CN107785174B - Cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt are to electrode - Google Patents
Cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt are to electrode Download PDFInfo
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Abstract
The present invention relates to field of dye-sensitized solar cells, a kind of cobalt-based for dye-sensitized solar cells or the Ni-based sulfide photonic crystal of Ni-based or cobalt are disclosed to electrode, S1: monodisperse polystyrene bead is self-assembled to by constant temperature vertical deposition method and forms colloidal crystal on electro-conductive glass；S2: cobalt/nickel cobalt nickel deposition is filled into inside the colloidal crystal and obtains composite colloid crystal by electrochemical deposition method；S3: removing the polystyrene sphere in the composite colloid crystal, obtains cobalt or nickel or cobalt nickel photonic crystal；S4: sulphur source is introduced in the cobalt or nickel or cobalt nickel photonic crystal using hydro-thermal method, obtains cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt.The binding ability of cobalt or nickel or cobalt nickel photonic crystal and electro-conductive glass in the present invention is preferable, it is more to active site number in electrode, electrolyte diffusion fast speed, its work function matches preferably with electrolyte potential, higher to the dye-sensitized solar cells energy conversion efficiency of electrode with its work.
Description
Technical field
The present invention relates to dye-sensitized solar cells to electrode field, in particular to a kind of to be used for the dye sensitization sun
The cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt of energy battery are to electrode.
Background technique
As global energy crisis increasingly sharpens, solar energy is resourceful, widely distributed, environmentally friendly because having many advantages, such as,
As the research hotspot in energy field.Dye-sensitized solar cells (DSSC) possess higher theoretical energy transfer efficiency, at
This is low, simple process, it is environmental-friendly the features such as, as a kind of most promising one of photovoltaic power generation technology, receive wide
General concern.It is the indispensable important component of DSSC to electrode.Noble metal platinum has good electric conductivity and catalytic activity,
It is most common to electrode material.But that there are resources is limited, at high cost, in I for platinum-/ I- 3It is perishable equal scarce in electrolyte system
Point.Therefore, how to be had excellent performance, inexpensively, it is stable be always the academic problem faced with industry to electrode material.Hair
Exhibition has excellent performance, inexpensively, the stable hot research direction that DSSC is not only to electrode material, and it is new also to be compliant with China
The demand of material, new energy and the strategy of sustainable development.
In recent years, that has explored is broadly divided into four classes, i.e. carbon material, conducting polymer, compound (such as carbon to electrode material
Compound, nitride, oxide, sulfide, selenides) and alloy material (such as cobalt-nickel alloy, platinum alloy).All multipair electrode materials
Material has all shown good catalytic activity and electric conductivity.And what is had excellent performance will not only have high catalytic activity to electrode material
With strong electric conductivity, but also there is chemical stability, bigger serface and its work function and electrolyte potential to match characteristic.
This is because being to influence one of the principal element of DSSC stability on the dissolution of electrode, specific surface area affects electro catalytic activity position
Point number, work function and electrolyte potential matching properties also affect electrocatalysis characteristic.In all multipair electrode materials, sulfide
Not only with nano material shared characteristic, but also optics, in terms of also have property, be increasingly becoming energy
Storage and a research hotspot in converting material.In DSSC research, sulfide not only has at low cost, preparation work to electrode
Skill is simple, good chemical stability, but also shows and the comparable electrocatalysis characteristic of platinum electrode.But sulfide is to electricity
Still there is also critical issues not yet to solve for pole, as the electro catalytic activity of sulfide and its DSSC photoelectric properties of composition all need
It further increases.To solve these problems, it is necessary to deeper design construction and phenetic analysis sulfide nano-material.
