CN107785174A - The Ni-based sulfide photonic crystal of cobalt/nickel cobalt for DSSC is to electrode - Google Patents
The Ni-based sulfide photonic crystal of cobalt/nickel cobalt for DSSC is to electrode Download PDFInfo
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- CN107785174A CN107785174A CN201710777106.6A CN201710777106A CN107785174A CN 107785174 A CN107785174 A CN 107785174A CN 201710777106 A CN201710777106 A CN 201710777106A CN 107785174 A CN107785174 A CN 107785174A
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- cobalt
- nickel
- photonic crystal
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- electrode
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 88
- 239000010941 cobalt Substances 0.000 title claims abstract description 88
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004038 photonic crystal Substances 0.000 title claims abstract description 83
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 67
- 239000000084 colloidal system Substances 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 239000004793 Polystyrene Substances 0.000 claims abstract description 33
- 229920002223 polystyrene Polymers 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000011324 bead Substances 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 22
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 239000004202 carbamide Substances 0.000 claims description 26
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 14
- 238000009713 electroplating Methods 0.000 claims description 12
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims description 11
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- SVMHVVMANJMZLD-UHFFFAOYSA-N [Co].[Ni].[Ni] Chemical compound [Co].[Ni].[Ni] SVMHVVMANJMZLD-UHFFFAOYSA-N 0.000 claims description 2
- 229940075397 calomel Drugs 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000006870 function Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to field of dye-sensitized solar cells, discloses a kind of Ni-based sulfide photonic crystal of cobalt/nickel cobalt for DSSC to electrode, S1：Monodisperse polystyrene bead is self-assembled to by constant temperature vertical deposition method colloidal crystal is formed 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：The polystyrene sphere in the composite colloid crystal is removed, obtains cobalt/nickel cobalt nickel photonic crystal；S4：Sulphur source is introduced in the cobalt/nickel cobalt nickel photonic crystal using hydro-thermal method, obtains the Ni-based sulfide photonic crystal of cobalt/nickel cobalt.The binding ability of cobalt/nickel cobalt nickel photonic crystal and electro-conductive glass in the present invention is preferable, catalytic active site in electrode is counted out more, electrolyte diffusion speed, its work function matches preferably with electrolyte potential, higher to the DSSC energy conversion efficiency of electrode with its work.
Description
Technical field
It is more particularly to a kind of to be used for the dye sensitization sun the present invention relates to DSSC to electrode field
The Ni-based sulfide photonic crystal of cobalt/nickel cobalt of energy battery is to electrode.
Background technology
As global energy crisis increasingly sharpens, solar energy is because having the advantages that aboundresources, widely distributed, environmentally friendly,
As the study hotspot in energy field.DSSC (DSSC) possess higher theoretical energy conversion efficiency, into
The features such as this is low, technique is simple, environment-friendly, as a kind of one of most promising photovoltaic power generation technology, receive wide
General concern.It is the indispensable important components of DSSC to electrode.Noble metal platinum has good electric conductivity and catalytic activity,
It is the most frequently used to electrode material.But there is resource-constrained, cost height, in I in platinum-/I- 3Perishable grade lacks in electrolyte system
Point.Therefore, excellent performance how is obtained, the problem that cheap, stable and industrial quarters always academic to electrode material faces.Hair
Excellent performance, cheap, the stable hot research direction that DSSC is not only to electrode material are opened up, 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 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.
Because the dissolving on electrode is one of principal element for influenceing DSSC stability, specific surface area affects electro catalytic activity position
Count out, work function also contributes to electrocatalysis characteristic with electrolyte potential matching properties.In all multipair electrode materials, sulfide
Not only there is the shared characteristic of nano material, and also there is property in optics, electricity etc., be increasingly becoming energy
Storage and a study hotspot in converting material.DSSC research in, sulfide to electrode not only have cost it is low, prepare work
Skill is simple, good chemical stability, but also shows the electrocatalysis characteristic suitable with platinum electrode.But sulfide is to electricity
Still also there is key issue and not yet solve in pole, as the electro catalytic activity of sulfide and its DSSC photoelectric properties of composition all need
Further improve.Want solve these problems, it is necessary to deeper design construction and phenetic analysis sulfide nano-material.
