CN103985551A - Dye-sensitized solar cell photo-anode and preparing method thereof - Google Patents

Dye-sensitized solar cell photo-anode and preparing method thereof Download PDF

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CN103985551A
CN103985551A CN201410199283.7A CN201410199283A CN103985551A CN 103985551 A CN103985551 A CN 103985551A CN 201410199283 A CN201410199283 A CN 201410199283A CN 103985551 A CN103985551 A CN 103985551A
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tio
pan
naco
dye
solar cell
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CN103985551B (en
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何泓材
任双双
王宁
胡巍
陈海军
钱能
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Chengdu Zhongjin Liyang New Material Technology Co Ltd
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University of Electronic Science and Technology of China
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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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention provides a dye-sensitized solar cell photo-anode and a preparing method of the dye-sensitized solar cell photo-anode and belongs to the technical field of solar cell manufacturing. According to the photo-anode, on the basis of a porous titanium dioxide nanocrystalline thin film for a dye-sensitized solar cell, and a coaxial nanometer cable is additionally arranged on the surface of the porous titanium dioxide nanocrystalline thin film in an attached mode; crystalline state TiO2 is used as a case layer of the coaxial nanometer cable, one of NaCo2O4, Sb2Te3, Bi2Te3, HgTe, Bi2Se3, ZnSb, SbTe, PbTe, Bi(SiSb2) and Bi2(GeSe)3 is used as a core layer of the coaxial nanometer cable, a core layer material has high conductivity, a fast transmission channel for electrons can be effectively formed in the core layer, and therefore photoproduction electron-hole pairs in dye molecules can be separated fast and easily; moreover, the electron conduction capacity in the whole process is improved, and the photoelectric conversion efficiency of the dye-sensitized solar cell is improved.

Description

A kind of dye-sensitized solar cell anode and preparation method thereof
Technical field
The invention belongs to technical field of solar cell manufacturing, be specifically related to a kind of dye-sensitized solar cell anode and preparation method thereof.
Background technology
Along with social develop rapidly, the mankind increase day by day to the demand of the energy.At present; fossil energy (coal, oil and natural gas etc.) still occupy leading position in energy resource structure; yet exhaustive exploitation and the energy crisis and the problem of environmental pollution that use fossil energy to cause display gradually, and become the decisive factor that restriction economic society continues, develops in a healthy way.Renewable Energy Development (being new forms of energy) is one of effective way addressing the above problem.In many new forms of energy, solar energy is with the advantage of its abundant energy storage, cleanliness without any pollution and be subject to extensive concern compared with little regional limits.The utilization of solar energy is mainly comprised to photo-thermal conversion, opto-electronic conversion and 3 kinds of forms of photochemistry conversion.Solar cell is a kind of electrooptical device that solar energy is converted to electric energy, and it can also can generate electricity by way of merging two or more grid systems directly for compact electric apparatus provides electric energy, has very wide application prospect.
DSSC (DSSC) belongs to a kind of of solar cell, and it is by having adsorbed nano porous semiconductor film (light anode), the redox electrolytes matter of sensitizing dyestuff and electrode being formed.Wherein, dye sensitizing agent absorbs sunlight and is also excited, electronics by ground state transition to excitation state; The dye molecule of excitation state is by electronic injection in semi-conductive conduction band, and the electronics in conduction band transfers to light anode in nanocrystalline networks, enters external circuit, and the dyestuff that loses electronics (is mainly I by the reducing agent in electrolyte -) reduction, thereby dyestuff regenerated, reducing agent in electrolyte is oxidized (is mainly I 3 -), the dithizone in electrolyte (is mainly I 3 -) be diffused into obtaining electronics on electrode, electrolyte regeneration, thus a cyclic process of photoelectric current completed.
