CN103500663A - Three-dimensional compound light photocathode of P-type dye-sensitized solar cell and preparation method thereof - Google Patents
Three-dimensional compound light photocathode of P-type dye-sensitized solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional compound light photocathode of a P-type dye-sensitized solar cell. The three-dimensional compound light photocathode is characterized by comprising a three-dimensional multi-hole conductive substrate and a P-type semiconductor oxide layer which is deposited on the inner surface of a hole channel of the three-dimensional multi-hole conductive substrate. Due to the fact that the three-dimensional compound light photocathode is designed, the dye load is improved on the premise that the P-type semiconductor sull thickness is not increased, photon-generated carrier injection volume is increased, and injected photon-generated carriers are effectively transferred to an outer circuit. According to the prepared three-dimensional compound light photocathode of the P-type dye-sensitized solar cell, after cell assembly, the photoelectric converting efficiency of the three-dimensional compound light photocathode is improved by 26% compared with that of a plane-structure photoelectrode on equal conditions, and the short-circuit photocurrent is improved by 77%. The three-dimensional compound light photocathode of the P-type dye-sensitized solar cell is simple in technology and method, mild in reaction condition and convenient to produce, control and popularize, and has great significance to the development of high-efficiency P-type and Pn-type dye-sensitized solar cells.
Description
Technical field
The present invention relates to the DSSC technical field, be specifically related to three-dimensional Hybrid Photocathode of a kind of P type dye sensitization solar battery and preparation method thereof.
Technical background:
Solar cell is directly electric energy by transform light energy, is the important directions of clean energy resource development.DSSC, due to low cost, preparation technology simply reaches potential high conversion efficiency becomes the current research focus.At present, the conversion efficiency of n-type dye sensitization solar battery record has reached 12%(Science, and 2011,334,629-634.).As battery design becomes the two poles of the earth sensitization structure, be pn-type dye sensitization solar battery, its theoretical transformation efficiency is 43%(Chem.Rev., 2010,110,6595-6663.), will provide greater room for battery conversion efficiency improves.With respect to n-type dye sensitization solar battery, the research of p-type dye sensitization solar battery is still immature, and p-type dye sensitization solar battery design of material and preparation are become to the basic and crucial of development high efficiency dye sensitization solar battery.
Thereby the operation principle of P type dye sensitization solar battery is after dyestuff absorption light, p-type semiconductor valence band to be injected in hole to realize separation of charge.With n-type dye sensitization solar battery, compare, p-type dye sensitization solar battery photoelectric conversion efficiency is lower, particularly short circuit current (Jsc) is only 1/3rd (Coordination Chemistry Reviews.2012 of n-DSSC, 256,2414 – 2423), can't meet pn type dye sensitization solar battery currents match demand.
In order to improve short circuit current, at first need optoelectronic pole to adsorb more dyestuff at present, thus researchers be devoted to prepare thick and fine and close p-type optoelectronic pole (Energy Environ.Sci., 2012,5,8896-8900.).But due to the carrier mobility of p-type semi-conducting material low (than low 3 orders of magnitude of n-type semi-conducting material), the mean free path in hole is short, the thickness of p-type optoelectronic pole limited (1～2 μ m), the load capacity of dyestuff is few, and the upper limit of photogenerated current is caused to restriction.Therefore how, when increasing the dye load amount, will show the more effective external circuit that is transferred to of separative electric charge and go, become the key that improves p-type DSSC performance.
Summary of the invention:
Purpose of the present invention is in order to address the above problem, a kind of three-dimensional Hybrid Photocathode of P type dye sensitization solar battery is provided, the p-dye-sensitized cell of three-dimensional Hybrid Photocathode structure, increase to a certain extent p-type semiconductor oxide membrane electrode absorbing dye area, but do not increase the thickness of p-type oxide semiconductor film, make the effective external circuit shifted of photo-generated carrier injected, improve electricity conversion.The present invention also provides the preparation method of the three-dimensional Hybrid Photocathode of P type dye sensitization solar battery.
The technical scheme that the present invention adopted for achieving the above object is:
A kind of three-dimensional Hybrid Photocathode of P type dye sensitization solar battery, is characterized in that, it comprises three-dimensional porous conductive substrates and P type semiconductor oxide skin(coating), and described P type semiconductor oxide layer deposition is at three-dimensional porous conductive substrates duct inner surface.
Described three-dimensional porous conductive substrates is that the fluorine doping stannic oxide is attached to transparent conducting glass FTO above, the including transparent conducting oxide layer with three-dimensional IPN loose structure of formation.
