CN104485230A - Novel counter electrode for dye-sensitized solar cell and preparation method thereof - Google Patents
Novel counter electrode for dye-sensitized solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a novel counter electrode for a dye-sensitized solar cell and a preparation method thereof. The novel counter electrode is characterized in that a conductive substrate in the counter electrode is coated with an electrocatalytic layer and a light scattering layer in sequence, wherein the electrocatalytic layer comprises one of a carbon composite material, a platinum-like material and platinum; the light scattering layer comprises zirconium oxide and/or titanium oxide.
Description
Technical field
The present invention relates to DSSC Material Field, particularly relate to a kind of novel low-cost for DSSC to electrode and preparation method thereof.
Background technology
After entering 21st century, traditional silicon solar cell progressively enters practical stage, but such solar cell still also also exists production equipment and complex manufacturing technology, easily causes the problem such as secondary environmental pollution and energy consumption height.Thus send out environmental protection a kind of, the novel solar battery of low cost become research topic very important at present.There is due to DSSC (DSSC) features such as theoretical conversion efficiencies is high, preparation technology simple, environmental friendliness, become the extensive concern one class solar cell by academia and industrial circle.In addition, it is high that DSSC has energy conversion efficiency under the low light level, affects less by the factor such as ambient temperature and incident angle of light, can be made into the advantages such as flexibility, colorful, artistic and translucent battery.Therefore, DSSC is that one has good market potential, is expected the novel solar battery realizing industrialization.
At present, the industrialization of DSSC also also exist that energy conversion efficiency is lower, material cost is high and long durability can be poor etc. problem.Therefore, be only improved the energy conversion efficiency of battery, reduce the material cost of DSSC and improve the stability of battery, DSSC just can be made to occupy one seat in solar cell market with keen competition.
In order to solve the bottleneck problem that above-mentioned DSSC develops, there is the upsurge researched and developed for the low-cost counter electrode of DSSC in recent years.Traditional to electrode material-noble metal platinum (Pt) by substituting with the electrocatalysis material of low cost, the material cost of DSSC can be reduced; By optimizing the component of lower cost materials and the preparation technology to electrode, the electro catalytic activity of low-cost counter electrode can be improved, make its electrocatalysis characteristic be better than conventional P t electrode; By using not easily by the material of iodine electrolytic corrosion (Pt there will be situation about being corroded in iodine electrolyte), the endurance quality of DSSC can be improved.But, low-cost counter electrode has also occurred that in application process some are needed badly and has dealt with problems: this type of electrode mostly not light scattering or light scattering difference of tool, in order to improve the utilance of DSSC to light, light scattering layer must be printed on light anode, and on light anode, print light scattering layer not only can affect dye sensitization process, also can promote the increase of dark current, the opto-electronic conversion performances such as the short circuit current (Jsc) of final battery, open circuit voltage (Voc) and photoelectric conversion efficiency (η) decline; In addition, the conductive material in electrode is in use had to the situation (when especially using flexibility to electrode basement) come off, this can cause internal short-circuit of battery, and durability is deteriorated.
Therefore, the performance how improving DSSC is a kind of important research direction of those skilled in the art all the time.
Summary of the invention
The present invention is intended to the performance parameter promoting DSSC further, the invention provides a kind of for DSSC to electrode and preparation method thereof.
The invention provides a kind of for DSSC to electrode, describedly be coated with Electrocatalytic Layer and light scattering layer successively in conductive substrates in electrode, wherein, the composition of Electrocatalytic Layer comprise carbon composite, class alloy platinum material, platinum, at least one, the composition of light scattering layer comprises zirconia and/or titanium oxide.
Preferably, the composition of Electrocatalytic Layer is not separately platinum.
Preferably, the material of conductive substrates comprises metal, metal nitride, conductive oxide or has the macromolecular material of conductivity.
Preferably, carbon composite comprises the meso-porous carbon material that meso-porous carbon material and/or load have carbide, and wherein, meso-porous carbon material comprises at least one in carbon fiber, colour black, carbon nano-tube, carbon nanohorn, carbon nano rod, carbon ball; Carbide comprises at least one in niobium carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, vanadium carbide, carbonization key, ramet.
Preferably, class alloy platinum material comprises at least one in molybdenum nitride, tantalum nitride, vanadium nitride, niobium nitride, zirconium nitride, chromium nitride, tungsten nitride.
Preferably, the thickness of Electrocatalytic Layer is 5 ~ 50 μm, and the thickness of light scattering layer is 1 ~ 10 μm.
