DSSC, wherein said filler are to be selected from following group: TiO
2, ZnO, SnO
2, In
2O
3, CdS, ZnS, CdSe, GaP, CdTe, MoSe
2, WSe
2, Nb
2O
5, WO
3, KTaO
3, ZrO
2, SrTiO
3, SiO
2, CdS and combination thereof.
Aforesaid DSSC, wherein said filler are to be selected from following group: TiO
2, ZnO, SnO
2, SiO
2And combination.
Aforesaid DSSC, wherein said macromolecule is to be selected from following group: polyethers, polyacrylonitrile, poly-acryl, polypyridine, polyaniline, polypyrrole, polystyrene, poly-to benzene, polythiophene, polyacetylene, poly-3,4-ethyl bis ether thiophene, 3-isobutyl group-4-oxygen base-tricosanic acid benzyl esters, polyvinyl pyridine, sulfolane, the dendritic macromolecule of polyamide, volution two fluorenes, poly-(N-vinylcarbazole), poly-3,4-ethene dioxythiophene, poly(ethylene oxide), poly-difluoroethylene, EU and combination thereof.
Aforesaid DSSC, wherein said EU are polytrimethylene ether toluenediamine esters.
Aforesaid DSSC, wherein said oxidation-reduction pair are to be selected from following group: I
3 -/ I
-, Br
-/ Br
2, SeCN
-/ (SeCN)
2, SCN
-/ (SCN)
2And combination.
Aforesaid DSSC, wherein said electric conducting material are to be selected from following group: gold, platinum, plation, silver, aluminium, carbon and compound thereof, transparent conductive oxide, conducting polymer and combination thereof.
The object of the invention to solve the technical problems realizes in addition more by the following technical solutions.The manufacture method of a kind of DSSC that proposes according to the present invention, it comprises following steps: one first electrode is provided; And forming a dielectric substrate and one second electrode in regular turn in the top of described first electrode, wherein said dielectric substrate comprises the electrolyte of illiquidity; And described second electrode comprises an electric conducting material, and its restrictive condition is not for comprising substrate.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
The manufacture method of aforesaid DSSC, wherein said first electrode comprises: be formed at a conductive layer, the semi-conductor layer on the substrate in regular turn and be adsorbed in a sensitizing dyestuff of this semiconductor layer surface.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, DSSC of the present invention and method for making thereof have following advantage and beneficial effect at least: DSSC of the present invention, only use single substrate, can significantly reduce manufacturing cost, and the manufacture method of DSSC of the present invention is to finish the preparation of each assembly in regular turn with overlapped way, so but continued operation has more economic benefit.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is the schematic diagram of DSSC one embodiment of the present invention.
Embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, DSSC and its embodiment of method for making, structure, manufacture method, step, feature and effect thereof that foundation the present invention is proposed are elaborated.In addition, for the purpose of clear and definite, may lavish praise on oneself the size in each assembly and zone in graphic, and not illustrate according to actual ratio.
DSSC of the present invention is only used single substrate, can effectively reduce production costs.With reference to shown in Figure 1, be the schematic diagram of DSSC one embodiment of the present invention.The DSSC 1 of one embodiment of the invention comprises: one first electrode 12, a dielectric substrate 14 and one second electrode 16.First electrode 12 comprises a substrate 121a, a conductive layer 121b, semi-conductor layer 123 and a sensitizing dyestuff 125.The above-mentioned dielectric substrate 14 and second electrode 16 are the tops that are formed at first electrode 12 in regular turn.
Generally speaking, the substrate 121a that the surface is coated with conductive layer 121b is called electrically-conductive backing plate 121, and the thickness of electrically-conductive backing plate 121 is usually adjusted according to the usefulness of final solar battery product and application; Wherein, the thickness of conductive layer 121b is extremely about 1000 nanometers of about 300 nanometers, is preferably about 500 nanometers to about 800 nanometers.