In order to improve sulfide to the electrocatalysis characteristic of electrode, nanocrystalline, porous structure is probed into, hollow structure, has received
The cobalt-based or the Ni-based sulfide of Ni-based or cobalt of rice piece etc. different morphologies and object phase are to electrode.It is generally acknowledged that can there are mainly three types of mode
To improve cobalt-based or the Ni-based sulfide of Ni-based or cobalt to the electrocatalysis characteristic of electrode.The first is the catalytic activity increased to electrode
Number of loci.Under normal conditions, material specific surface area is bigger, and active site number is also more, to be conducive to mention
The catalytic activity of high material.Constructing porous structure in material internal and reduce material particle size to obtain nanocrystalline is to increase material ratio
Two kinds of important ways of surface area, such as: the synthesis of the nanocrystalline sulfides of NiS porous structure, NiS.Second is to improve electricity
Matter is solved to the diffusion velocity on electrode.It is generally acknowledged that electrolyte bigger to the diffusion velocity on electrode, more helps to improve
To the electro catalytic activity of electrode.And porous structure not only increases effective catalytic active area to electrode, and can be electrolysis
Matter provides diffusion duct, is conducive to the diffusion velocity for improving electrolyte, such as: CoNi2S4The vulcanization such as nanostructure, NiS nanometer sheet
The synthesis of object.The third is object phase, structure and surface topography of the design construction to electrode material, regulates and controls its work function.In DSSC
In, it is matched better with electrolyte potential to electrodes work functions, charge transmission resistance is more advantageously reduced, to improve to electrode
Electro catalytic activity.The work function of material can be typically expressed as the difference of vacuum level and fermi level, thus pass through construction material
Object phase, structure and surface topography, can Effective Regulation its work function.
By being analyzed above it is found that if effectively can just greatly improve cobalt-based or Ni-based or cobalt nickel in conjunction with these three modes
Electro catalytic activity of the base sulfide to electrode.And effective combination of first two mode is only realized currently with porous structure.Though
So obtain effectively mentioning compared with the battery efficiency based on platinum electrode based on DSSC energy conversion efficiency of the photonic crystal to electrode
Height, but there are also to be further improved for stability of the photonic crystal to electrode.Mainly since photonic crystal exists and conductive glass
Glass binding force is weaker, layer by layer between connect the problems such as poor, easy to fall off.This results in cobalt-based or the Ni-based vulcanization object light of Ni-based or cobalt
Sub- crystal obtains extensively and systematic research the application in electrode in DSSC not yet.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, the present invention provides a kind of for dye sensitization of solar electricity
The knot of the cobalt-based in pond or the Ni-based sulfide photonic crystal of Ni-based or cobalt to electrode, cobalt or nickel or cobalt nickel photonic crystal and electro-conductive glass
Conjunction ability is preferable, more to active site number in electrode, electrolyte diffusion fast speed, work function and electrolyte electricity
Position matching is preferably, higher to the dye-sensitized solar cells energy conversion efficiency of electrode with its work.
Technical solution: the present invention provides a kind of cobalt-based for dye-sensitized solar cells or the Ni-based sulphur of Ni-based or cobalt
Compound photonic crystal is to electrode, which is characterized in that the preparation method is as follows: S1: monodisperse polystyrene bead is hung down by constant temperature
Straight sedimentation, which self-assembles to, forms colloidal crystal on electro-conductive glass；S2: cobalt/nickel cobalt nickel is deposited by electrochemical deposition method
It is filled into inside the colloidal crystal and obtains composite colloid crystal；S3: removing the polystyrene sphere in the composite colloid crystal,
Obtain cobalt or nickel or cobalt nickel photonic crystal；S4: sulphur source is introduced in the cobalt or nickel or cobalt nickel photonic crystal using hydro-thermal method, obtains cobalt
Base or the Ni-based sulfide photonic crystal of Ni-based or cobalt.
Further, in the S4, the hydro-thermal method is the following steps are included: S4-1: configured urea liquid is turned
It moves in autoclave, and is put into the cobalt or nickel or cobalt nickel photonic crystal, 6 ~ 8h is reacted at a temperature of 110 DEG C ~ 130 DEG C,
After natural cooling respectively use deionized water and washes of absolute alcohol sample, vacuum dried sample, obtain basic cobaltous carbonate or nickel or
Cobalt nickel photonic crystal；S4-2: configured Sodium Sulphate Nine Hydroxide solution is transferred in autoclave, and is put into the alkali formula
Cobalt carbonate or nickel or cobalt nickel photonic crystal react 6 ~ 8h at a temperature of 150 DEG C ~ 170 DEG C, use deionization respectively after natural cooling
Water and washes of absolute alcohol sample, vacuum dried sample obtain the cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt.
Further, in the S4-1, in the urea liquid, the amount of the substance of urea is cobalt or nickel or cobalt nickel photon
2 ~ 4 times of the amount of the substance of crystal, the volume of the urea liquid are the 70% ~ 80% of autoclave volume.