The basic structure of existing dye-sensitized solar cell anode is the poriferous titanium dioxide nano-crystal film that is made in transparent conductive glass surface, and poriferous titanium dioxide nano-crystal film surface is absorbing dye sensitizer again.Existing dye-sensitized solar cell anode, it is born in the poriferous titanium dioxide nano-crystal film of separation of charge and electronics transportation, owing to existing a large amount of interface resistances between titanium dioxide nanocrystalline grain, can form the energy barrier that electronics transmits, limited the fast transferring of oxide conduction band electron in oxide porous network thin-film, thereby make light induced electron-hole in dye molecule to can not be effectively separated, restrict the raising of DSSC photoelectric conversion efficiency.Therefore, guaranteeing TiO 2mating with the energy level of dyestuff, when not affecting Dye Adsorption and electronic injection, improve the electronic conduction ability of light anode, is to realize the key point that improves DSSC battery short circuit current density and then promote cell photoelectric conversion efficiency.At present, main employing carries out to titanium dioxide photo anode the photoelectric conversion efficiency that physical chemistry modifying improves DSSC, mainly comprises doping, TiCl 4the method such as process, coated.Doping is mainly at TiO 2in add all kinds of metal ions, but its photoelectric conversion efficiency to final raising DSSC has little significance.And TiCl 4it is ripe that treatment process has been tending towards, and development prospect is little.Coated method is in mechanism and technical more complicated, but the raising of performance is had more to potentiality, and the selection of coating has diversity, thereby attracted more researchers' concern.The coated processing of light anode mainly refers to the core-shell structure of preparing light anode, and adopting at present more is electrostatic spinning technique, and the light anode treatment method that this technique is more traditional is more complicated.Existing is mainly with TiO about the coated processing method of light anode 2for sandwich layer, with other metal oxides (ZnO, Al 2o 3, MgO etc.) be shell, the energy barrier forming at shell can suppress TiO 2conduction band electron and dye well are electrolytical compound, or in core shell interface, form the injection efficiency that dipole layer improves electronics, strengthen the electronic conduction ability of light anode, thereby improve its photoelectric conversion efficiency (Du Pingfan, Xiong Jie, Song Lixin, Xi Zhenqiang, the preparation method of titanium dioxide-zinc oxide nuclear shell structure nanometer fiber membrane for dye sensitized battery: China: 201110399850.X.).Yet due to TiO 2with associated metal oxide (ZnO, Al 2o 3, MgO etc.) structural similarity, energy gap is close, and does not possess very strong conductive capability, so the effect aspect raising photoelectric conversion efficiency is still limited, can not make full use of the advantage of this special construction of core-shell, improve to greatest extent photoelectric conversion efficiency.
Summary of the invention
The invention provides a kind of dye-sensitized solar cell anode and preparation method thereof, this light anode is on the basis of existing used by dye sensitization solar battery poriferous titanium dioxide nano-crystal film, increased the coaxial nano cable that one deck is attached to poriferous titanium dioxide nano-crystal film surface, this coaxial nano cable is with crystalline state TiO 2for shell, with NaCo 2o 4, Sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2), Bi 2(GeSe) 3in a kind of be sandwich layer, core material has high conductivity, in sandwich layer, can effectively form the fast transport passage of electronics, be conducive to the right quick separation in light induced electron-hole in dye molecule, accelerate the electronic conduction ability of whole process, thereby improve the photoelectric conversion efficiency of DSSC.
The technical solution used in the present invention is as follows:
A kind of dye-sensitized solar cell anode, as shown in Figure 1, comprise electro-conductive glass 8, be positioned at the titanium dioxide nanocrystalline film 9 on electro-conductive glass 8, the coaxial nano cable 10 of dyestuff that has been positioned at absorption on titanium dioxide nanocrystalline film 9, described coaxial nano cable is vertically to adhere on titanium dioxide nanocrystalline film 9, described coaxial nano cable be align and the degree of order be 60%～100%, the shell of described coaxial nano cable is crystalline state TiO 2, sandwich layer is NaCo 2o 4, Sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2), Bi 2(GeSe) 3in a kind of.