The shape and the material that can be used for substrate 121a of the present invention there is no particular restriction, say it for example, the shape of substrate 121a can be a plane or have rule or irregular solid figure, for example is triangle, quadrangle or polygon, also can be arc or the oval column with angle.The material of substrate 121a can be selected from following group: metal, metal alloy, glass, plastics and combination thereof.When using metal, the material that substrate 121a can be selected from following group constitutes: the alloy of iron, aluminium, copper, titanium, gold, aforementioned metal and combination thereof; When using plastics, the material that substrate 121a can be selected from following group constitutes: and mylar, polyacrylate resin, polystyrene resin, vistanex, poly-cyclic olefin resins, polyimide resin, polycarbonate resin, polyurethane resin, Triafol T (triacetyl cellulose, TAC), PLA (polylactic acid) and combination thereof.According to a specific embodiment of the present invention, substrate 121a is made of glass.The material of conductive layer 121b can be selected transparent conductive oxide (transparent conducting oxide for use, TCO), say it for example, can be selected from following group: fluorine-doped tin oxide (fluorine-doped tin oxide, FTO), antimony-doped tin oxide (antimony-doped tin oxide, ATO), aluminium-doped zinc oxide (aluminum-doped zinc oxide, AZO), tin indium oxide (indium tin oxide, ITO) and the combination.According to of the present invention one preferred specific embodiment, the material of conductive layer 121b is FTO.
The material of semiconductor layer 123 can be any suitable conductor oxidate and is pore structure usually, preferably selects the nano semiconductor oxide for use.Say it for example, the material of semiconductor layer 123 can be selected from following group: TiO
2, ZnO, SnO
2, In
2O
3, CdS, ZnS, CdSe, GaP, CdTe, MoSe
2, WSe
2, Nb
2O
5, WO
3, KTaO
3, ZrO
2, SrTiO
3, SiO
2, CdS and combination, preferably TiO
2, SnO
2Or ZnO.In part implementation method of the present invention, the material of semiconductor layer 123 is TiO
2
The thickness of semiconductor layer 123 generally is about 1 micron to about 50 microns, preferably is about 4 microns to about 20 microns.Cross (as less than about 1 micron) when thin when the thickness of semiconductor layer 123, prepared DSSC 1 usefulness is not good, when the thickness of semiconductor layer 123 blocked up (as greater than about 50 microns), the situation of embrittlement takes place easily then.According to of the present invention one preferred specific embodiment, the thickness of semiconductor layer 123 is about 4 microns to about 10 microns.
The employed sensitizing dyestuff 125 of dye-sensitized solar battery of the present invention, it can be the known any sensitizing dyestuff of persond having ordinary knowledge in the technical field of the present invention, say it for example, sensitizing dyestuff 125 can be selected from following group: square acids, portion spend cyanines class (chlorophyll), rhodamine class (rhodamine), azobenzene, cyanine class (cyanine), thiophene-based (thiophene), metal complex (as ruthenium metal complex) and combination thereof.In part implementation method of the present invention, be to use ruthenium metal complex N719 as sensitizing dyestuff 125.According to the present invention, sensitizing dyestuff 125 is the material surfaces that are adsorbed in semiconductor layer 123, shown in the 1st figure.
In the present invention, dielectric substrate 14 be formed at described first electrode 12 on, and have about 10
-2S/cm is to about 10
-6The electrical conductivity of S/cm is to provide battery required usefulness.Wherein, the definition of electrical conductivity (K) is as follows:
K＝G×L/A
G is electric conduction quantity (S), and L is that distance (cm) and the A between two-plate is pole plate area (cm
2).
With regard to DSSC, the used electrolyte overwhelming majority all is a liquid electrolyte at present.Cause but the organic solvent in the liquid electrolyte is volatile that prescription changes electrolyte in, and then cause battery failure, even the generation phenomenon of leakage and cause environmental pollution.Given this, dielectric substrate 14 of the present invention is the electrolyte that comprise illiquidity, and above-mentioned electrolyte comprises an oxidation-reduction pair and an additive.In general, the electrolytical dielectric substrate 14 that the present invention comprises illiquidity can for example form in the following manner: mix suitable additive, oxidation-reduction pair and solvent or suitable additive is added in the liquid electrolyte solution, change flow of solution, obtain the electrolyte solution of an illiquidity, then the gained electrolyte solution is dripped as on first electrode 12, and place a period of time, solution is slowly permeated, to be infiltrated fully after, carry out drying steps, drain partly or whole solvents and making.The electrolyte of illiquidity of the present invention comprises colloidal electrolyte, solid electrolyte or its combination, is preferably solid electrolyte.