The tin ash that the including transparent conducting oxide layer of described three-dimensional IPN loose structure is the fluorine doping forms, and its thickness is 5～20 μ m, and aperture is 450～2000nm.
The ternary oxide CuMO that described P type semiconductor oxide skin(coating) is nickel oxide NiO or copper
2, M is one of Al, Ga or Cr.
The preparation method of the three-dimensional Hybrid Photocathode of a kind of above-mentioned p-type DSSC, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 500～2000nm, through the constant temperature vertical deposition method, the polystyrene moulding of self assembly 5～20 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, calcine under 400～600 ℃ 1～4 hour, remove described polystyrene moulding, obtain three-dimensional porous conductive substrates;
(3) adopt the three-dimensional Hybrid Photocathode material of chemical bath deposition method or template synthesis p-type DSSC; Described chemical bath deposition method, for the described three-dimensional porous conductive substrates constant temperature of step (2) is deposited in the nickel oxide NiO precursor aqueous solution containing catalyst, is calcined and within 0.5～4 hour, is obtained the Hybrid Photocathode material under 350～500 ℃; The ternary oxide CuMO that described template is the copper that will contain the nickel oxide NiO presoma of nonionic surface active agent or contain cationic surfactant
2presoma is filled in three-dimensional porous conductive substrates duct, calcines under 350～500 ℃ and within 0.5～4 hour, obtains three-dimensional Hybrid Photocathode material.
In the described fluorine-doped tin oxide presoma of step (2), the mol ratio of fluorine and tin is fluorine 0.1～5: tin 1.
In the nickel oxide NiO that contains catalyst in the described chemical bath deposition method of step (3), nickeliferous inorganic salts are six hydration nickel sulfate, nickel acetate or nickel chloride; Described catalyst is potassium peroxydisulfate or sodium peroxydisulfate and ammoniacal liquor, and the solvent of this catalyst is deionized water, and depositing temperature is 20～30 ℃, and sedimentation time is 20～40 minutes.
In the described template of step (3), nonionic surface active agent is triblock copolymer F108, P123 or F88; Described cationic surfactant is softex kw; In described nickel oxide NiO, nickeliferous inorganic salts are six hydration nickel sulfate, nickel acetate or nickel chloride; The ternary oxide CuMO of described copper
2the inorganic salts of middle cupric are copper sulphate, copper nitrate or Schweinfurt green, the ternary oxide CuMO of described copper
2in containing the inorganic salts of M, be one of aluminum sulfate, gallium sulfate, chromium sulfate, aluminum nitrate, gallium nitrate or chromic nitrate, described M is Al, Ga or Cr; The solvent of described presoma is ethylene glycol, ethanol, isopropyl alcohol or butanols.
The mass ratio of described nonionic surface active agent and nickel oxide NiO presoma is (0.1～4): 1, and the ternary oxide CuMO of described cationic surfactant and copper
2the mol ratio of presoma is cationic surfactant 0.1～1:CuMO
2presoma 1.
The invention has the beneficial effects as follows: 1. the present invention is by the three-dimensional Hybrid Photocathode of design, do not increasing under p-type oxide semiconductor film thickness prerequisite, improve the load capacity of dyestuff, thereby increased the injection rate of photo-generated carrier, and make the photo-generated carrier injected effectively transfer to external circuit.
2. the three-dimensional Hybrid Photocathode of the p-type DSSC that prepared by the present invention, after assembled battery, through the photoelectric properties test, electricity conversion improves 26% than equal conditions planar structure optoelectronic pole, and short-circuit photocurrent improves 77%.
3. process of the present invention is simple, and the reaction condition gentleness is convenient to production control and popularization, significant to developing high efficiency p-type and pn-DSSC.
Embodiment
Embodiment 1: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, it comprises three-dimensional porous conductive substrates and P type semiconductor oxide skin(coating), and described P type semiconductor oxide layer deposition is at three-dimensional porous conductive substrates duct inner surface.
Described three-dimensional porous conductive substrates is that the fluorine doping stannic oxide is attached to transparent conducting glass FTO above, the including transparent conducting oxide layer with three-dimensional IPN loose structure of formation.
The tin ash that the including transparent conducting oxide layer of described three-dimensional IPN loose structure is the fluorine doping forms, and its thickness is 5～20 μ m, and aperture is 450～2000nm.
The ternary oxide CuMO that described P type semiconductor oxide skin(coating) is nickel oxide NiO or copper
2, M is one of Al, Ga or Cr.