A preparation method for dye-sensitized solar cell anode, comprises the following steps:
Step 1: prepare colloidal tio 2;
Step 2: prepare (TiO 2/ PVP) shell layer spinning solution and (NaCo 2o 4/ PAN) sandwich layer spinning solution: first add polyvinylpyrrolidone (PVP) and nano-TiO in absolute ethyl alcohol 2particle, wherein polyvinylpyrrolidone (PVP), absolute ethyl alcohol, nano-TiO 2the mass ratio of particle is 1:40:1, stirring and dissolving, the calgon that then adds 0.03%～0.06% mass percent as surfactant to improve nano-TiO 2the dispersiveness of particle, ultrasonic dissolution, and react 1h under 50 ℃～100 ℃ conditions, obtain (TiO 2/ PVP) shell layer spinning solution; DMF (dimethyl formamide) solution that preparation PAN (polyacrylonitrile) quality percentage composition is 6.4wt%, obtain PAN solution, then in PAN solution, add sodium acetate and cobalt acetate, wherein, the mass ratio of sodium acetate, cobalt acetate and PAN solution is 0.27:1:1.35, through magnetic agitation, dissolve, obtain (NaCo 2o 4/ PAN) sandwich layer spinning solution;
Step 3:(TiO 2/ PVP)/(NaCo 2o 4/ PAN) preparation of directed coaxial composite fibre: adopt cylinder coaxial electrostatic spinning silk device preparation (TiO as shown in Figure 3 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre, first by (NaCo 2o 4/ PAN) sandwich layer spinning solution adds in interior liquid storage container (2), by (TiO 2/ PVP) shell layer spinning solution adds in outer liquid storage container (3), then between sandwich layer 2 shell 3 solution and cylinder receiving screen 6, apply the voltage of 10～35kV, wherein positive pole connects sandwich layer solution and shell solution, negative pole connects cylinder receiving screen, the surface tension that sandwich layer 2 and shell 3 solution overcome self under the effect of electric field forms the ejection from inner nozzle 4 and outer nozzle 5 respectively of injection thread, along with the volatilization of solvent, spray thread and solidify to form (TiO 2/ PVP)/(NaCo 2o 4/ PAN) composite fibre, sprays (the TiO that thread solidify to form 2/ PVP)/(NaCo 2o 4/ PAN) composite fibre be take the form of circumference and is attached on the aluminium foil on the cylinder receiving screen that rotating speed is 700r/min～1250r/min, and wherein the distance of 6 of outer nozzle 5 and cylinder receiving screens is 5～25cm, thereby obtains (TiO 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre;
Step 4:TiO 2/ NaCo 2o 4the preparation of coaxial nano cable: the colloidal tio 2 of first preparing in electro-conductive glass 8 surface-coated steps 1; Then (TiO step 3 being obtained 2/ PVP)/(NaCo 2o 4/ PAN) aluminium foil that directed coaxial composite fibre is accepted screen from cylinder is torn, and cutting area is not higher than the (TiO of titanium dioxide nanocrystalline film size 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre, vertically adhere on the titanium dioxide nanocrystalline film on electro-conductive glass, and be positioned in Muffle furnace, after being warming up to 500 ℃～900 ℃ with 1～5 ℃/min heating rate, keep 2～24h, naturally cool to room temperature, obtain being attached to the TiO of titanium dioxide nanocrystalline film surface on electro-conductive glass 2/ NaCo 2o 4coaxial nano cable, then adsorpting dye molecule obtains described smooth anode.
Colloidal tio 2 described in step 1 is commercially available P25 colloidal tio 2.
4 diameters of inner nozzle described in step 3 are 0.1～0.7mm, and outer nozzle 5 diameters are 0.5～1.2mm, and inner nozzle mouth is jet hole top 0.3～0.7mm outside.