Further, in the S4-2, in the Sodium Sulphate Nine Hydroxide solution, the amount of the substance of Sodium Sulphate Nine Hydroxide is
3 ~ 5 times of the amount of the substance of the basic cobaltous carbonate or nickel or cobalt nickel photonic crystal, the volume of the Sodium Sulphate Nine Hydroxide solution
It is the 70% ~ 80% of autoclave volume.
Further, in the S1, the constant temperature vertical deposition method is the following steps are included: S1-1: by the polyphenyl second
Alkene bead is scattered in formation colloid bead solution in solvent；S1-2: the colloid bead solution is heated to preset temperature, Xiang Qi
The middle insertion electro-conductive glass, and keep temperature constant, it slowly volatilizees to solvent completely, obtains the colloidal crystal；S1-3: by institute
It states colloidal crystal and is placed at 30 DEG C ~ 60 DEG C and 1 ~ 6h is dried；S1-4: at a temperature of 100 DEG C ~ 110 DEG C, to the glue
Body crystal carries out 1 ~ 5min of heat treatment.
Preferably, described in the colloid bead solution if the solvent is deionized water in the S1-1
The mass fraction of polystyrene sphere is 0.05wt% ~ 0.5wt%；If the solvent is dehydrated alcohol, in the colloid bead
In solution, the mass fraction of the polystyrene sphere is 0.5wt% ~ 2.0wt%.
Preferably, the particle size range of the polystyrene sphere is 200 ~ 800nm.
It preferably, is to add with thermostatic water bath if the partial size of the polystyrene sphere is less than 350nm in the S1-2
Hot equipment, if the solvent is deionized water, the preset temperature range is 50 DEG C ~ 60 DEG C, if the solvent is anhydrous second
Alcohol, then the preset temperature range is 20 DEG C ~ 35 DEG C；If the partial size of the polystyrene sphere is more than or equal to 350nm, with vacuum
Drying box is heating equipment, if the solvent is deionized water, the preset temperature range is 60 DEG C ~ 70 DEG C, if described molten
Agent is dehydrated alcohol, then the preset temperature range is 35 DEG C ~ 45 DEG C.
Further, in the S2, the electrochemical deposition method is the following steps are included: S2-1: configuration electroplating solution
And the pH value of the electroplating solution is adjusted to 3 ~ 4；If the composite colloid crystal is cobalt-based composite colloid crystal, the plating
The raw material of solution are as follows: Cobalt monosulfate heptahydrate, cobalt chloride hexahydrate, boric acid and lauryl sodium sulfate, molar concentration are respectively
0.01mol/L ~ 0.5mol/L, 0.01mol/L ~ 0.5mol/L, 0.02mol/L ~ 1mol/L and 0.6mmol/L ~ 30mmol/L；
If the composite colloid crystal is Ni-based composite colloid crystal, the raw material of the electroplating solution are as follows: six hydration nickel sulfate, six water
Close nickel chloride, boric acid and lauryl sodium sulfate, molar concentration be respectively 0.01mol/L ~ 0.5mol/L, 0.002mol/L ~
0.1mol/L, 0.012mol/L ~ 0.6mol/L and 0.5mmol/L ~ 25mmol/L；If the composite colloid crystal is that cobalt is Ni-based
Composite colloid crystal, the then raw material of the electroplating solution are as follows: Cobalt monosulfate heptahydrate, six hydration nickel sulfate, Nickel dichloride hexahydrate, boron
Acid and lauryl sodium sulfate, molar concentration be respectively 0.001mol/L ~ 0.05mol/L, 0.01mol/L ~ 0.5mol/L,
0.002mol/L ~ 0.1mol/L, 0.013mol/L ~ 0.65mol/L and 0.06mmol/L ~ 3mmol/L；S2-2: with the glue
Body crystal is working electrode, and platinum guaze is to electrode, and being saturated calomel or silver/silver chloride electrode is reference electrode, using constant potential mould
The composite colloid crystal is prepared in the electrochemical deposition method of formula.
Preferably, in the S2-2, the constant potential is -0.5 ~ -1.0V.
Preferably, in the S3, the composite colloid crystal is put into tetrahydrofuran or toluene solution described in removing
Polystyrene sphere obtains the cobalt or nickel or cobalt nickel photonic crystal.
Preferably, the electro-conductive glass is the stannic oxide FTO electro-conductive glass or tin-doped indium oxide ITO conduction glass of fluorine doped
Glass.