In order to improve electrocatalysis characteristic of the sulfide to electrode, nanocrystalline, loose structure, hollow structure probed into, have received
The Ni-based sulfide of cobalt/nickel cobalt of rice piece etc. different morphologies and thing phase is to electrode.It is generally acknowledged that mainly there are three kinds of modes to improve
Electrocatalysis characteristic of the Ni-based sulfide of cobalt/nickel cobalt to electrode.The first is that increase is counted out to the catalytic active site of electrode.It is logical
Often in the case of, material specific surface area is bigger, its catalytic active site count out it is also more, so as to be advantageous to improve material catalysis
Activity.It is to increase two kinds of material specific surface area to construct loose structure in material internal and reduce material particle size to obtain nanocrystalline
Important way, such as：The synthesis of the nanocrystalline sulfides of NiS loose structures, NiS.Second is to improve electrolyte to electrode
On diffusion velocity.It is generally acknowledged that diffusion velocity of the electrolyte on to electrode is bigger, more it is favorably improved and the electricity of electrode is urged
Change activity.And loose structure not only increases effective catalytic active area to electrode, and diffusion hole can be provided for electrolyte
Road, be advantageous to improve the diffusion velocity of electrolyte, such as：CoNi2S4The synthesis of nanostructured, NiS nanometer sheet sulfides.The
Three kinds are thing phase, structure and surface topography of the design construction to electrode material, regulate and control its work function.In DSSC, to electrode work(
Function matches better with electrolyte potential, more advantageously reduces electric charge transmission resistance, so as to which the electro-catalysis improved to electrode is lived
Property.The work function of material can be typically expressed as the difference of vacuum level and fermi level, thus thing phase, the structure for passing through construction material
And surface topography, with regard to its work function of energy Effective Regulation.
Analyzed more than, if the Ni-based vulcanization of cobalt/nickel cobalt can just be greatly improved effectively with reference to these three modes
Electro catalytic activity of the thing to electrode.And effective combination of first two mode is only realized currently with loose structure.Although it is based on
Photonic crystal is effectively improved to the DSSC energy conversion efficiencies of electrode compared with the battery efficiency based on platinum electrode, but
It is that photonic crystal is also to be further improved to the stability of electrode.Exist mainly due to photonic crystal and combined with electro-conductive glass
Power is weaker, layer by layer between connect the problems such as poor, easy to fall off.This results in the Ni-based sulfide photonic crystal of cobalt/nickel cobalt in DSSC
Application in electrode is not obtained also extensively and systematic research.
The content of the invention
Goal of the invention：For problems of the prior art, the present invention provides a kind of for dye sensitization of solar electricity
The Ni-based sulfide photonic crystal of cobalt/nickel cobalt in pond to electrode, the binding ability of cobalt/nickel cobalt nickel photonic crystal and electro-conductive glass compared with
It is good, catalytic active site in electrode is counted out more, electrolyte diffusion speed, its work function matched with electrolyte potential compared with
It is good, it is higher to the DSSC energy conversion efficiency of electrode with its work.
Technical scheme：The invention provides a kind of Ni-based vulcanization object light of cobalt/nickel cobalt for DSSC
Sub- crystal is to electrode, it is characterised in that preparation method is as follows：S1：Monodisperse polystyrene bead is passed through into constant temperature vertical deposition
Method, which self-assembles to, forms colloidal crystal on electro-conductive glass；S2：Cobalt/nickel cobalt nickel deposition is filled into by electrochemical deposition method
Composite colloid crystal is obtained inside the colloidal crystal；S3：Remove the polystyrene sphere in the composite colloid crystal, obtain cobalt/
Nickel cobalt nickel photonic crystal；S4：Sulphur source is introduced in the cobalt/nickel cobalt nickel photonic crystal using hydro-thermal method, obtains cobalt/nickel cobalt nickel
Base sulfide photonic crystal.
Further, in the S4, the hydro-thermal method comprises the following steps：S4-1：The urea liquid configured is turned
Move in autoclave, and be put into the cobalt/nickel cobalt nickel photonic crystal, 6 ~ 8h is reacted at a temperature of 110 DEG C ~ 130 DEG C, is treated
Deionized water and washes of absolute alcohol sample, vacuum dried sample are used after natural cooling respectively, obtains basic cobaltous carbonate/nickel cobalt nickel
Photonic crystal；S4-2：The nine hydrated sodium sulfide solution configured are transferred in autoclave, and are put into the basic carbonate
Cobalt/nickel cobalt nickel photonic crystal, 6 ~ 8h is reacted at a temperature of 150 DEG C ~ 170 DEG C, uses deionized water and nothing respectively after natural cooling
Water-ethanol cleaning sample, vacuum dried sample, obtain the Ni-based sulfide photonic crystal of the cobalt/nickel cobalt.