Can be used for colloidal electrolyte of the present invention and comprise the additive that an oxidation-reduction pair and is selected from following group: specific area is at least about 30m
2The filler of/g, molecular weight about 1,000 are to about 5,000,000 macromolecule and combination thereof.The preferably about 30m of the specific area of above-mentioned filler
2/ g is to about 160m
2/ g; Molecular weight polymeric preferably about 500,000 is to about 5,000,000.Simultaneously, the content of additive is at least about 3 weight % with the total restatement of electrolyte, is advisable to be no more than 20 weight %, and preferably about 3 weight % are to about 10 weight %.
Can be used for solid electrolyte of the present invention and comprise the additive that an oxidation-reduction pair and is selected from following group: specific area is at least about 30m
2The filler of/g, molecular weight about 500 are to about 4,000,000 macromolecule and combination thereof, and the content of described additive is about at least 50 weight % with the total restatement of described electrolyte.The preferably about 30m of the specific area of above-mentioned filler
2/ g is to about 160m
2The filler of/g.Preferably, described additive is that molecular weight about 500 to about macromolecule of 4,000,000 and its content is that about 60 weight % are to about 95 weight % with the total restatement of described electrolyte.
Can be used for filler of the present invention and can be selected from following group: TiO
2, ZnO, SnO
2, In
2O
3, CdS, ZnS, CdSe, GaP, CdTe, MoSe
2, WSe
2, Nb
2O
5, WO
3, KTaO
3, ZrO
2, SrTiO
3, SiO
2, CdS and combination thereof; Preferably be selected from TiO
2, ZnO, SnO
2, SiO
2And combination.
Can be used for macromolecule of the present invention and can be selected from following group: polyethers, polyacrylonitrile, poly-acryl, polypyridine, polyaniline, polypyrrole, polystyrene, poly-to benzene, polythiophene, polyacetylene, poly-3,4-ethyl bis ether thiophene, 3-isobutyl group-4-oxygen base-tricosanic acid benzyl esters (3-sec-butyl-4-oxo-tricosanoic acid benzyl ester), polyvinyl pyridine (polyvinylpyridine, PVP), sulfolane (sulfolane), the dendritic macromolecule of polyamide (poly (amidoamine) dendritic derivatives, PPDD), volution two fluorenes (spiro-OMeTAD), poly-(N-vinylcarbazole) (poly (N-vinylcarbazole), PVK), poly-3,4-ethene dioxythiophene (poly (3,4-ethylenedioxythiophene)), poly(ethylene oxide) (poly (ethylene oxide)), poly-difluoroethylene (poly (vinylidene fluoride), EU (polyether urethane) and combination thereof.According to of the present invention one preferred specific embodiment, macromolecule is the EU for tool formula (I):
R-{NH-COO-[(CH
2)
n-O]
m-H}
k????(I)
Wherein R is aryl or the C3-6 cyclic hydrocarbon radical that is substituted or is unsubstituted; N is 2 to 4 integer; M is 6 to 50 integer, is preferably 6 to 15 integer; And k is 2 to 4 integer.According to a preferred implementation method, the R in the formula (I) is a tolyl, and k is 2, that is, and and the structure of EU tool following formula (I1),
Wherein, n is that 2 to 4 integer and m are 6 to 15 integer.
According to another preferred implementation method, EU is the structure of polytrimethylene ether toluenediamine ester tool following formula (I2).
Wherein, m is 6 to 15 integer.
EU used in the present invention, can be by hydroxy-containing compounds and isocyanates polymerization and form, aforesaid isocyanates is such as but not limited to being selected from following group: toluene di-isocyanate(TDI) (toluene diisocyanate, TDI), '-diphenylmethane diisocyanate (methylenediphenylene diisocyanate, MDI), IPDI (isophoronediisocyanate, IPDI), bicyclohexane methylene diisocyanate (dicyclohexanemethylene diisocyanate), XDI (xylenediisocyanate), hydrogenated xylene diisocyanate (hydrogenated xylenediisocyanate) and combination thereof are preferably toluene di-isocyanate(TDI).Aforesaid hydroxy-containing compounds is the compound that comprises one or more hydroxyls, or comprise mixture with different number hydroxy compounds, for example be selected from the group who forms according to following: polyethylene glycol (polyethylene glycol, PEG), polypropylene glycol (polypropyleneglycol, PPG) and polytetramethylene glycol (polytetramethyleneglycol, PTMG).Preferred person is a polyethylene glycol.