The utility model has the advantages that the present invention is using colloidal crystal as template, using colloidal crystal template-electrochemical deposition-hydro-thermal phase
In conjunction with the stable cobalt-based of method preparation structure or the Ni-based sulfide photonic crystal of Ni-based or cobalt, realize and mentioned in background technique
Improve the combination of cobalt-based or the Ni-based sulfide of Ni-based or cobalt to three kinds of modes of electrocatalysis characteristic of electrode: small by polystyrene
The colloidal crystal template that ball is prepared, more porous due to having inside colloidal crystal, subsequent electrochemical deposition can incite somebody to action
Cobalt/nickel cobalt nickel deposits in above-mentioned pore structure, obtains the cobalt with ordered 3 D structure after then removing polystyrene sphere
Or nickel or cobalt nickel photonic crystal react with above-mentioned cobalt or nickel or cobalt nickel photonic crystal finally with hydro-thermal method introducing sulphur source and generate cobalt
Base or the Ni-based sulfide photonic crystal of Ni-based or cobalt.Firstly, since cobalt-based or the Ni-based sulphur of Ni-based or cobalt that this method is prepared
Compound photonic crystal has ordered 3 D structure, so its specific surface area is larger, and by the introduction of background technique it is found that comparing table
Area is bigger, and electro catalytic activity number of loci is more, so that catalytic activity is higher (this is first way)；Secondly, porous knot
Structure not only increases effective catalytic active area to electrode, and diffusion duct can be provided for electrolyte, is conducive to improve electricity
Solve the diffusion velocity of matter, and electrolyte is bigger to the diffusion velocity on electrode, the electro-catalysis more helped to improve to electrode is living
Property (this is the second way)；Finally, cobalt/nickel cobalt nickel that the present invention is prepared by way of first electrochemical deposition again hydro-thermal
Sulfide photonic crystal has a variety of object phases, structure and surface topography, being capable of Effective Regulation cobalt/nickel cobalt nickel sulfide photon crystalline substance
The work function of body, to reach the matched purpose of itself and electrolyte potential, and in dye-sensitized solar cells, to electrode work content
Number is matched better with electrolyte potential, charge transmission resistance is more advantageously reduced, to improve the electro catalytic activity to electrode
(this is the third mode).
With photonic crystal be to electrode, can not only to provide porous structure to electrode and optimizing work function matching, and
There is the regulating and controlling effect of back reflection in photonic band gap region to incident light, while also reducing the light loss of reflected light, be conducive to
Light anode is further increased to the capture rate of incident light.
Form colloidal crystal after polystyrene sphere is first passed through in the present invention in conjunction with electro-conductive glass, then by cobalt/nickel cobalt nickel
It is electrodeposited into the pore structure inside colloidal crystal, then removing polystyrene sphere again and being formed has ordered 3 D structure
Cobalt or nickel or cobalt nickel photonic crystal, effectively increase the binding ability of cobalt or nickel or cobalt nickel photonic crystal and electro-conductive glass, simply
Say, binding ability is because the present invention increases electrochemical deposition method before hydro-thermal method and first constructs cobalt or nickel or cobalt nickel by force
The ordered 3 D structure of photonic crystal.
In conclusion using in the present invention cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt as the dye sensitization sun
Energy battery has the advantages of electrode:
1) possess more active site number；
2) more diffusion duct is provided；
3) work function of the Effective Regulation to electrode；
4) light anode is improved to the capture rate of incident light.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram piece for the colloidal crystal being self-assembly of by polystyrene sphere；
Fig. 2 is the scanning electron microscope diagram piece of cobalt photonic crystal；
Fig. 3 is the scanning electron microscope diagram piece of nickel photonic crystal；
Fig. 4 is the cross section structure schematic diagram of cobalt-based or the Ni-based photonic crystal of Ni-based or cobalt；
Fig. 5 is the cross section structure schematic diagram of cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt；
Fig. 6 is the face-centered cubic FCC configuration schematic diagram of cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt；
Fig. 7 be as cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt be to dye sensitization made of electrode assembling too
The cross section structure schematic diagram of positive energy battery.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
Embodiment 1:
Present embodiments provide for a kind of cobalt-based sulfide photonic crystals for dye-sensitized solar cells to electrode,
Preparation method is as follows:
S1: it disperses the monodisperse polystyrene bead that partial size is 300nm in deionized water, it is small to be prepared into polystyrene
The mass fraction of ball is the colloid bead solution of 0.05wt%；Colloid bead solution is heated to 55 DEG C using thermostatic water bath, Xiang Qi
Middle insertion FTO electro-conductive glass, and keep temperature constant, it slowly volatilizees completely to the water in colloid bead solution, obtains colloidal crystal；
Colloidal crystal is placed at 35 DEG C, 2h is dried, then at 105 DEG C, heat treatment 3min is carried out to colloidal crystal, such as
Fig. 1.