Again, present invention also offers a kind of above-mentioned preparation method to electrode, described preparation method comprises:
1) constitutive material of described Electrocatalytic Layer, binding agent, viscosity modifier and solvent is taken, obtained Electrocatalytic Layer slurry after Homogeneous phase mixing;
2) constitutive material of described light scattering layer, viscosity modifier and solvent is taken, obtained light scattering layer slurry after Homogeneous phase mixing;
3) by step 1) the Electrocatalytic Layer slurry prepared and step 2) the light scattering layer slurry prepared is coated on successively in conductive substrates, obtains electrode biscuit, wherein, dry after each slurry coating through heat treatment;
4) by step 3) prepare to electrode biscuit, at 150-550 DEG C calcining obtain described to electrode.
Preferably, step 1) and step 2) in, Homogeneous phase mixing comprises each for slurry component mixing, it is made to mix through homogenate dispersion process, wherein, homogenate dispersion process comprise in magnetic agitation, ball milling, high shear, ultrasonic disperse one or more, the homogenate dispersion process of Electrocatalytic Layer slurry is 10 ~ 24 hours, and the homogenate dispersion process of light scattering layer slurry is 5-12 hour.
Preferably, described binding agent is titanium oxide, zirconia and/or tin oxide, this binding agent raw material is selected from least one in titania powder, TiO 2 sol, Zirconium dioxide powder, zirconia sol, tin ash powder, tin ash colloidal sol, and in described powder or colloidal sol, the particle diameter of solute is 10 ~ 400nm; Viscosity modifier comprises at least one in the derivative of cellulose, cellulosic salt, cellulosic derivative, starch, the salt of starch, starch; Solvent comprises alcohol and/or terpenoid.
Preferably, Electrocatalytic Layer slurry comprises Electrocatalytic Layer constitutive material, 1 ~ 30wt% binding agent, 1 ~ 30wt% viscosity modifier and the 10 ~ 95wt% solvent that 0.3 ~ 30wt% is made up of at least one in carbon composite, class alloy platinum material, platinum, and each percentage composition is 100%; Painting method comprises silk screen printing, the printing of steel version, rod painting method, scraper coating process, spin-coating method and/or spraying process.
Preferably, light scattering layer slurry comprises 10 ~ 30wt% light scattering layer constitutive material, 5 ~ 30wt% viscosity modifier and 40 ~ 85wt% solvent, and each percentage composition is 100%; Painting method comprises silk screen printing, the printing of steel version, rod painting method, scraper coating process, spin-coating method and/or spraying process.
Preferably, the temperature that heat treatment is dried is 60 ~ 150 DEG C, and baking duration is 1 ~ 20 minute.
Preferably, calcine at 200-550 DEG C, calcination time is 5 ~ 60 minutes.
Beneficial effect of the present invention:
(1) novel low-cost of the present invention's proposition is to electrode and preparation method thereof, can realize the low platinum of DSSC to electrode, even without platinum preparation, the material cost of DSSC is reduced;
(2) novel low-cost of the present invention's proposition is to electrode and preparation method thereof, imparting can not only be made electrode scattering, the function that reflects the incident light, and more electrolyte can be packed in light scattering layer, be of value to and promote (to be generally I to electrode electrical catalyze reduction oxidation state electrolyte
3 -);
(3) novel low-cost mentioned of the present invention is to electrode and preparation method thereof, the preparation technology of DSSC light anode can not only be simplified, namely without the need to printing light scattering layer on light anode, but also the present invention the probability of photoanode surface back of the body reaction can be reduced, because can avoid light scattering layer at the too much electrolyte of photoanode surface enrichment;
(4) novel low-cost mentioned of the present invention is to electrode and preparation method thereof, the opto-electronic conversion performances such as the open circuit voltage (Voc) of battery, short circuit current (Jsc), fill factor, curve factor (FF), inside battery parallel resistance (Rsh) and photoelectric conversion efficiency (η) can not only be improved, can also avoid coming off to the electric conducting material on electrode, cause internal short-circuit of battery or parallel resistance on the low side.
Accompanying drawing explanation
Fig. 1 show utilize embodiment 1 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 2 show utilize embodiment 2 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 3 show utilize embodiment 3 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 4 show utilize embodiment 4 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 5 show utilize embodiment 5 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 6 show utilize comparative example 1 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 7 show utilize comparative example 2 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 8 show utilize comparative example 3 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Fig. 9 show utilize comparative example 4 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Figure 10 show utilize comparative example 5 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition;
Figure 11 show utilize comparative example 6 obtained the battery that electrode is assembled at AMl.5, I000W/m
2the 1-V curve recorded under standard test condition.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that accompanying drawing and following execution mode are only for illustration of the present invention, and unrestricted the present invention.
In order to solve the problem that above-mentioned obstruction low-cost counter electrode is applied in DSSC, the invention provides a kind of novel low-cost for DSSC to electrode and preparation method thereof, to prepare the low cost DSSC of high-photoelectric transformation efficiency, high-durability, DSSC production technology can also be made to be simplified, to be easy to realize.