The oxidation-reduction pair that is applicable to DSSC there is no certain limitation, (HighestOccupied Molecular Orbital HOMO) is complementary and gets final product as long as redox that oxidation-reduction pair produced can rank can be filled out the electronic energy rank with dyestuff the highest.I for example
3 -/ I
-, Br
-/ Br
2, SeCN
-/ (SeCN)
2, or SCN
-/ (SCN)
2Wherein, because the diffusion rate of iodide ion is very fast, so preferred oxidation-reduction pair is I
3 -/ I
-
The solvent that preparation dielectric substrate 14 is used can provide the environment of the institute's electrolyte intermediate ion that forms transmission, also can be used for dissolving additive (as above-mentioned filler and macromolecule).The solvent that can be used among the present invention can be selected from following group usually: nitrile (as acetonitrile, methoxypropionitrile, valeronitrile), ester class (as ethylene carbonate, propene carbonate), oxolane, dimethyl formamide, N-methyl 2-pyrrolidone N-and combination thereof.
Colloidal electrolyte of the present invention or solid electrolyte also can select to add polyethylene glycol oxide (polyethylene oxide, PEO), polyethylene glycol oxide is the crystalline macromolecule of a kind of linearity, the big element of electronegative such as aerobic can show polar bond (polar bonding) on the main chain, can help to dissociate.Can be used for the polyethylene glycol oxide among the present invention, purity need reach more than 90%, and average molecular weight range is 500,000 to 8,000,000, and preferred mean molecule quantity is 4,000, and 000 to 5,000, person in 000 scope.
In addition, colloidal electrolyte of the present invention or solid electrolyte also can select to add any known additive, generally speaking, are to add conductor oxidate relevant nature in order to the decorated nanometer level to improve the additive of battery efficiency.Typical additives can be selected from following group: tributyl pyridine (4-tert-butylpyridine, TBP), N-tolimidazole (N-methyl-benzimidazole, MBI), 1,2-dimethyl-3-propyl imidazole salt compounded of iodine (1,2-Dimethyl-3-Propylimidazolium Iodide, DMP II), lithium iodide (LiI) and sodium iodide (NaI).When lithium iodide that in electrolyte, adds small size or sodium iodide, lithium ion (Li
+) or sodium ion (Na
+) can absorption conductor oxidate the surface, can shorten resistance and distance that the conduction band electronics transmits between adjacent or non-conterminous conductor oxidate, can improve the transmission of electronics, improve the short-circuit current density (JSC) of solar cell on the conductor oxidate surface, but Li at the same time,
+-e
-With I in the electrolyte
- 3The speed of combination is also fast again, and voltage (VOC) is reduced.Therefore, by adding tributyl pyridine (4-tert-butylpyridine, TBP), 1,2-dimethyl-3-propyl imidazole salt compounded of iodine or N-tolimidazole can improve minimum electronic energy rank (the LowestUnoccupied Molecular Orbital that do not fill out of dyestuff, LUMO) and the fermi level between the conduction band of conductor oxidate, increase the voltage of battery.For considering the performance of each character of battery, additive that usually can be two or more merges use.
DSSC of the present invention, its surfactant package also can comprise a diaphragm, and for example polyethylene film, heat shrinkage film or known encapsulating material are to intercept aqueous vapor.
The method that in the past prepared DSSC must use two substrates as electrode, and two substrates must separate machined be handled, cause discontinuous on the manufacture process, DSSC of the present invention is only used single substrate, except that significantly reducing its manufacturing cost, owing to can overlapped way finish the preparation of each assembly, so but continued operation has more economic benefit.
The present invention about a kind of manufacture method of above-mentioned DSSC, comprises following steps in addition:
(a) provide one first electrode 12; And
(b) form a dielectric substrate 14 and one second electrode 16 in regular turn in the top of described first electrode,
Wherein said dielectric substrate comprises the electrolyte of illiquidity; And described second electrode comprises an electric conducting material, and its restrictive condition is not for comprising substrate.
First electrode 12 of the present invention, comprise: be formed at a conductive layer 121b, the semi-conductor layer 123 on the substrate 121a in regular turn and be adsorbed in a sensitizing dyestuff 125 of this semiconductor layer surface, but the method preparation that the mat persond having ordinary knowledge in the technical field of the present invention is known, it for example comprises the following step: (1) plates a conductive layer 121b on a substrate 121a, form an electrically-conductive backing plate 121; (2) the nano semiconductor oxide evenly is coated on the electrically-conductive backing plate 121; (3) carry out a curing schedule, for example under 400 ℃ to 600 ℃, carry out sintering, form semi-conductor layer 123; (4) impregnated in sensitizing dyestuff 125 solution, carry out dyestuff absorption.The coating method of above-mentioned steps (2) is such as but not limited to blade coating, wire mark, rotary coating or spraying.