S2: deionization is dispersed by a certain amount of Cobalt monosulfate heptahydrate, cobalt chloride hexahydrate, lauryl sodium sulfate and boric acid
In water, and concentration is respectively 0.25mol/L, 0.25mol/L, 15mmol/L and 0.5mol/ L, with sulphur acid for adjusting pH value to 3.5,
It is arranged to electroplating solution；Using colloidal crystal obtained in S1 as working electrode, platinum guaze is to electrode, and saturated calomel electrode is reference
Cobalt-based composite colloid crystal is prepared using the constant potential electrochemical deposition of -0.7V in electrode；
S3: cobalt-based composite colloid crystal is put into tetrahydrofuran solution and removes polystyrene sphere, obtains cobalt photonic crystal；
Such as Fig. 2.
S4: urea being dissolved in deionized water and is configured to urea liquid, and the amount of the substance of urea is cobalt light in urea liquid
3 times of the amount of the substance of sub- crystal, urea liquid is transferred in autoclave, and the volume of urea liquid accounts for autoclave
The 75% of volume；It is put into cobalt photonic crystal, reacts 7h at 120 DEG C, uses deionized water and dehydrated alcohol respectively after natural cooling
Cleaning sample, vacuum dried sample obtain basic cobaltous carbonate photonic crystal；
Configured Sodium Sulphate Nine Hydroxide solution is transferred in autoclave, the volume of Sodium Sulphate Nine Hydroxide solution accounts for
The 75% of autoclave volume, the amount of the substance of Sodium Sulphate Nine Hydroxide is basic cobaltous carbonate photon in Sodium Sulphate Nine Hydroxide solution
4 times of the amount of the substance of crystal；It is put into basic cobaltous carbonate photonic crystal in Sodium Sulphate Nine Hydroxide solution, is reacted at 160 DEG C
7h uses deionized water and washes of absolute alcohol sample, vacuum dried sample respectively after natural cooling, obtains cobalt-based sulfide photon
Crystal.
Embodiment 2:
Present embodiments provide for a kind of Ni-based sulfide photonic crystals for dye-sensitized solar cells to electrode,
Preparation method is as follows:
S1: it disperses the monodisperse polystyrene bead that partial size is 500nm in dehydrated alcohol, it is small to be prepared into polystyrene
The mass fraction of ball is the colloid bead solution of 1.0wt%；Colloid bead solution is heated to 40 DEG C using vacuum oven, to
It is wherein inserted into ITO electro-conductive glass, and keeps temperature constant, slowly volatilizees completely, obtains to the dehydrated alcohol in colloid bead solution
Colloidal crystal；Colloidal crystal is placed at 50 DEG C, 4h is dried, then at 100 DEG C, hot place is carried out to colloidal crystal
Manage 5min.
S2: deionization is dispersed by a certain amount of six hydration nickel sulfate, Nickel dichloride hexahydrate, lauryl sodium sulfate and boric acid
In water, and concentration is respectively that 0.25mol/L, 0.05mol/L, 15mmol/L and 0.3mol/ L are matched with sulphur acid for adjusting pH value to 4
Set to obtain electroplating solution；Using colloidal crystal obtained in S1 as working electrode, platinum guaze is to electrode, and silver/silver chloride electrode is reference
Ni-based composite colloid crystal is prepared using the constant potential electrochemical deposition of -0.55V in electrode.
S3: Ni-based composite colloid crystal is put into toluene solution and removes polystyrene sphere, obtains nickel photonic crystal；Such as figure
3。
S4: urea being dissolved in deionized water and is configured to urea liquid, and the amount of the substance of urea is cobalt light in urea liquid
4 times of the amount of the substance of sub- crystal, urea liquid is transferred in autoclave, and the volume of urea liquid accounts for autoclave
The 80% of volume；It is put into nickel photonic crystal, reacts 6h at 130 DEG C, uses deionized water and dehydrated alcohol respectively after natural cooling
Cleaning sample, vacuum dried sample obtain basic nickel carbonate photonic crystal；
Configured Sodium Sulphate Nine Hydroxide solution is transferred in autoclave, the volume of Sodium Sulphate Nine Hydroxide solution accounts for
The 80% of autoclave volume, the amount of the substance of Sodium Sulphate Nine Hydroxide is basic nickel carbonate photon in Sodium Sulphate Nine Hydroxide solution
5 times of the amount of the substance of crystal；It is put into basic nickel carbonate photonic crystal in Sodium Sulphate Nine Hydroxide solution, is reacted at 150 DEG C
8h uses deionized water and washes of absolute alcohol sample, vacuum dried sample respectively after natural cooling, obtains Ni-based sulfide photon
Crystal.