When the sandwich layer of coaxial nano cable is Sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2) or Bi 2(GeSe) 3time, the method of preparing dye-sensitized solar cell anode is identical with above-mentioned steps, the process of wherein preparing sandwich layer spinning solution is: first prepare DMF (dimethyl formamide) solution that PAN (polyacrylonitrile) quality percentage composition is 5wt%～15wt%, obtain PAN solution, then in PAN solution, add Sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2) or Bi 2(GeSe) 3, Sb wherein 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2) or Bi 2(GeSe) 3with the mass ratio of PAN solution be 0.6～0.8, through magnetic agitation, dissolve, obtain (Sb 2te 3/ PAN), (Bi 2te 3/ PAN), (HgTe/PAN), (Bi 2se 3/ PAN), (ZnSb/PAN), (SbTe/PAN), (PbTe/PAN), (Bi (SiSb 2)/PAN) or (Bi 2(GeSe) 3/ PAN) sandwich layer spinning solution.
Beneficial effect of the present invention is:
1, dye-sensitized solar cell anode provided by the invention adopts in original poriferous titanium dioxide nano-crystal film surface attachment coaxial nano cable structure, and coaxial nano cable is with crystalline state TiO 2for shell, with NaCo 2o 4, Sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2), Bi 2(GeSe) 3in a kind of be sandwich layer.Due to NaCo 2o 4deng thermoelectric material, there is high conductivity, in sandwich layer, can effectively form the fast transport passage of electronics, be conducive to the right quick separation in light induced electron-hole in dye molecule, accelerate the electronic conduction ability of whole process, be conducive to the raising of the photoelectric conversion efficiency of DSSC.
2, battery in use, illumination always produces a large amount of unwanted heat, between battery front side and the back side, certainly leads to temperature gradient, therefore at light anode two ends, certainly exists the temperature difference, and thermoelectric material all has Seebeck effect, the temperature difference at thermoelectric material two ends can produce electromotive force.In the present invention, select high performance NaCo 2o 4deng thermoelectric material, the thermoelectromotive force of light anode thermoelectricity inner core is increased, direction and the light anode that by controlling the type (p-type or N-shaped) of thermoelectric material, can control thermoelectromotive force inject electron motion direction, make thermoelectromotive force and photovoltaic effect stack obtain the photoelectric conversion efficiency strengthening.
3, TiO 2there is an energy level matching relationship with dye molecule, and NaCo 2o 4deng thermoelectricity sandwich layer, have excellent conductive performance, the thermoelectric material sandwich layer of high conductivity becomes the express passway of electrical conductivity, can quickly heap be attached to TiO 2the electric transmission on shell surface, in conduction band, reduces electron-hole recombinations probability, reduces dark current, is conducive to TiO 2carry out matched well with dyestuff energy level; The thermoelectromotive force simultaneously producing in Seebeck effect and the stack of the photovoltaic effect of light anode, be expected to make the short-circuit current density of DSSC battery significantly to improve, and then significantly improve the photoelectric conversion efficiency of battery.
4, the TiO on electro-conductive glass top layer in dye-sensitized solar cell anode provided by the invention 2nano-crystal film can effectively prevent TiO 2/ NaCo 2o 4cable floor directly contacts the short circuit phenomenon that may cause with electro-conductive glass.
In sum, dye-sensitized solar cell anode provided by the present invention and preparation method thereof is expected to play very large help to improving DSSC photoelectric conversion efficiency; And its preparation method is simple, required processing conditions is gentle, and process safety is reliable.
Accompanying drawing explanation
Fig. 1 is the structural representation of dye-sensitized solar cell anode provided by the invention.Wherein 8: electro-conductive glass, 9: titanium dioxide nanocrystalline film, 10: the coaxial nano cable that has adsorbed dyestuff.
Fig. 2 is coaxial nano cable radial cross-section.Wherein, 11 is sandwich layer, and 12 is shell.