Forming in regular turn of step in the above-mentioned method for manufacturing solar battery (b) is meant on the semiconductor layer 123 and sensitizing dyestuff 125 of first electrode 12, the electrolyte that applies an illiquidity forms a dielectric substrate 14 earlier, forms second electrode 16 afterwards on dielectric substrate 14.The mode that forms second electrode 16 is for example carried out the program of a sputter (sputting) metal (for example platinum) under vacuum; Or at metallizing predecessor under the antivacuum state (for example platinum predecessor) on dielectric substrate 14 and then heat-treat reducing program; Again or with the mixture of conducting polymer or conducting polymer and carbon black material prior to blending in the solvent after, spread upon and then carry out drying program on the dielectric substrate 14.
Now with following specific implementation method further to illustrate the present invention.
With TiO
2(Eternal company produces coating HT, particle diameter 20 nanometer to 50 nanometers, specific area 80-120m
2/ g) to coat a FTO on glass, and about 5 ± 1 microns of thickness carries out about 500 a ℃ sintering program, to form semiconductor layer.
The above-mentioned FTO glass that is covered with semiconductor layer contained to be dipped in carry out dyestuff absorption among the dye solution N719 (production of Solaronix company), last about 12 hours, make the work electrode (first electrode) of DSSC.Wherein, the used solvent of N719 is normal propyl alcohol and acetonitrile, and weight ratio is 1: 1.
After waiting to finish the absorption program and prepared work electrode being cleaned up, 2000 to 4000), 35 weight % polyethylene glycol oxide (molecular weight: 3,500,000 to 4 contain 35 weight % polytrimethylene ether toluenediamine esters (molecular weight: in its surface coated one, 000,000) and I
3 -/ I
-The solid electrolyte composition of the mixture of oxidation-reduction pair is drained electrolytical solvent composition after to be coated the finishing, form dielectric substrate.
Subsequently in the mode of vacuum splashing and plating at bath surface plating platinum, form DSSC to electrode (second electrode), make the DSSC A that the present invention only uses single substrate.To DSSC A carry out battery efficiency test and with outcome record in table 1.
Embodiment 2
Make DSSC B in the mode identical, but be to use conducting polymer PEDOT as material to electrode with embodiment 1.Wherein be after PEDOT is coated on the dielectric substrate surface, under vacuum environment and about 50 ± 10 ℃ temperature, solidify, to form electrode.To DSSC B carry out battery efficiency test and with outcome record in table 1.
Embodiment 3
Make DSSC C in the mode identical, but the mixture that is to use conducting polymer PEDOT and fullerene is as the material to electrode with embodiment 2.Wherein in the total weight of mixture, the about 95 weight % of the content of PEDOT, the about 5 weight % of the content of fullerene.To DSSC C carry out battery efficiency test and with outcome record in table 1.
Embodiment 4
Make DSSC D in the mode identical with embodiment 2.But the mixture that is to use conducting polymer PEDOT and CNT (carbon nano-tube) is as the material to electrode, wherein in the total weight of mixture, and the about 95 weight % of the content of PEDOT, the about 5 weight % of the content of CNT (carbon nano-tube).To DSSC D carry out battery efficiency test and with outcome record in table 1.
Embodiment 5
Make DSSC E in the mode identical with embodiment 4.But in the total weight to the mixture of electrode material, the about 90 weight % of the content of PEDOT, the about 10 weight % of the content of CNT (carbon nano-tube).To DSSC E carry out battery efficiency test and with outcome record in table 1.
The battery efficiency test
Solar cell test uses entire United States average illumination AM 1.5 (θ=48.2 °) to represent the average illumination (25 ℃ of temperature) of sunlight on the face of land usually, and its luminous intensity is about 100mW/cm
2Therefore to be to use luminous intensity be 100mW/cm in this test
2Simulated solar radiant (AM 1.5), test at having the prepared DSSC of the foregoing description, measure its electric current and voltage, and with the gained outcome record in following table 1.Wherein, AM 1.5 represents air quality (Air Mass) 1.5, the angle that on behalf of relative vertical incidence light, AM=1/cos (θ), θ depart from.