Further, in the S4-1, in the urea liquid, the amount of the material of urea is that cobalt/nickel cobalt nickel photon is brilliant
2 ~ 4 times of the amount of the material of body, the volume of the urea liquid are the 70% ~ 80% of autoclave volume.
Further, in the S4-2, in the nine hydrated sodium sulfides solution, the amount of the material of nine hydrated sodium sulfides is
3 ~ 5 times of the amount of the material of the basic cobaltous carbonate/nickel cobalt nickel photonic crystal, the volume of the nine hydrated sodium sulfides solution are
The 70% ~ 80% of autoclave volume.
Further, in the S1, the constant temperature vertical deposition method comprises the following steps：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 keeping temperature is constant, treats that solvent slowly volatilizees completely, obtains the colloidal crystal；S1-3：By institute
State colloidal crystal and be placed at 30 DEG C ~ 60 DEG C and 1 ~ 6h of processing 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, it is 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 absolute ethyl 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.
Preferably, in the S1-2, if the particle diameter of the polystyrene sphere is less than 350nm, using Water Tank with Temp.-controlled as plus
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 particle diameter of the polystyrene sphere is more than or equal to 350nm, with vacuum
Drying box is firing equipment, if the solvent is deionized water, the preset temperature range is 60 DEG C ~ 70 DEG C, if described molten
Agent is absolute ethyl alcohol, then the preset temperature range is 35 DEG C ~ 45 DEG C.
Further, in the S2, the electrochemical deposition method comprises the following steps：S2-1：Configure 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 is：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 is：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, then the raw material of the electroplating solution be：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 that saturation calomel or silver/silver chloride electrode are reference electrode, using constant potential mould to electrode
The composite colloid crystal is prepared in the electrochemical deposition method of formula.
Preferably, in the S2-3, 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, obtain the cobalt/nickel cobalt nickel photonic crystal.
Preferably, the electro-conductive glass is the tin ash FTO electro-conductive glass or tin-doped indium oxide ITO conduction glass of fluorine doped
Glass.
Beneficial effect：The present invention is using colloidal crystal as template, using colloidal crystal template-electrochemical deposition-hydro-thermal phase
With reference to the stable Ni-based sulfide photonic crystal of cobalt/nickel cobalt of method preparation structure, realize the raising mentioned in background technology
Combination of the Ni-based sulfide of cobalt/nickel cobalt to three kinds of modes of electrocatalysis characteristic of electrode：It is prepared by polystyrene sphere
Colloidal crystal template, due to having inside colloidal crystal compared with concrete dynamic modulus, subsequent electrochemical deposition just can be by cobalt/nickel cobalt nickel
Deposit in above-mentioned pore structure, the cobalt/nickel cobalt nickel light with ordered 3 D structure is obtained after then removing polystyrene sphere
Sub- crystal, sulphur source finally is introduced with hydro-thermal method, with above-mentioned cobalt/nickel cobalt nickel photonic crystal reaction generation Ni-based vulcanization of cobalt/nickel cobalt
Thing photonic crystal.Firstly, since the Ni-based sulfide photonic crystal of cobalt/nickel cobalt that this method is prepared has three-dimensional order knot
Structure, so its specific surface area is larger, and, electro catalytic activity number of sites bigger by the introduction of background technology, specific surface area
Mesh is more, so as to which catalytic activity is higher（This is first way）；Secondly, loose structure not only increases effectively urging to electrode
Change active area, and diffusion duct can be provided for electrolyte, be advantageous to improve the diffusion velocity of electrolyte, and electrolyte is right
Diffusion velocity on electrode is bigger, is more favorably improved the electro catalytic activity to electrode（This is the second way）；Finally, this hair
Bright cobalt/nickel cobalt nickel sulfide the photonic crystal prepared by way of first electrochemical deposition again hydro-thermal has a variety of thing phases, knot
Structure and surface topography, it is capable of the work function of Effective Regulation cobalt/nickel cobalt nickel sulfide photonic crystal, to reach itself and electrolyte electricity
The purpose of position matching, and in DSSC, what electrodes work functions were matched with electrolyte potential is better, more has
Beneficial to electric charge transmission resistance is reduced, so as to improve the electro catalytic activity to electrode（This is the third mode）.
Using photonic crystal as to electrode, can not only to provide electrode loose structure and optimization work function matching, and
There is the regulating and controlling effect of back reflection in photonic band gap region to incident light, while also reduce the light loss of reflected light, be advantageous to
Further improve capture rate of the light anode to incident light.