Embodiment 3:
Present embodiments provide for a kind of Ni-based sulfide photonic crystals of cobalt for dye-sensitized solar cells to electricity
Pole, preparation method are as follows:
S1: it disperses the monodisperse polystyrene bead that partial size is 700nm in dehydrated alcohol, it is small to be prepared into polystyrene
The mass fraction of ball is the colloid bead solution of 2.0wt%；Colloid bead solution is heated to 45 DEG C using vacuum oven, to
It is wherein inserted into FTO electro-conductive glass, and keeps temperature constant, slowly volatilizees completely, obtains to the dehydrated alcohol in colloid bead solution
Colloidal crystal；Colloidal crystal is placed at 60 DEG C, 5h is dried；Then at 110 DEG C, hot place is carried out to colloidal crystal
Manage 1min.
S2: by a certain amount of Cobalt monosulfate heptahydrate, six hydration nickel sulfate, Nickel dichloride hexahydrate, lauryl sodium sulfate and boron
Acid is scattered in deionized water, and concentration be respectively 0.025mol/L, 0.25mol/L, 0.05mol/L, 1.5mmol/L and
0.35mol/ L is arranged to electroplating solution with sulphur acid for adjusting pH value to 3；Using colloidal crystal obtained in S1 as working electrode, platinum
Net is to electrode, and silver/silver chloride electrode is reference electrode, and it is Ni-based that cobalt is prepared using the constant potential electrochemical deposition of -1.0V
Composite colloid crystal.
S3: the Ni-based composite colloid crystal of cobalt is put into tetrahydrofuran solution and removes polystyrene sphere, obtains cobalt nickel photon
Crystal；
S4: urea being dissolved in deionized water and is configured to urea liquid, and the amount of the substance of urea is cobalt light in urea liquid
2 times of the amount of the substance of sub- crystal, urea liquid is transferred in autoclave, and the volume of urea liquid accounts for autoclave
The 70% of volume；It is put into nickel photonic crystal, reacts 8h at 110 DEG C, uses deionized water and dehydrated alcohol respectively after natural cooling
Cleaning sample, vacuum dried sample obtain basic cobaltous carbonate nickel photonic crystal；
Configured Sodium Sulphate Nine Hydroxide solution is transferred in autoclave, the volume of Sodium Sulphate Nine Hydroxide solution accounts for
The 70% of autoclave volume, the amount of the substance of Sodium Sulphate Nine Hydroxide is basic cobaltous carbonate nickel light in Sodium Sulphate Nine Hydroxide solution
3 times of the amount of the substance of sub- crystal；Basic cobaltous carbonate nickel photonic crystal is put into Sodium Sulphate Nine Hydroxide solution, at 170 DEG C
6h is reacted, deionized water and washes of absolute alcohol sample, vacuum dried sample is used respectively after natural cooling, obtains the Ni-based vulcanization of cobalt
Object photonic crystal.
It is as shown in Figure 4 the section of the cobalt-based or the Ni-based photonic crystal of Ni-based or cobalt that are prepared by the respective embodiments described above
Scheme, number 1 indicates the skeleton of cobalt-based or the Ni-based photonic crystal of Ni-based or cobalt in figure, and number 2 indicates that cobalt-based or Ni-based or cobalt are Ni-based
Hole inside photonic crystal, number 3 indicate electro-conductive glass.
Cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt to be prepared by the respective embodiments described above as shown in Figure 5
Sectional view, number 4 indicates cobalt-based or the Ni-based sulfide of Ni-based or cobalt.
Fig. 6 show the cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt being prepared by the respective embodiments described above
Face-centered cubic FCC configuration schematic diagram.
It is as shown in Figure 7 to be used as above-mentioned cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt to made of electrode assembling
The cross section structure schematic diagram of dye-sensitized solar cells, number 5 indicate electrolyte, and number 6 indicates titanium dioxide granule, number
7 indicate dyestuff N719, and number 8 indicates electro-conductive glass.