Fig. 3 is that the present invention prepares the cylinder coaxial electrostatic spinning silk device schematic diagram that directed coaxial composite fibre adopts.Wherein, 1: high voltage source, 2: interior liquid storage container, 3: outer liquid storage container, 4: inner nozzle, 5: outer nozzle, 6: cylinder receiving screen, 7: motor.
Fig. 4 is the photoelectric current voltage-contrast curve chart of the DSSC of the embodiment of the present invention 1 resulting smooth anode assembling and the DSSC of comparative example's assembling.
Embodiment
Embodiment 1
A kind of dye-sensitized solar cell anode, as shown in Figure 1, comprise electro-conductive glass 8, be positioned at the titanium dioxide nanocrystalline film 9 on electro-conductive glass 8, the coaxial nano cable 10 of dyestuff that has been positioned at absorption on titanium dioxide nanocrystalline film 9, described coaxial nano cable is vertically to adhere on titanium dioxide nanocrystalline film 9, described coaxial nano cable be align and the degree of order be 80%, the shell of described coaxial nano cable is crystalline state TiO 2, sandwich layer is NaCo 2o 4.
Above-mentioned core material NaCo 2o 4for thermoelectric material, because thermoelectric material has high conductivity, in sandwich layer, can effectively form the fast transport passage of electronics, be conducive to the right quick separation in light induced electron-hole in dye molecule, accelerate the electronic conduction ability of whole process, be conducive to the raising of the photoelectric conversion efficiency of DSSC.Similar NaCo 2o 4sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2) or Bi 2(GeSe) 3thermoelectric material also can, as the core material of coaxial nano cable, obtain smooth anode of the present invention.
A preparation method for dye-sensitized solar cell anode, comprises the following steps:
Step 1: by the commercially available polyvinylpyrrolidone of 4g (PVP), the commercially available nano-TiO of 4g 2particle adds in 160g ethanol solution, then add 0.05g calgon as surfactant to improve TiO 2the dispersiveness of nano particle, ultrasonic agitation 30min, to dissolving, is then placed in 60 ℃ of insulating boxs and reacts 1h, obtains TiO 2/ PVP shell layer spinning solution;
Step 2: 0.1g PAN (polyacrylonitrile) is dissolved in 1.56g DMF (dimethyl formamide) solution and stirs 2h, make PAN solution.Get the above-mentioned PAN solution of 4mL, and add 54.62mg sodium acetate and 200mg cobalt acetate, through magnetic agitation 2h, it is fully dissolved, obtain NaCo 2o 4/ PAN sandwich layer spinning solution;
Step 3:(TiO 2/ PVP)/(NaCo 2o 4/ PAN) preparation of directed coaxial composite fibre: adopt cylinder coaxial electrostatic spinning silk device preparation (TiO as shown in Figure 3 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre, cylinder coaxial electrostatic spinning silk device adopts coaxial nozzle and cylinder receiving screen.Cylinder coaxial electrostatic spinning silk device is shown in Fig. 3, mainly by high voltage source 1, and interior liquid storage container 2, outer liquid storage container 3, inner nozzle 4, outer nozzle 5, cylinder receiving screen 6, motor 7 forms.Wherein interior outer nozzle is inside and outside two the stainless steel tubules that are nested together, and has formed coaxial nozzle.Wherein, inner nozzle 4 diameters are 0.7mm, and outer nozzle 5 diameters are 1.2mm, and inner nozzle mouth is jet hole top 0.5mm outside, and in regulating, the gap of outer nozzle can be flowed out smoothly to guarantee sandwich layer solution.By (the NaCo preparing 2o 4/ PAN) sandwich layer spinning solution adds in interior liquid storage container 2, by (TiO 2/ PVP) shell layer spinning solution adds in outer liquid storage container 3, then between sandwich layer 2 shell 3 solution and cylinder receiving screen 6, applies the voltage of 18kV, and wherein positive pole connects sandwich layer solution and shell solution, and negative pole connects cylinder receiving screen.Positive electric field