The preparation method of the three-dimensional Hybrid Photocathode of a kind of above-mentioned p-type DSSC, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 500～2000nm, through the constant temperature vertical deposition method, the polystyrene moulding of self assembly 5～20 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, calcine under 400～600 ℃ 1～4 hour, remove described polystyrene moulding, obtain three-dimensional porous conductive substrates;
(3) adopt the three-dimensional Hybrid Photocathode material of chemical bath deposition method or template synthesis p-type DSSC; Described chemical bath deposition method, for the described three-dimensional porous conductive substrates constant temperature of step (2) is deposited in the nickel oxide NiO precursor aqueous solution containing catalyst, is calcined and within 0.5～4 hour, is obtained the Hybrid Photocathode material under 350～500 ℃; The ternary oxide CuMO that described template is the copper that will contain the nickel oxide NiO presoma of nonionic surface active agent or contain cationic surfactant
2presoma is filled in three-dimensional porous conductive substrates duct, calcines under 350～500 ℃ and within 0.5～4 hour, obtains three-dimensional Hybrid Photocathode material.
In the described fluorine-doped tin oxide presoma of step (2), the mol ratio of fluorine and tin is fluorine 0.1～5: tin 1.
In the nickel oxide NiO that contains catalyst in the described chemical bath deposition method of step (3), nickeliferous inorganic salts are six hydration nickel sulfate, nickel acetate or nickel chloride; Described catalyst is potassium peroxydisulfate or sodium peroxydisulfate and ammoniacal liquor, and the solvent of this catalyst is deionized water, and depositing temperature is 20～30 ℃, and sedimentation time is 20～40 minutes.
In the described template of step (3), nonionic surface active agent is triblock copolymer F108, P123 or F88; In described nickel oxide NiO, nickeliferous inorganic salts are six hydration nickel sulfate, nickel acetate or nickel chloride; Described cationic surfactant is softex kw; The ternary oxide CuMO of described copper
2the inorganic salts of middle cupric are copper sulphate, copper nitrate or Schweinfurt green, the ternary oxide CuMO of described copper
2in containing the inorganic salts of M, be one of aluminum sulfate, gallium sulfate, chromium sulfate, aluminum nitrate, gallium nitrate or chromic nitrate, described M is Al, one of Ga or Cr; The solvent of described presoma is ethylene glycol, ethanol, isopropyl alcohol or butanols.
The mass ratio of described nonionic surface active agent and nickel oxide NiO presoma is (0.1～4): 1, and the ternary oxide CuMO of described cationic surfactant and copper
2the mol ratio of presoma is cationic surfactant 0.1～1:CuMO
2presoma 1.
Embodiment 2: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 1, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 600nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 6 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 450nm;
(3) adopt chemical bath deposition method to prepare the three-dimensional Hybrid Photocathode material of p-type DSSC, get the 1M six hydration nickel sulfate and the 0.25M potassium peroxydisulfate mixes in room temperature, slowly drip ammoniacal liquor (25～28%) under strong agitation, by vertical being immersed in solution of the described three-dimensional porous conductive substrates of step (2), standing 30 minutes in 25 ℃, use washed with de-ionized water after taking out, in 75 ℃ of oven for drying, under 400 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 2 hours.
Embodiment 3: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 1, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 1000nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 10 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 750nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, getting copper nitrate and gallium nitrate mixes with softex kw, the mol ratio of copper nitrate and gallium nitrate and softex kw is 1:1:0.1, add deionized water ethylene glycol to be configured to mixed solution, getting a certain amount of mixed solution is spin-coated on above-mentioned three-dimensional porous conductive substrates, in 75 ℃ of oven for drying, under 400 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 2 hours.
Embodiment 4: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 3, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 1500nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 15 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 1120nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, get respectively the 1g nickel acetate, 1g triblock copolymer, 3g deionized water and 6g ethanol are configured to mixed solution, be configured to slurry in 30 ℃ of centrifugal filtrations after standing 3 days, get a certain amount of slurry for rotary coating on above-mentioned three-dimensional porous conductive substrates, in room temperature, after standing 30 minutes, under 450 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 1.5 hours.
Embodiment 5: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 3, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 2000nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 20 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.1:1, presoma is spun on polystyrene moulding, under 400 ℃, calcining is 1 hour, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 2000nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, getting copper sulphate and chromium sulfate softex kw mixes, the mol ratio of copper sulphate and chromic nitrate and softex kw is 1:1:1, add deionized water ethanol to be configured to mixed solution, getting a certain amount of mixed solution is spin-coated on above-mentioned three-dimensional porous conductive substrates, in 75 ℃ of oven for drying, under 400 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 2 hours.