The technical concepts and features of above embodiment only to illustrate the invention, its object is to allow be familiar with technique
People cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent transformation or modification that Spirit Essence is done, should be covered by the protection scope of the present invention.
Claims (12)
1. it is a kind of for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photonic crystal of Ni-based or cobalt to electrode, it is special
Sign is, the preparation method is as follows:
S1: monodisperse polystyrene bead is self-assembled to by constant temperature vertical deposition method and forms colloidal crystal on electro-conductive glass；
S2: cobalt/nickel cobalt nickel deposition is filled into inside the colloidal crystal by electrochemical deposition method and obtains composite colloid crystalline substance
Body；
S3: removing the polystyrene sphere in the composite colloid crystal, obtains cobalt or nickel or cobalt nickel photonic crystal；
S4: sulphur source is introduced in the cobalt or nickel or cobalt nickel photonic crystal using hydro-thermal method, obtains cobalt-based or the Ni-based sulphur of Ni-based or cobalt
Compound photonic crystal.
2. according to claim 1 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S4, the hydro-thermal method the following steps are included:
S4-1: configured urea liquid is transferred in autoclave, and is put into the cobalt or nickel or cobalt nickel photonic crystal,
6 ~ 8h is reacted at a temperature of 110 DEG C ~ 130 DEG C, uses deionized water and washes of absolute alcohol sample, vacuum respectively after natural cooling
Drying sample obtains basic cobaltous carbonate or nickel or cobalt nickel photonic crystal；
S4-2: configured Sodium Sulphate Nine Hydroxide solution is transferred in autoclave, and be put into the basic cobaltous carbonate or
Nickel or cobalt nickel photonic crystal react 6 ~ 8h at a temperature of 150 DEG C ~ 170 DEG C, respectively with deionized water and anhydrous after natural cooling
Ethyl alcohol cleaning sample, vacuum dried sample obtain the cobalt-based or the Ni-based sulfide photonic crystal of Ni-based or cobalt.
3. according to claim 2 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S4-1, in the urea liquid, the amount of the substance of urea is cobalt or nickel or cobalt
2 ~ 4 times of the amount of the substance of nickel photonic crystal, the volume of the urea liquid are the 70% ~ 80% of autoclave volume.
4. according to claim 2 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S4-2, in the Sodium Sulphate Nine Hydroxide solution, and the substance of Sodium Sulphate Nine Hydroxide
Amount be 3 ~ 5 times of amount of substance of the basic cobaltous carbonate or nickel or cobalt nickel photonic crystal, the Sodium Sulphate Nine Hydroxide solution
Volume be the 70% ~ 80% of autoclave volume.
5. according to claim 1 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S1, the constant temperature vertical deposition method the following steps are included:
S1-1: formation colloid bead solution in solvent is dispersed by the polystyrene sphere；
S1-2: being heated to preset temperature for the colloid bead solution, be inserted into the electro-conductive glass thereto, and keeps temperature permanent
It is fixed, it slowly volatilizees to solvent completely, obtains the colloidal crystal；
S1-3: the colloidal crystal is placed at 30 DEG C ~ 60 DEG C, 1 ~ 6h is dried；
S1-4: at a temperature of 100 DEG C ~ 110 DEG C, 1 ~ 5min of heat treatment is carried out to the colloidal crystal.
6. according to claim 5 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S1-1,
If the solvent is deionized water, in the colloid bead solution, the mass fraction of the polystyrene sphere is
0.05wt%~0.5wt%；
If the solvent is dehydrated alcohol, in the colloid bead solution, the mass fraction of the polystyrene sphere is
0.5wt%~2.0wt%。
7. according to claim 6 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that the particle size range of the polystyrene sphere is 200 ~ 800nm.
8. according to claim 7 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S1-2,
If the partial size of the polystyrene sphere is less than 350nm, using thermostatic water bath as heating equipment, if the solvent is deionization
Water, then the preset temperature range is 50 DEG C ~ 60 DEG C, if the solvent is dehydrated alcohol, the preset temperature range is 20
℃~35℃；
If the partial size of the polystyrene sphere is more than or equal to 350nm, using vacuum oven as heating equipment, if the solvent is
Deionized water, then the preset temperature range is 60 DEG C ~ 70 DEG C, if the solvent is dehydrated alcohol, the preset temperature model
Enclose is 35 DEG C ~ 45 DEG C.