The invention provides a kind of novel low-cost for DSSC to electrode and preparation method thereof.This comprises the Electrocatalytic Layer be made up of lower cost materials and the light scattering layer with light scattering function to electrode.This comprises the preparation process of electrode and is 1. coated in conductive substrates by the slurry containing Low-cost electric catalysis material, 2. the slurry containing Low-cost electric catalysis material is dried in heat treatment, 3. the slurry containing light-scattering material is coated on Electrocatalytic Layer, 4. the slurry containing light-scattering material is dried in heat treatment, 5. the electrode that 4. step obtains is heat-treated oven dry or high-temperature calcination, described in obtained this patent to electrode.
Described Low-cost electric catalysis material is the mixture of a kind of carbon composite, class alloy platinum material or more than one class alloy platinum material, or the mixture of carbon composite, class alloy platinum material and platinum (Pt).
Carbon composite is a kind of meso-porous carbon material, or load has the meso-porous carbon material of carbide.
Described carbide is one in niobium carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, vanadium carbide, carbonization key, ramet or its mixture.
Described class alloy platinum material comprises one in molybdenum nitride, tantalum nitride, vanadium nitride, niobium nitride, zirconium nitride, chromium nitride, tungsten nitride or its mixture.
This light-scattering material is made up of zirconia, titanium dioxide or mixture.
Step 1. and 3. mentioned painting method comprises silk screen printing, steel version is printed, rod is coated with method, scraper coating process, spin-coating method and spraying process etc.
The described slurry containing Low-cost electric catalysis material, the preparation of this slurry is mixed each component, then makes it mix through the homogenate dispersion process of 10 ~ 24 hours.Homogenate dispersion process is by magnetic agitation, and ball milling, high shear, one or more in ultrasonic disperse carry out.
The described slurry containing light-scattering material, the preparation of this slurry is mixed each component, then makes it mix through the homogenate dispersion process of 5 ~ 12 hours.Homogenate dispersion process is by centrifugal, magnetic agitation, and ball milling, high shear, one or more in ultrasonic disperse carry out.
The described slurry containing Low-cost electric catalysis material, containing 0.3 ~ 30wt% Low-cost electric catalysis material, 1 ~ 30wt% binding agent, 1 ~ 30wt% viscosity modifier and 10 ~ 95wt% solvent in this slurry.
The described slurry containing light-scattering material, containing 10 ~ 30wt% light-scattering material, 5 ~ 30wt% viscosity modifier and 40 ~ 85wt% solvent in this slurry.
This binding agent is titania powder and/or its colloidal sol, or Zirconium dioxide powder and/or its colloidal sol, or tin ash powder and/or its colloidal sol, or the mixture of above-mentioned binding agent; The particle diameter of described binding agent is 10 ~ 400nm.
This viscosity modifier is cellulose and/or its salt and/or its derivative; Starch and or its salt or derivatives thereof.
This solvent is alcohols, as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, ethylene glycol, propylene glycol, phenmethylol etc.; Or terpenoid, as borneol, isoborneol, thatch ketone, borneol, thatch alkane, menthones, menthol, terpinol etc.; Or N-methyl--pyrrolidones (NMP) and derivative thereof.
The temperature of the heat treatment oven dry that step is 2., 4. and 5. mentioned is 60 ~ 150 DEG C, and baking duration is 1 ~ 20min.
Step 5. in the temperature of high-temperature calcination be 200 ~ 550 DEG C, calcination time is 5 ~ 60min.
This base material can be metal or metal nitride or conductive oxide or has the macromolecular material of conductivity.
The thickness of this Electrocatalytic Layer is 5 ~ 50 μm.
The thickness of this light scattering layer is 1 ~ 10 μm.
The advantages such as this kind is compared with platinum (Pt) electrode in traditional DSSC electrode, has cost low, and electrocatalysis characteristic is excellent, easy production; Compare with traditional low-cost counter electrode, there is excellent light scattering property, can alleviate and electrode material is come off to electrode, cause internal short-circuit of battery or parallel resistance (Rsh) on the low side, the technique of printing light scattering layer on light anode can also be saved simultaneously, there are better market prospects.The present invention is DSSC, especially brand-new thinking is provided to the preparation of electrod assembly and structure optimization, technical scheme of the present invention is easy to realize, battery cost can be reduced, improve the opto-electronic conversion performances such as the open circuit voltage (Voc) of battery, short circuit current (Jsc), fill factor, curve factor (FF) and photoelectric conversion efficiency (η).