Embodiment 6: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 3,5, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 2000nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 20 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.1:1, presoma is spun on polystyrene moulding, under 400 ℃, calcining is 1 hour, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 2000nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, getting copper nitrate Schweinfurt green and aluminum nitrate mixes with softex kw, the mol ratio of copper nitrate and chromic nitrate and softex kw is 1:1:0.5, add the deionized water isopropyl alcohol to be configured to mixed solution, getting a certain amount of mixed solution is spin-coated on above-mentioned three-dimensional porous conductive substrates, in 75 ℃ of oven for drying, under 400 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 2 hours.
Embodiment 7: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 3,5,6, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 1000nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 10 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mass ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 750nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, getting copper nitrate and chromic nitrate mixes with softex kw, the mol ratio of copper nitrate and chromic nitrate and softex kw: 1:1:0.3 mixes, add the deionized water butanols to be configured to mixed solution, getting a certain amount of mixed solution is spin-coated on above-mentioned three-dimensional porous conductive substrates, in 75 ℃ of oven for drying, under 400 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 2 hours.
Embodiment 8: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 1,2, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 500nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 5 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 5:1, presoma is spun on polystyrene moulding, under 600 ℃, calcining is 1 hour, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 500nm;
(3) adopt chemical bath deposition method to prepare the three-dimensional Hybrid Photocathode material of p-type DSSC, get the 1M nickel acetate and the 0.25M sodium peroxydisulfate mixes in room temperature, slowly drip ammoniacal liquor (25～28%) under strong agitation, by vertical being immersed in solution of the described three-dimensional porous conductive substrates of step (2), standing 40 minutes in 20 ℃, use washed with de-ionized water after taking out, in 75 ℃ of oven for drying, under 500 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 0.5 hour.
Embodiment 9: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 1,2 and 8, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 600nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 6 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 450nm;
(3) adopt chemical bath deposition method to prepare the three-dimensional Hybrid Photocathode material of p-type DSSC, get the 1M nickel chloride and the 0.25M potassium peroxydisulfate mixes in room temperature, slowly drip ammoniacal liquor (25～28%) under strong agitation, by vertical being immersed in solution of the described three-dimensional porous conductive substrates of step (2), standing 20 minutes in 30 ℃, use washed with de-ionized water after taking out, in 75 ℃ of oven for drying, under 350 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 4 hours.
Embodiment 10: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 3 and 4, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 1500nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 15 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 1120nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, get respectively the 1g six hydration nickel sulfate, 0.1g triblock copolymer, 3g deionized water and 6g ethanol are configured to mixed solution, be configured to slurry in 30 ℃ of centrifugal filtrations after standing 3 days, get a certain amount of slurry for rotary coating on above-mentioned three-dimensional porous conductive substrates, in room temperature, after standing 30 minutes, under 450 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 1.5 hours.
Embodiment 11: the three-dimensional Hybrid Photocathode of the P type dye sensitization solar battery that the present embodiment provides, and its component and step are basic identical with embodiment 3,4 and 10, and its difference is:
The three-dimensional Hybrid Photocathode of described P type dye sensitization solar battery, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 1500nm, through the constant temperature vertical deposition method, the polystyrene moulding that self assembly thickness is 15 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, in presoma, fluorine and tin mol ratio are 0.7:1, presoma is spun on polystyrene moulding, under 450 ℃, calcining is 4 hours, remove described polystyrene moulding, obtaining aperture is the three-dimensional porous conductive substrates of 1120nm;
(3) adopt the three-dimensional Hybrid Photocathode material of template synthesis p-type DSSC, get respectively the 1g nickel chloride, 4g triblock copolymer, 3g deionized water and 6g ethanol are configured to mixed solution, be configured to slurry in 30 ℃ of centrifugal filtrations after standing 3 days, get a certain amount of slurry for rotary coating on above-mentioned three-dimensional porous conductive substrates, in room temperature, after standing 30 minutes, under 450 ℃, calcining obtains three-dimensional Hybrid Photocathode material in 1.5 hours.
But the foregoing is only better possible embodiments of the present invention, not in order to limit to the scope of the claims of the present invention, therefore the equivalent structure that all utilizations specification of the present invention is done changes, all be included in protection scope of the present invention.