Table 1
| DSSC | Open circuit voltage Voc a??(V oc) | Short-circuit current density Jsc b??(mA/cm 2) | Fill factor, curve factor FF c | Photoelectric conversion efficiency η (%) |
| ??A | ??0.42 | ??5.31 | ??0.47 | ??1.06 |
| ??B | ??0.15 | ??0.95 | ??0.26 | ??0.04 |
| ??C | ??0.44 | ??7.61 | ??0.28 | ??0.95 |
| ??D | ??0.54 | ??2.23 | ??0.47 | ??0.56 |
| ??E | ??0.56 | ??2.95 | ??0.40 | ??0.65 |
The a open circuit voltage (open circuit photovoltage, Voc): the solar cell foreign current voltage that Shi Suoliang arrives that opens circuit.
The b short-circuit current density (short-circuit current density, Jsc): when solar cell is zero in load, the value that output current and assembly area are divided by.
(fill factor, FF): the operand power output of solar cell and the ratio of ideal power output are important parameters representing the solar cell properties quality to the c fill factor, curve factor.
In sum, DSSC of the present invention is only used single substrate, can significantly reduce manufacturing cost, and in the present invention, the manufacture method of DSSC is to finish the preparation of each assembly in regular turn with overlapped way, so but continued operation has more economic benefit.Really can implement the tool industrial utilization according to this by the provable DSSC of the present invention of the test result of table 1.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (15)
1, a kind of DSSC is characterized in that it comprises:
One first electrode comprises: a substrate, a conductive layer, semi-conductor layer and a sensitizing dyestuff;
One dielectric substrate comprises the electrolyte of illiquidity; And
One second electrode comprises an electric conducting material, and this second electrode does not comprise substrate,
Wherein said dielectric substrate and described second electrode are the tops that is formed at first electrode in regular turn.
2, DSSC as claimed in claim 1 is characterized in that the electrolyte of wherein said illiquidity comprises a colloidal electrolyte, a solid electrolyte or its combination.
3, DSSC as claimed in claim 1 is characterized in that wherein said electrolytical electrical conductivity is 10
-2S/cm to 10
-6S/cm.
4, DSSC as claimed in claim 2, it is characterized in that wherein said colloidal electrolyte comprises the additive that an oxidation-reduction pair and is selected from following group: specific area is 30m at least
2The filler of/g, molecular weight 1,000 to 5,000,000 macromolecule and combination thereof, and the content of described additive is at least 3 weight % with the total restatement of described electrolyte.
5, DSSC as claimed in claim 4 is characterized in that wherein said additive is to be selected from following group: the about 30m of specific area
2/ g is to about 160m
2The filler of/g, molecular weight 500,000 to 5,000,000 macromolecule and combination thereof, and the content of described additive is 3 weight % to 10 weight % with the total restatement of described electrolyte.
6, DSSC as claimed in claim 2, it is characterized in that wherein said solid electrolyte comprises the additive that an oxidation-reduction pair and is selected from following group: specific area is 30m at least
2The filler of/g, molecular weight 500 to 4,000,000 macromolecule and combination thereof, and the content of described additive is with the total restatement at least 50 weight % of described electrolyte.
7, DSSC as claimed in claim 6 is characterized in that wherein said additive is a molecular weight 500 to 4,000, and 000 macromolecule and its content are 60 weight % to 95 weight % with the total restatement of described electrolyte.
8,, it is characterized in that wherein said filler is to be selected from following group: TiO as claim 4 or 6 described DSSC
2, ZnO, SnO
2, In
2O
3, CdS, ZnS, CdSe, GaP, CdTe, MoSe
2, WSe
2, Nb
2O
5, WO
3, KTaO
3, ZrO
2, SrTiO
3, SiO
2, CdS and combination thereof.
9, DSSC as claimed in claim 8 is characterized in that wherein said filler is to be selected from following group: TiO
2, ZnO, SnO
2, SiO
2And combination.
10, as claim 4 or 6 described DSSC, it is characterized in that wherein said macromolecule is to be selected from following group: polyethers, polyacrylonitrile, poly-acryl, polypyridine, polyaniline, polypyrrole, polystyrene, poly-to benzene, polythiophene, polyacetylene, poly-3,4-ethyl bis ether thiophene, 3-isobutyl group-4-oxygen base-tricosanic acid benzyl esters, polyvinyl pyridine, sulfolane, the dendritic macromolecule of polyamide, volution two fluorenes, poly-(N-vinylcarbazole), gather 3, the 4-ethene dioxythiophene, poly(ethylene oxide), poly-difluoroethylene, EU and combination thereof.