The specific experiment step of the performance to electrode of test mentioned by the present invention is as follows:
The preparation of the smooth anode of step one:
Titania slurry to be screen-printed on FTO (as with the low-cost counter electrode assembled battery without light scattering layer, light anode also needs print additional one deck light scattering layer), Muffle furnace 510 DEG C calcining 30 minutes, takes out after being cooled to room temperature;
The sensitization of step 2 light anode
The FTO being printed on titanium dioxide film is placed in ready dye solvent, and dye solvent is DMSO or acetonitrile/tert-butyl alcohol (volume mixture ratio the is 1:1) mixed solvent of Z991.Soak 24 ~ 48h to take out, light anode after obtained sensitization;
The assembling of step 3 battery
What having of being mentioned with the present invention respectively by the light anode after sensitization was mentioned in the low-cost counter electrode of light scattering layer and comparative example uses adhesive to fit to electrode, and inject electrolyte from hand-hole afterwards, electrolyte is conventional iodin-containing liquid body electrolyte.Use thin glass sheet seals the electrolyte injecting hole on titanium plate afterwards, obtained battery;
Step 4 cell photoelectric conversion performance is tested
Test battery each opto-electronic conversion performance parameter under AMl.5 simulated solar irradiation.
Beneficial effect of the present invention:
(1) novel low-cost of the present invention's proposition is to electrode and preparation method thereof, can realize the low platinum of DSSC to electrode, even without platinum preparation, the material cost of DSSC is reduced;
(2) novel low-cost of the present invention's proposition is to electrode and preparation method thereof, imparting can not only be made electrode scattering, the function that reflects the incident light, and more electrolyte can be packed in light scattering layer, be of value to and promote (to be generally I to electrode electrical catalyze reduction oxidation state electrolyte
3 -);
(3) novel low-cost mentioned of the present invention is to electrode and preparation method thereof, the preparation technology of DSSC light anode can not only be simplified, namely without the need to printing light scattering layer on light anode, but also the present invention the probability of photoanode surface back of the body reaction can be reduced, because can avoid light scattering layer at the too much electrolyte of photoanode surface enrichment;
(4) novel low-cost mentioned of the present invention is to electrode and preparation method thereof, the opto-electronic conversion performances such as the open circuit voltage (Voc) of battery, short circuit current (Jsc), fill factor, curve factor (FF), inside battery parallel resistance (Rsh) and photoelectric conversion efficiency (η) can not only be improved, can also avoid coming off to the electric conducting material on electrode, cause internal short-circuit of battery or parallel resistance on the low side.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned execution mode that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following technological parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1:
(1) preparation of the slurry containing Low-cost electric catalysis material:
20g carbon fiber, 5g carbon nanohorn powder and 5g vanadium nitride powder are mixed, add 15g particle diameter 30nm titania powder afterwards, with 20g ethyl cellulose, after suitable mixing, add 100g N-methyl--pyrrolidones (NMP), centrifugal mixing 30min, then ball milling mixing 12h obtains the slurry of Low-cost electric catalysis material;
(2) preparation of the slurry containing light-scattering material:
By 10g 200nm titania powder and the mixing of 10g 200nm Zirconium dioxide powder, add 10g ethyl cellulose afterwards, suitably after mixing, add 100g terpinol, centrifugal mixing 30min, then ball milling mixing 10h obtains the slurry of light-scattering material;
(3) preparation of conductive substrates (TiN plate):
TiN plate is used respectively deionized water and acetone ultrasonic cleaning 25min, the TiN plate after ultrasonic cleaning is dried up, stand-by;
(4) the slurry coating of Low-cost electric catalysis material:
Utilize in silk screen print method TiN substrate after cleaning and apply Low-cost electric catalysis material slurry, dry 5min at 150 DEG C, obtain the Electrocatalytic Layer that thickness is 25 μm;
(5) coating of light-scattering material slurry:
Utilize scraper cladding process to apply light-scattering material slurry on the Electrocatalytic Layer obtained by step (4), at 110 DEG C, dry 5min, obtain the light scattering layer that thickness is 5 μm;
(6) heat treatment of low-cost counter electrode is dried:
5min is dried in electrode obtained for step (5) heat treatment at 150 DEG C, the obtained low-cost counter electrode with light scattering function described in this patent.
Embodiment 2:
(1) preparation of the slurry containing Low-cost electric catalysis material:
By 20g carbon fiber, the mixing of 5g colour carbon black powder, add 15g particle diameter 200nm titania powder afterwards, and 30g ethyl cellulose, after suitable mixing, add 300g terpinol, centrifugal mixing 30min, then ball milling mixing 12h obtains the slurry of Low-cost electric catalysis material;
(2) preparation of the slurry containing light-scattering material:
After 20g 400nm titania powder and the mixing of 10g ethyl cellulose, add 100g terpinol, high shear mixing 30min, then ball milling mixing 5h obtains the slurry of light-scattering material;
(3) preparation of conductive substrates (Ti paper tinsel):
Ti paper tinsel is used respectively deionized water and acetone ultrasonic cleaning 25min, the Ti paper tinsel after ultrasonic cleaning is dried up, stand-by;
(4) the slurry coating of Low-cost electric catalysis material:
Utilize in silk screen print method Ti paper tinsel substrate after cleaning and apply Low-cost electric catalysis material slurry, dry 10min at 110 DEG C, obtain the Electrocatalytic Layer that thickness is 20 μm;
(5) coating of light-scattering material slurry:
Utilize scraper cladding process to apply light-scattering material slurry on the Electrocatalytic Layer obtained by step (4), at 110 DEG C, dry 5min, obtain the light scattering layer that thickness is 5 μm;
(6) calcination processing of low-cost counter electrode:
The electrode that step (5) is obtained calcines 25min at 450 DEG C, the obtained low-cost counter electrode with light scattering function described in this patent.