First passed through in the present invention and colloidal crystal is formed after polystyrene sphere is combined with electro-conductive glass, then by cobalt/nickel cobalt nickel
It is electrodeposited into the pore structure inside colloidal crystal, then removes polystyrene sphere again and formed with ordered 3 D structure
Cobalt/nickel cobalt nickel photonic crystal, the binding ability of cobalt/nickel cobalt nickel photonic crystal and electro-conductive glass is effectively increased, briefly,
Binding ability is because the present invention adds electrochemical deposition method before hydro-thermal method and first constructs cobalt/nickel cobalt nickel photon crystalline substance by force
The ordered 3 D structure of body.
In summary, DSSC is used as using the Ni-based sulfide photonic crystal of cobalt/nickel cobalt in the present invention
Have to the advantages of electrode：
1) possess more catalytic active site to count out；
2) more diffusion duct is provided；
3) work function of the Effective Regulation to electrode；
4) capture rate of the light anode to incident light is improved.
Brief description of the drawings
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 the Ni-based photonic crystal of cobalt/nickel cobalt；
Fig. 5 is the cross section structure schematic diagram of the Ni-based sulfide photonic crystal of cobalt/nickel cobalt；
Fig. 6 is the face-centered cubic FCC configuration schematic diagram of the Ni-based sulfide photonic crystal of cobalt/nickel cobalt；
It by the Ni-based sulfide photonic crystal of cobalt/nickel cobalt is the DSSC that is formed to electrode assembling that Fig. 7, which is,
Cross section structure schematic diagram.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings.
Embodiment 1：
Present embodiments provide for a kind of cobalt-based sulfide photonic crystal for DSSC to electrode, it is made
Preparation Method is as follows：
S1：The monodisperse polystyrene bead that particle diameter is 300nm is scattered in deionized water, is prepared into polystyrene sphere
Mass fraction is 0.05wt% colloid bead solution；Colloid bead solution is heated to 55 DEG C using Water Tank with Temp.-controlled, inserted thereto
Enter FTO electro-conductive glass, and keeping temperature is constant, treats that the water in colloid bead solution slowly volatilizees completely, obtains colloidal crystal；By glue
Body crystal, which is placed at 35 DEG C, is dried processing 2h, and then at 105 DEG C, heat treatment 3min, such as Fig. 1 are carried out to colloidal crystal.
S2：A certain amount of Cobalt monosulfate heptahydrate, cobalt chloride hexahydrate, lauryl sodium sulfate and boric acid are scattered in deionization
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 obtained colloidal crystal in S1 as working electrode, platinum guaze is that saturated calomel electrode is reference to electrode
Electrode, cobalt-based composite colloid crystal is prepared using -0.7V constant potential electrochemical deposition；
S3：Cobalt-based composite colloid crystal is put into tetrahydrofuran solution and removes polystyrene sphere, obtains cobalt photonic crystal；Such as figure
2。
S4：Urea is dissolved in deionized water and is configured to urea liquid, the amount of the material of urea is cobalt light in urea liquid
3 times of the amount of the material of sub- crystal, urea liquid is transferred in autoclave, and the volume of urea liquid accounts for autoclave
The 75% of volume；Cobalt photonic crystal is put into, reacts 7h at 120 DEG C, uses deionized water and absolute ethyl alcohol respectively after natural cooling
Cleaning sample, vacuum dried sample, obtain basic cobaltous carbonate photonic crystal；
The nine hydrated sodium sulfide solution configured are transferred in autoclave, the volume of nine hydrated sodium sulfide solution accounts for high pressure
The 75% of reactor volume, the amount of the material of nine hydrated sodium sulfides is basic cobaltous carbonate photonic crystal in nine hydrated sodium sulfide solution
4 times of amount of material；Basic cobaltous carbonate photonic crystal is put into nine hydrated sodium sulfide solution, 7h is reacted at 160 DEG C, treats
Deionized water and washes of absolute alcohol sample, vacuum dried sample are used after natural cooling respectively, obtains cobalt-based sulfide photonic crystal.