11, DSSC as claimed in claim 10 is characterized in that wherein said EU is a polytrimethylene ether toluenediamine ester.
12,, it is characterized in that wherein said oxidation-reduction pair is to be selected from following group: I as claim 4 or 6 described DSSC
3 -/ I
-, Br
-/ Br
2, SeCN
-/ (SeCN)
2, SCN
-/ (SCN)
2And combination.
13, DSSC as claimed in claim 1 is characterized in that wherein said electric conducting material is to be selected from following group: gold, platinum, plation, silver, aluminium, carbon and compound thereof, transparent conductive oxide, conducting polymer and combination thereof.
14, a kind of manufacture method of DSSC is characterized in that comprising following steps:
One first electrode is provided; And
Form a dielectric substrate and one second electrode in regular turn in the top of described first electrode,
Wherein said dielectric substrate comprises the electrolyte of illiquidity; And described second electrode comprises an electric conducting material, and do not comprise substrate.
15, the manufacture method of DSSC as claimed in claim 14 is characterized in that wherein said first electrode comprises a sensitizing dyestuff that is formed at a conductive layer, the semi-conductor layer on the substrate in regular turn and is adsorbed in this semiconductor layer surface.
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| CNA2009101600454A CN101609750A (en) | 2009-07-16 | 2009-07-16 | DSSC and method for making thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101600454A CN101609750A (en) | 2009-07-16 | 2009-07-16 | DSSC and method for making thereof |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102444811A Division CN102800494A (en) | 2009-07-16 | 2009-07-16 | Dye-sensitized solar cell and manufacturing method thereof |
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|---|---|
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Family
ID=41483446
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102194577A (en) * | 2010-03-10 | 2011-09-21 | 北京大学 | Solar cell and method for making same |
| CN102621759A (en) * | 2011-01-26 | 2012-08-01 | 介面光电股份有限公司 | Three-dimensional image display device and electrochromic module thereof |
| CN102629522A (en) * | 2012-04-29 | 2012-08-08 | 西安电子科技大学 | Manufacture method of dye sensitized solar battery based on gallium nitride (GaN) nanometer post structure |
| CN102775807A (en) * | 2011-05-09 | 2012-11-14 | 台湾永光化学工业股份有限公司 | Dye compound, solar cell using the same, and dye solution |
| CN103578783A (en) * | 2013-07-31 | 2014-02-12 | 营口奥匹维特新能源科技有限公司 | Dye-sensitized solar cell |
| CN104211691A (en) * | 2014-08-13 | 2014-12-17 | 安徽大学 | Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof |
| TWI678404B (en) * | 2017-11-29 | 2019-12-01 | 住華科技股份有限公司 | Pressure sensitive adhesive composition, electrode composite film and manufacturing method for the same |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102194577A (en) * | 2010-03-10 | 2011-09-21 | 北京大学 | Solar cell and method for making same |
| CN102194577B (en) * | 2010-03-10 | 2013-02-06 | 北京大学 | Solar cell and method for making same |
| CN102621759A (en) * | 2011-01-26 | 2012-08-01 | 介面光电股份有限公司 | Three-dimensional image display device and electrochromic module thereof |
| CN102775807A (en) * | 2011-05-09 | 2012-11-14 | 台湾永光化学工业股份有限公司 | Dye compound, solar cell using the same, and dye solution |
| CN102629522A (en) * | 2012-04-29 | 2012-08-08 | 西安电子科技大学 | Manufacture method of dye sensitized solar battery based on gallium nitride (GaN) nanometer post structure |
| CN103578783A (en) * | 2013-07-31 | 2014-02-12 | 营口奥匹维特新能源科技有限公司 | Dye-sensitized solar cell |
| CN103578783B (en) * | 2013-07-31 | 2016-04-13 | 营口奥匹维特新能源科技有限公司 | A kind of DSSC |
| CN104211691A (en) * | 2014-08-13 | 2014-12-17 | 安徽大学 | Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof |
| TWI678404B (en) * | 2017-11-29 | 2019-12-01 | 住華科技股份有限公司 | Pressure sensitive adhesive composition, electrode composite film and manufacturing method for the same |
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