Embodiment 3:
(1) preparation of the slurry containing Low-cost electric catalysis material:
By 20g carbon fiber, the mixing of 5g tantalum carbide powder, add 15g particle diameter 200nm titania powder afterwards, with 30g ethyl cellulose, after suitable mixing, add 300g N-methyl--pyrrolidones (NMP), centrifugal mixing 30min, then ball milling mixing 15h obtains the slurry of Low-cost electric catalysis material;
(2) preparation of the slurry containing light-scattering material:
After 20g 200nm titania powder and the mixing of 10g ethyl cellulose, add 200g terpinol, high shear mixing 30min, then ball milling mixing 3h obtains the slurry of light-scattering material;
(3) preparation of conductive substrates (FTO):
FTO is used respectively deionized water and acetone ultrasonic cleaning 25min, the FTO after ultrasonic cleaning is dried up, stand-by;
(4) the slurry coating of Low-cost electric catalysis material:
Utilize in spin-coating method FTO conduction after cleaning and apply Low-cost electric catalysis material slurry, dry 10min at 150 DEG C, obtain the Electrocatalytic Layer that thickness is 7 μm;
(5) coating of light-scattering material slurry:
Utilize spin-coating method to apply light-scattering material slurry on the Electrocatalytic Layer obtained by step (4), at 150 DEG C, dry 5min, obtain the light scattering layer that thickness is 5 μm;
(6) heat treatment of low-cost counter electrode is dried:
Electrode obtained for step (5) heat treatment at 150 DEG C is dried, the obtained low-cost counter electrode with light scattering function described in this patent.
Embodiment 4:
(1) preparation of the slurry containing Low-cost electric catalysis material:
By 20g carbon fiber, the mixing of 5g colour carbon black powder, add 15g particle diameter 200nm titania powder afterwards, with 30g ethyl cellulose, after suitable mixing, add 10mL 10wt% platinum acid chloride solution and 90g terpinol, centrifugal mixing 30min, then ball milling mixing 24h obtains the slurry of Low-cost electric catalysis material;
(2) preparation of the slurry containing light-scattering material:
After 20g 400nm Zirconium dioxide powder and the mixing of 15g ethyl cellulose, add 200g terpinol, high shear mixing 30min, then ball milling mixing 2h obtains the slurry of light-scattering material;
(3) preparation of conductive substrates (Ti paper tinsel):
Ti paper tinsel is used respectively deionized water and acetone ultrasonic cleaning 20min, the Ti paper tinsel after ultrasonic cleaning is dried up, stand-by;
(4) the slurry coating of Low-cost electric catalysis material:
Utilize in silk screen print method Ti paper tinsel substrate after cleaning and apply Low-cost electric catalysis material slurry, dry 10min at 110 DEG C, obtain the Electrocatalytic Layer that thickness is 30 μm;
(5) coating of light-scattering material slurry:
Utilize spin-coating method to apply light-scattering material slurry on the Electrocatalytic Layer obtained by step (4), at 110 DEG C, dry 10min, obtain the light scattering layer that thickness is 2 μm;
(6) calcination processing of low-cost counter electrode:
The electrode that step (5) is obtained calcines 60min at 400 DEG C, the obtained low-cost counter electrode with light scattering function described in this patent.
Embodiment 5:
(1) preparation of the slurry containing Low-cost electric catalysis material:
20g colour carbon black powder 15g particle diameter 200nm titania powder is mixed, after suitably mixing with 30g ethyl cellulose, add 10mL 5wt% platinum acid chloride solution and 90g terpinol, high shear mixing 30min, then ball milling mixing 10h obtains the slurry of Low-cost electric catalysis material;
(2) preparation of the slurry containing light-scattering material:
After 20g 400nm Zirconium dioxide powder and the mixing of 15g ethyl cellulose, add 100g terpinol, centrifugal mixing 90min, then ball milling mixing 2h obtains the slurry of light-scattering material;
(3) preparation of conductive substrates (Ti plate):
Ti plate is used respectively deionized water and acetone ultrasonic cleaning 20min, the Ti paper tinsel after ultrasonic cleaning is dried up, stand-by;
(4) the slurry coating of Low-cost electric catalysis material:
Utilize in silk screen print method Ti plate substrate after cleaning and apply Low-cost electric catalysis material slurry, dry 10min at 110 DEG C, obtain the Electrocatalytic Layer that thickness is 35 μm;
(5) coating of light-scattering material slurry:
Utilize steel mesh print process to apply light-scattering material slurry on the Electrocatalytic Layer obtained by step (4), at 110 DEG C, dry 10min, obtain the light scattering layer that thickness is 8 μm;
(6) calcination processing of low-cost counter electrode:
The electrode that step (5) is obtained calcines 10min at 500 DEG C, the obtained low-cost counter electrode with light scattering function described in this patent.