is added on sandwich layer 2 and shell 3 solution, the sandwich layer 2 spraying from the nozzle of inside and outside two coaxial but different-diameters and the liquid of shell 3 form concentric stratified flow, and ejection in 4 and 5 from nozzle separately respectively, along with solvent evaporates, spray after thread solidifies rapidly and form (TiO 2/ PVP)/(NaCo 2o 4/ PAN) composite fibre, sprays (the TiO that thread solidify to form 2/ PVP)/(NaCo 2o 4/ PAN) composite fibre be take the form of circumference and is attached on the aluminium foil of the cylinder receiving screen that rotating speed is 1250r/min, and wherein the distance of 6 of outer nozzle 5 and cylinder receiving screens is 15cm, thereby obtains (TiO 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre;
Step 4:TiO 2/ NaCo 2o 4the preparation of coaxial nano cable: first apply commercially available P25 colloidal tio 2 at FTO conductive glass surface; Then (TiO step 3 being obtained 2/ PVP)/(NaCo 2o 4/ PAN) aluminium foil that directed coaxial composite fibre is accepted screen from cylinder is torn, cutting and the equirotal (TiO of titanium dioxide nanocrystalline film 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre, vertically adhere on the titanium dioxide nanocrystalline film on FTO electro-conductive glass, and be positioned in Muffle furnace, after being warming up to 500 ℃ with 1 ℃/min heating rate, keep 2h, naturally cool to room temperature, obtain being attached to the TiO of titanium dioxide nanocrystalline film surface on FTO electro-conductive glass 2/ NaCo 2o 4coaxial nano cable, then 2 * 10 -4in the N719 solution of mol/L, soak 24h, absorption N719 dye molecule obtains described smooth anode.
The dye-sensitized solar cell anode of above-mentioned preparation is become to battery with the transparent conducting glass of iodine/lithium iodide electrolyte and platinum plating to electrode assembling, and carry out photoelectric properties test.The effective area of the battery that in experiment, assembling obtains is 0.64cm 2.In Fig. 4, solid line is that embodiment 1 assembles the photoelectric current voltage curve of the DSSC obtaining.In Fig. 4, solid line is known, and the short-circuit current density of dye sensitization of solar light anode cell is 16.03mA/cm 2, open circuit voltage is 0.71V, and fill factor, curve factor is 0.564, and electricity conversion is 6.43%,
Comparative example
Adopt commercially available P25 colloidal tio 2 similarly to Example 1 to prepare the nanocrystalline smooth anode of ordinary titanium dioxide, and with the electro-conductive glass of iodine/lithium iodide electrolyte and platinum plating, electrode assembling is become to battery, carry out photoelectric properties test.The battery effective area that in experiment, assembling obtains is 0.64cm 2.Its test result is as shown in the dotted line in Fig. 4, and can calculate and adopt the short-circuit current density of the nanocrystalline smooth anode cell of used by dye sensitization solar battery ordinary titanium dioxide described in comparative example is 14.32mA/cm 2, open circuit voltage is 0.70V, and fill factor, curve factor is 0.561, and electricity conversion is 5.67%.Visible, adopt the short circuit current of the battery of dye-sensitized solar cell anode structure provided by the invention to improve 11.9%, electricity conversion has improved 13.4%.

Claims (4)

1. a dye-sensitized solar cell anode, comprise electro-conductive glass (8), be positioned at the titanium dioxide nanocrystalline film (9) on electro-conductive glass (8), be positioned at absorption on titanium dioxide nanocrystalline film (9) coaxial nano cable of dyestuff (10), described coaxial nano cable is vertically to adhere on titanium dioxide nanocrystalline film (9), described coaxial nano cable be align and the degree of order be 60%～100%, the shell of described coaxial nano cable is crystalline state TiO 2, sandwich layer is NaCo 2o 4, Sb 2te 3, Bi 2te 3, HgTe, Bi 2se 3, ZnSb, SbTe, PbTe, Bi (SiSb 2), Bi 2(GeSe) 3in a kind of.