Claims (9)
1. the three-dimensional Hybrid Photocathode of a P type dye sensitization solar battery, is characterized in that, it comprises three-dimensional porous conductive substrates and P type semiconductor oxide skin(coating), and described P type semiconductor oxide layer deposition is at three-dimensional porous conductive substrates duct inner surface.
2. the three-dimensional Hybrid Photocathode of P type dye sensitization solar battery according to claim 1, it is characterized in that, described three-dimensional porous conductive substrates is that the fluorine doping stannic oxide is attached to transparent conducting glass FTO above, the including transparent conducting oxide layer with three-dimensional IPN loose structure of formation.
3. the three-dimensional Hybrid Photocathode of P type dye sensitization solar battery according to claim 2, is characterized in that, the tin ash that described including transparent conducting oxide layer is the fluorine doping forms, and its thickness is 5～20 μ m, and aperture is 450～2000nm.
4. the three-dimensional Hybrid Photocathode of P type dye sensitization solar battery according to claim 1, is characterized in that, the ternary oxide CuMO that described P type semiconductor oxide skin(coating) is nickel oxide NiO or copper
2, M is one of Al, Ga or Cr.
5. the preparation method of the three-dimensional Hybrid Photocathode of the described p-type DSSC of one of claim 1～4, is characterized in that, it comprises the following steps:
(1) get the polystyrene microsphere that particle diameter is 500～2000nm, through the constant temperature vertical deposition method, the polystyrene moulding of self assembly 5～20 μ m on transparent conducting glass;
(2) introduce the tin oxide presoma of fluorine doping on the described polystyrene moulding of step (1) surface, calcine under 400～600 ℃ 1～4 hour, remove described polystyrene moulding, obtain three-dimensional porous conductive substrates;
(3) adopt the three-dimensional Hybrid Photocathode material of chemical bath deposition method or template synthesis p-type DSSC; Described chemical bath deposition method, for the described three-dimensional porous conductive substrates constant temperature of step (2) is deposited in the nickel oxide NiO precursor aqueous solution containing catalyst, is calcined and within 0.5～4 hour, is obtained the Hybrid Photocathode material under 350～500 ℃; The ternary oxide CuMO that described template is the copper that will contain the nickel oxide NiO presoma of nonionic surface active agent or contain cationic surfactant
2presoma is filled in three-dimensional porous conductive substrates duct, calcines under 350～500 ℃ and within 0.5～4 hour, obtains three-dimensional Hybrid Photocathode material.
6. the preparation method of the three-dimensional Hybrid Photocathode of p-type DSSC according to claim 5, is characterized in that, in the described fluorine-doped tin oxide presoma of step (2), the mol ratio of fluorine and tin is fluorine 0.1～5: tin 1.
7. the preparation method of the three-dimensional Hybrid Photocathode of p-type DSSC according to claim 5, it is characterized in that, step (3) specifically also comprises following content, in described chemical bath deposition method, contain in the nickel oxide NiO of catalyst, nickeliferous inorganic salts are six hydration nickel sulfate, nickel acetate or nickel chloride; Described catalyst is potassium peroxydisulfate or sodium peroxydisulfate and ammoniacal liquor, and the solvent of this catalyst is deionized water, and depositing temperature is 20～30 ℃, and sedimentation time is 20～40 minutes.
8. the preparation method of the three-dimensional Hybrid Photocathode of p-type DSSC according to claim 5, is characterized in that, step (3) specifically also comprises following content, and in described template, nonionic surface active agent is triblock copolymer; Described cationic surfactant is softex kw; In described nickel oxide NiO, nickeliferous inorganic salts are six hydration nickel sulfate, nickel acetate or nickel chloride; The ternary oxide CuMO of described copper
2the inorganic salts of middle cupric are copper sulphate, copper nitrate or Schweinfurt green, the ternary oxide CuMO of described copper
2in containing the inorganic salts of M, be one of aluminum sulfate, gallium sulfate, chromium sulfate, aluminum nitrate, gallium nitrate or chromic nitrate, described M is Al, one of Ga or Cr; The solvent of described presoma is ethylene glycol, ethanol, isopropyl alcohol or butanols.
9. the preparation method of the three-dimensional Hybrid Photocathode of p-type DSSC according to claim 8, it is characterized in that, the mass ratio of described nonionic surface active agent and nickel oxide NiO presoma is (0.1～4): 1, and the ternary oxide CuMO of described cationic surfactant and copper
2the mol ratio of presoma is cationic surfactant 0.1～1:CuMO
2presoma 1.
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