Comparative example 1:
(1) preparation of the slurry containing Low-cost electric catalysis material:
With embodiment 1 step (1);
(2) preparation of conductive substrates (TiN plate):
With embodiment 1 step (3);
(3) the slurry coating of Low-cost electric catalysis material:
With embodiment 1 step (4);
(4) heat treatment of low-cost counter electrode is dried:
With embodiment 1 step (6).
Comparative example 2:
(1) preparation of the slurry containing Low-cost electric catalysis material:
With embodiment 2 step (1);
(2) preparation of conductive substrates (Ti paper tinsel):
With embodiment 2 step (3);
(3) the slurry coating of Low-cost electric catalysis material:
With embodiment 2 step (4);
(4) heat treatment of low-cost counter electrode is dried:
With embodiment 2 step (6).
Comparative example 3:
(1) preparation of the slurry containing Low-cost electric catalysis material:
With embodiment 3 step (1);
(2) preparation of conductive substrates (FTO):
With embodiment 3 step (3);
(3) the slurry coating of Low-cost electric catalysis material:
With embodiment 3 step (4);
(4) heat treatment of low-cost counter electrode is dried:
With embodiment 3 step (6).
Comparative example 4:
(1) preparation of the slurry containing Low-cost electric catalysis material:
With embodiment 4 step (1);
(2) preparation of conductive substrates (Ti paper tinsel plate):
With embodiment 4 step (3);
(3) the slurry coating of Low-cost electric catalysis material:
With embodiment 4 step (4);
(4) heat treatment of low-cost counter electrode is dried:
With embodiment 41 step (6).
Comparative example 5:
(1) preparation of the slurry containing Low-cost electric catalysis material:
With embodiment 5 step (1);
(2) preparation of conductive substrates (Ti plate):
With embodiment 5 step (3);
(3) the slurry coating of Low-cost electric catalysis material:
With embodiment 5 step (4);
(4) heat treatment of low-cost counter electrode is dried:
With embodiment 5 step (6).
Comparative example 6:
(1) preparation of conductive substrates (FTO):
With embodiment 3 step (3);
(1) Pt is to the magnetron sputtering of electrode:
Utilize magnetically controlled sputter method to sputter the high-purity platinum target of 99.99%, make its deposit thickness on FTO conducting surface reach 150 ~ 200nm, namely obtain Pt to electrode.
Effect example DSSC photoelectric properties are tested
Utilize obtained by embodiment 1 ~ 5 and comparative example 1 ~ 6 to electrode, make DSSC in accordance with the following steps and test the performance of respective battery.
The preparation of the smooth anode of step one:
Titania slurry to be screen-printed on FTO (as with the low-cost counter electrode assembled battery without light scattering layer, light anode also needs print additional one deck light scattering layer), Muffle furnace 510 DEG C calcining 30 minutes, takes out after being cooled to room temperature;
The sensitization of step 2 light anode
The FTO being printed on titanium dioxide film is placed in ready dye solvent, and dye solvent is DMSO or acetonitrile/tert-butyl alcohol (volume mixture ratio the is 1:1) mixed solvent of Z991.Soak 24 ~ 48h to take out, light anode after obtained sensitization;
The assembling of step 3 battery
What having of being mentioned with the present invention respectively by the light anode after sensitization was mentioned in the low-cost counter electrode of light scattering layer and comparative example uses adhesive to fit to electrode, and inject electrolyte from hand-hole afterwards, electrolyte is conventional iodin-containing liquid body electrolyte.Use thin glass sheet seals the electrolyte injecting hole on titanium plate afterwards, obtained battery;
Step 4 cell photoelectric conversion performance is tested
Test battery each opto-electronic conversion performance parameter under AMl.5 simulated solar irradiation.