2. a preparation method for dye-sensitized solar cell anode, comprises the following steps:
Step 1: prepare colloidal tio 2;
Step 2: prepare (TiO 2/ PVP) shell layer spinning solution and (NaCo 2o 4/ PAN) sandwich layer spinning solution: first add polyvinylpyrrolidone and nano-TiO in absolute ethyl alcohol 2particle, wherein polyvinylpyrrolidone, absolute ethyl alcohol, nano-TiO 2the mass ratio of particle is 1:40:1, and then stirring and dissolving adds the calgon of 0.03%～0.06% mass percent, ultrasonic dissolution, and react 1h under 50 ℃～100 ℃ conditions, obtain (TiO 2/ PVP) shell layer spinning solution; The DMF solution that preparation PAN quality percentage composition is 6.4wt%, obtains PAN solution, then in PAN solution, adds sodium acetate and cobalt acetate, wherein, the mass ratio of sodium acetate, cobalt acetate and PAN solution is 0.27:1:1.35, through magnetic agitation, dissolves, and obtains (NaCo 2o 4/ PAN) sandwich layer spinning solution;
Step 3:(TiO 2/ PVP)/(NaCo 2o 4/ PAN) preparation of directed coaxial composite fibre: first by (NaCo 2o 4/ PAN) sandwich layer spinning solution adds in interior liquid storage container (2), by (TiO 2/ PVP) shell layer spinning solution adds in outer liquid storage container (3), then between sandwich layer (2) shell (3) solution and cylinder receiving screen (6), apply the voltage of 10～35kV, wherein positive pole connects sandwich layer solution and shell solution, negative pole connects cylinder receiving screen, the surface tension that sandwich layer (2) and shell (3) solution overcome self under the effect of electric field forms the ejection from inner nozzle (4) and outer nozzle (5) respectively of injection thread, along with the volatilization of solvent, spray thread and solidify to form (TiO 2/ PVP)/(NaCo 2o 4/ PAN) composite fibre, sprays (the TiO that thread solidify to form 2/ PVP)/(NaCo 2o 4/ PAN) composite fibre be take the form of circumference and is attached on the aluminium foil on the cylinder receiving screen that rotating speed is 700r/min～1250r/min, and wherein the distance between outer nozzle (5) and cylinder receiving screen (6) is 5～25cm, thereby obtains (TiO 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre;
Step 4:TiO 2/ NaCo 2o 4the preparation of coaxial nano cable: the colloidal tio 2 of first preparing in electro-conductive glass (8) surface-coated step 1; Then (TiO step 3 being obtained 2/ PVP)/(NaCo 2o 4/ PAN) aluminium foil that directed coaxial composite fibre is accepted screen from cylinder is torn, and cutting area is not higher than the (TiO of titanium dioxide nanocrystalline film size 2/ PVP)/(NaCo 2o 4/ PAN) directed coaxial composite fibre, vertically adhere on the titanium dioxide nanocrystalline film on electro-conductive glass, and be positioned in Muffle furnace, after being warming up to 500 ℃～900 ℃ with 1～5 ℃/min heating rate, keep 2～24h, naturally cool to room temperature, obtain being attached to the TiO of titanium dioxide nanocrystalline film surface on electro-conductive glass 2/ NaCo 2o 4coaxial nano cable, then adsorpting dye molecule obtains described smooth anode.
3. the preparation method of dye-sensitized solar cell anode according to claim 2, is characterized in that, colloidal tio 2 described in step 1 is commercially available P25 colloidal tio 2.
4. the preparation method of dye-sensitized solar cell anode according to claim 2, is characterized in that, inner nozzle described in step 3 (4) diameter is 0.1～0.7mm, and outer nozzle (5) diameter is 0.5～1.2mm.
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