9. according to claim 1 for the cobalt-based of dye-sensitized solar cells or the Ni-based sulfide photon of Ni-based or cobalt
Crystal is to electrode, which is characterized in that in the S2, the electrochemical deposition method the following steps are included:
S2-1: configuration electroplating solution simultaneously adjusts the pH value of the electroplating solution to 3 ~ 4；
If the composite colloid crystal is cobalt-based composite colloid crystal, the raw material of the electroplating solution are as follows: Cobalt monosulfate heptahydrate,
Cobalt chloride hexahydrate, boric acid and lauryl sodium sulfate, molar concentration are respectively 0.01mol/L ~ 0.5mol/L, 0.01mol/
L ~ 0.5mol/L, 0.02mol/L ~ 1mol/L and 0.6mmol/L ~ 30mmol/L；
If the composite colloid crystal is Ni-based composite colloid crystal, the raw material of the electroplating solution are as follows: six hydration nickel sulfate,
Nickel dichloride hexahydrate, boric acid and lauryl sodium sulfate, molar concentration be respectively 0.01mol/L ~ 0.5mol/L,
0.002mol/L ~ 0.1mol/L, 0.012mol/L ~ 0.6mol/L and 0.5mmol/L ~ 25mmol/L；
If the composite colloid crystal is the Ni-based composite colloid crystal of cobalt, the raw material of the electroplating solution are as follows: seven hydrated sulfuric acids
Cobalt, six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and lauryl sodium sulfate, molar concentration be respectively 0.001mol/L ~
0.05mol/L, 0.01mol/L ~ 0.5mol/L, 0.002mol/L ~ 0.1mol/L, 0.013mol/L ~ 0.65mol/L and
0.06mmol/L~3mmol/L；
S2-2: using the colloidal crystal as working electrode, platinum guaze is to be saturated calomel to electrode or silver/silver chloride electrode is reference
The composite colloid crystal is prepared using the electrochemical deposition method of potentiostatic mode in electrode.
10. according to claim 9 for the cobalt-based of dye-sensitized solar cells or the Ni-based vulcanization object light of Ni-based or cobalt
Sub- crystal is to electrode, which is characterized in that in the S2-2, the constant potential is -0.5 ~ -1.0V.
11. the cobalt-based or Ni-based or cobalt according to any one of claim 1 to 10 for dye-sensitized solar cells
Ni-based sulfide photonic crystal is to electrode, which is characterized in that in the S3, the composite colloid crystal is put into tetrahydrofuran
Or the polystyrene sphere is removed in toluene solution, obtain the cobalt or nickel or cobalt nickel photonic crystal.
12. the cobalt-based or Ni-based or cobalt according to any one of claim 1 to 10 for dye-sensitized solar cells
Ni-based sulfide photonic crystal is to electrode, which is characterized in that the electro-conductive glass be fluorine doped stannic oxide FTO electro-conductive glass or
Tin-doped indium oxide ITO electro-conductive glass.
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| CN101844743A (en) * | 2010-03-26 | 2010-09-29 | 北京化工大学 | Method for preparing metallic submicron microsphere array film and electric deposition device |
| WO2014180780A1 (en) * | 2013-05-06 | 2014-11-13 | Greatcell Solar S.A. | Organic-inorganic perovskite based solar cell |
| CN104492460A (en) * | 2014-12-11 | 2015-04-08 | 浙江大学 | Metallic oxide/metal sulfide hollow nanospheres as well as preparation method and application thereof |
| CN105719836A (en) * | 2016-01-01 | 2016-06-29 | 三峡大学 | Preparation method of dye-sensitized solar battery cobalt-nickel sulfide counter electrode |
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| CN101844743A (en) * | 2010-03-26 | 2010-09-29 | 北京化工大学 | Method for preparing metallic submicron microsphere array film and electric deposition device |
| WO2014180780A1 (en) * | 2013-05-06 | 2014-11-13 | Greatcell Solar S.A. | Organic-inorganic perovskite based solar cell |
| CN104492460A (en) * | 2014-12-11 | 2015-04-08 | 浙江大学 | Metallic oxide/metal sulfide hollow nanospheres as well as preparation method and application thereof |
| CN105719836A (en) * | 2016-01-01 | 2016-06-29 | 三峡大学 | Preparation method of dye-sensitized solar battery cobalt-nickel sulfide counter electrode |
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