Result shows:
As shown in Figure 1, the battery that electrode is assembled that embodiment 1 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.785V, and short circuit current (Jsc) is 17.49mA/cm
2, fill factor, curve factor (FF) is 70.62%, parallel resistance (Rsh) for 1967ohm and photoelectric conversion efficiency (η) be 9.69%;
As shown in Figure 2, the battery that electrode is assembled that embodiment 2 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.794V, and short circuit current (Jsc) is 17.36mA/cm
2, fill factor, curve factor (FF) is 69.60%, parallel resistance (Rsh) for 5328ohm and photoelectric conversion efficiency (η) be 9.60%;
As shown in Figure 3, the battery that electrode is assembled that embodiment 3 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.789V, and short circuit current (Jsc) is 17.15mA/cm
2, fill factor, curve factor (FF) is 71.45%, parallel resistance (Rsh) for 3891ohm and photoelectric conversion efficiency (η) be 9.67%;
As shown in Figure 4, the battery that electrode is assembled that embodiment 4 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.782V, and short circuit current (Jsc) is 17.68mA/cm
2, fill factor, curve factor (FF) is 71.24%, parallel resistance (Rsh) for 2156ohm and photoelectric conversion efficiency (η) be 9.84%;
As shown in Figure 5, the battery that electrode is assembled that embodiment 5 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.775V, and short circuit current (Jsc) is 17.28mA/cm
2, fill factor, curve factor (FF) is 71.82%, parallel resistance (Rsh) for 2798ohm and photoelectric conversion efficiency (η) be 9.61%.
As shown in Figure 6, the battery that electrode is assembled that comparative example 1 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.754V, and short circuit current (Jsc) is 17.28mA/cm
2, fill factor, curve factor (FF) is 71.61%, parallel resistance (Rsh) for 267ohm and photoelectric conversion efficiency (η) be 9.33%;
As shown in Figure 7, the battery that electrode is assembled that comparative example 2 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.759V, and short circuit current (Jsc) is 17.72mA/cm
2, fill factor, curve factor (FF) is 69.24%, parallel resistance (Rsh) for 79ohm and photoelectric conversion efficiency (η) be 9.31%;
As shown in Figure 8, the battery that electrode is assembled that comparative example 3 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.758V, and short circuit current (Jsc) is 17.37mA/cm
2, fill factor, curve factor (FF) is 69.86%, parallel resistance (Rsh) for 178ohm and photoelectric conversion efficiency (η) be 9.20%;
As shown in Figure 9, the battery that electrode is assembled that comparative example 4 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.762V, and short circuit current (Jsc) is 17.50mA/cm
2, fill factor, curve factor (FF) is 67.11%, parallel resistance (Rsh) for 115ohm and photoelectric conversion efficiency (η) be 8.95%;
As shown in Figure 10, the battery that electrode is assembled that comparative example 5 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.758V, and short circuit current (Jsc) is 17.08mA/cm
2, fill factor, curve factor (FF) is 69.74%, parallel resistance (Rsh) for 398ohm and photoelectric conversion efficiency (η) be 9.03%;
As shown in figure 11, the battery that electrode is assembled that comparative example 6 is obtained is utilized, at AMl.5, I000W/m
2under standard test condition, recording its open circuit voltage (Voc) is 0.756V, and short circuit current (Jsc) is 16.71mA/cm
2, fill factor, curve factor (FF) is 68.70%, parallel resistance (Rsh) for 3586ohm and photoelectric conversion efficiency (η) be 8.69%.
Table 1 is the data summarization of the corresponding battery performance of embodiment 1 ~ 5, and table 2 is the data summarization of the corresponding battery performance of comparative example 1 ~ 5, and table 3 is the data of the corresponding battery performance of comparative example 6.
The performance data of the corresponding battery of table 1 embodiment 1 ~ 5 gathers
The performance data of the corresponding battery of table 2 comparative example 1 ~ 5 gathers
The performance data of the corresponding battery of table 3 comparative example 6
| DSSCs | Voc[V] | Jsc[mA/cm 2] | FF[％] | Eff[％] | Rsh[ohm] |
| The corresponding battery of comparative example 6 | 0.756 | 16.71 | 68.70 | 8.69 | 3586 |
Above-mentioned data are contrasted, can find out:
Utilize novel low-cost mentioned by the present invention prepared by method for DSSC, with traditional Pt electrode compared and not only electrode cost is reduced, and the opto-electronic conversion performance of battery, comprise the opto-electronic conversion performances such as the open circuit voltage (Voc) of battery, short circuit current (Jsc), fill factor, curve factor (FF) and photoelectric conversion efficiency (η) and all have remarkable lifting, mainly owing to utilizing the novel low-cost mentioned by the present invention prepared by method to compare electrode with Pt electrode, there is better electrocatalysis characteristic; The electrolyte can filled in its porous laminated structure, this not only can promote the oxidationreduction in electrolyte electric to the reaction on electrode, and oxidationreduction electricity can also be suppressed the back of the body reaction on light anode;
Utilize novel low-cost mentioned by the present invention prepared by method for DSSC, with not printing comparing electrode of light scattering layer, the open circuit voltage (Voc) of battery, the opto-electronic conversion performances such as short fill factor, curve factor (FF) and photoelectric conversion efficiency (η) all have remarkable lifting, the function to electrode light scattering not only can be being given to printed on electrodes light scattering layer mainly due to battery, and light scattering layer also add the thickness to its porous laminated structure of electrode, can increase the electrolyte of filling in electrode porous layer accordingly, this can play and promote the oxidationreduction electricity in electrode By Electrolysis liquid the electric effect to back of the body reaction of oxidationreduction in reaction and suppression light anode.In addition, utilize novel low-cost mentioned by the present invention to electrode and preparation method thereof, can make on light anode without the need to printing additional light scattering layer, and then simplify light anode preparation technology, but also conductivity can be alleviated electrode material is come off the situation causing internal short-circuit or cell parallel resistance Rsh to reduce.
Claims (13)
1. one kind for DSSC to electrode, it is characterized in that, describedly be coated with Electrocatalytic Layer and light scattering layer successively in conductive substrates in electrode, wherein, the composition of Electrocatalytic Layer comprise carbon composite, class alloy platinum material, platinum, at least one, the composition of light scattering layer comprises zirconia and/or titanium oxide.
2. according to claim 1 to electrode, it is characterized in that, the composition of Electrocatalytic Layer is not separately platinum.
3. according to claim 1 and 2 to electrode, it is characterized in that, the material of conductive substrates comprises metal, metal nitride, conductive oxide or has the macromolecular material of conductivity.
4. according to arbitrary described to electrode in claim 1-3, it is characterized in that, carbon composite comprises the meso-porous carbon material that meso-porous carbon material and/or load have carbide, wherein, meso-porous carbon material comprises at least one in carbon fiber, colour black, carbon nano-tube, carbon nanohorn, carbon nano rod, carbon ball; Carbide comprises at least one in niobium carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, vanadium carbide, carbonization key, ramet.
5., according to arbitrary described to electrode in claim 1-4, it is characterized in that, class alloy platinum material comprises at least one in molybdenum nitride, tantalum nitride, vanadium nitride, niobium nitride, zirconium nitride, chromium nitride, tungsten nitride.
6., according to arbitrary described to electrode in claim 1-5, it is characterized in that, the thickness of Electrocatalytic Layer is 5-50 μm, and the thickness of light scattering layer is 1-10 μm.
7. an arbitrary described preparation method to electrode in claim 1-6, it is characterized in that, described preparation method comprises:
1) constitutive material of described Electrocatalytic Layer, binding agent, viscosity modifier and solvent is taken, obtained Electrocatalytic Layer slurry after Homogeneous phase mixing;
2) constitutive material of described light scattering layer, viscosity modifier and solvent is taken, obtained light scattering layer slurry after Homogeneous phase mixing;
3) the Electrocatalytic Layer slurry prepared by step 1) and step 2) the light scattering layer slurry prepared is coated on successively in conductive substrates, obtains electrode biscuit, wherein, dry after each slurry coating through heat treatment;
4) prepared by step 3) to electrode biscuit, at 150-550 DEG C calcining obtain described to electrode.
8. preparation method according to claim 7, it is characterized in that, step 1) and step 2) in, Homogeneous phase mixing comprises each for slurry component mixing, make it mix through homogenate dispersion process, wherein, homogenate dispersion process comprise in magnetic agitation, ball milling, high shear, ultrasonic disperse one or more, the homogenate dispersion process of Electrocatalytic Layer slurry is 10-24 hour, and the homogenate dispersion process of light scattering layer slurry is 5-12 hour.
9. the preparation method according to claim 7 or 8, it is characterized in that, described binding agent is titanium oxide, zirconia and/or tin oxide, this binding agent raw material is selected from least one in titania powder, TiO 2 sol, Zirconium dioxide powder, zirconia sol, tin ash powder, tin ash colloidal sol, and in described powder or colloidal sol, the particle diameter of solute is 10-400nm; Described viscosity modifier comprises at least one in the derivative of cellulose, cellulosic salt, cellulosic derivative, starch, the salt of starch, starch; Solvent comprises alcohol and/or terpenoid.
10. according to described preparation method arbitrary in claim 7-9, it is characterized in that, Electrocatalytic Layer slurry comprises Electrocatalytic Layer constitutive material, 1-30wt% binding agent, 1-30wt% viscosity modifier and the 10-95wt% solvent that 0.3-30wt% is made up of at least one in carbon composite, class alloy platinum material, platinum, and each percentage composition is 100%; Painting method comprises silk screen printing, the printing of steel version, rod painting method, scraper coating process, spin-coating method and/or spraying process.
11. according to described preparation method arbitrary in claim 7-10, and it is characterized in that, light scattering layer slurry comprises 10-30wt% light scattering layer constitutive material, 5-30wt% viscosity modifier and 40-85wt% solvent, and each percentage composition is 100%; Painting method comprises silk screen printing, the printing of steel version, rod painting method, scraper coating process, spin-coating method and/or spraying process.
12. according to described preparation method arbitrary in claim 7-11, and it is characterized in that, the temperature that heat treatment is dried is 60-150 DEG C, and baking duration is 1-20 minute.
13. according to described preparation method arbitrary in claim 7-12, and it is characterized in that, calcine at 200-550 DEG C, calcination time is 5-60 minute.
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