Embodiment 2：
Present embodiments provide for a kind of Ni-based sulfide photonic crystal for DSSC to electrode, it is made
Preparation Method is as follows：
S1：The monodisperse polystyrene bead that particle diameter is 500nm is scattered in absolute ethyl alcohol, is prepared into polystyrene sphere
Mass fraction is 1.0wt% colloid bead solution；Colloid bead solution is heated to 40 DEG C using vacuum drying chamber, thereto
ITO electro-conductive glass is inserted, and keeping temperature is constant, treats that the absolute ethyl alcohol in colloid bead solution slowly volatilizees completely, obtains colloid
Crystal；Colloidal crystal is placed at 50 DEG C processing 4h is dried, then at 100 DEG C, colloidal crystal is heat-treated
5min。
S2：A certain amount of six hydration nickel sulfate, Nickel dichloride hexahydrate, lauryl sodium sulfate and boric acid are scattered in deionization
In water, and concentration is respectively 0.25mol/L, 0.05mol/L, 15mmol/L and 0.3mol/ L, with sulphur acid for adjusting pH value to 4, is matched somebody with somebody
Put to obtain electroplating solution；Using obtained colloidal crystal in S1 as working electrode, platinum guaze is that silver/silver chloride electrode is reference to electrode
Electrode, Ni-based composite colloid crystal is prepared using -0.55V constant potential electrochemical deposition.
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 is dissolved in deionized water and is configured to urea liquid, the amount of the material of urea is cobalt light in urea liquid
4 times of the amount of the material of sub- crystal, urea liquid is transferred in autoclave, and the volume of urea liquid accounts for autoclave
The 80% of volume；Nickel photonic crystal is put into, reacts 6h at 130 DEG C, uses deionized water and absolute ethyl alcohol respectively after natural cooling
Cleaning sample, vacuum dried sample, obtain basic nickel carbonate photonic crystal；
The nine hydrated sodium sulfide solution configured are transferred in autoclave, the volume of nine hydrated sodium sulfide solution accounts for high pressure
The 80% of reactor volume, the amount of the material of nine hydrated sodium sulfides is basic nickel carbonate photonic crystal in nine hydrated sodium sulfide solution
5 times of amount of material；Basic nickel carbonate photonic crystal is put into nine hydrated sodium sulfide solution, 8h is reacted at 150 DEG C, treats
Deionized water and washes of absolute alcohol sample, vacuum dried sample are used after natural cooling respectively, obtains Ni-based sulfide photonic crystal.
Embodiment 3：
Present embodiments provide for a kind of Ni-based sulfide photonic crystal of cobalt for DSSC to electrode, its
Preparation method is as follows：
S1：The monodisperse polystyrene bead that particle diameter is 700nm is scattered in absolute ethyl alcohol, is prepared into polystyrene sphere
Mass fraction is 2.0wt% colloid bead solution；Colloid bead solution is heated to 45 DEG C using vacuum drying chamber, thereto
FTO electro-conductive glass is inserted, and keeping temperature is constant, treats that the absolute ethyl alcohol in colloid bead solution slowly volatilizees completely, obtains colloid
Crystal；Colloidal crystal is placed at 60 DEG C processing 5h is dried；Then at 110 DEG C, colloidal crystal is heat-treated
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, with sulphur acid for adjusting pH value to 3, it is arranged to electroplating solution；So that obtained colloidal crystal is working electrode in S1, platinum
Net is that silver/silver chloride electrode is reference electrode, and it is Ni-based that cobalt is prepared using -1.0V constant potential electrochemical deposition to electrode
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 is dissolved in deionized water and is configured to urea liquid, the amount of the material of urea is cobalt photon crystalline substance in urea liquid
2 times of the amount of the material of body, urea liquid is transferred in autoclave, and the volume of urea liquid accounts for autoclave volume
70%；Nickel photonic crystal is put into, reacts 8h at 110 DEG C, uses deionized water and washes of absolute alcohol respectively after natural cooling
Sample, vacuum dried sample, obtain basic cobaltous carbonate nickel photonic crystal；
The nine hydrated sodium sulfide solution configured are transferred in autoclave, the volume of nine hydrated sodium sulfide solution accounts for high pressure
The 70% of reactor volume, the amount of the material of nine hydrated sodium sulfides is basic cobaltous carbonate nickel photon crystalline substance in nine hydrated sodium sulfide solution
3 times of the amount of the material of body；Basic cobaltous carbonate nickel photonic crystal is put into nine hydrated sodium sulfide solution, is reacted at 170 DEG C
6h, use deionized water and washes of absolute alcohol sample, vacuum dried sample respectively after natural cooling, obtain the Ni-based vulcanization object light of cobalt
Sub- crystal.
It is as shown in Figure 4 the sectional view for the Ni-based photonic crystal of cobalt/nickel cobalt being prepared by the respective embodiments described above, figure
Middle numbering 1 represents the skeleton of the Ni-based photonic crystal of cobalt/nickel cobalt, and numbering 2 represents the hole inside the Ni-based photonic crystal of cobalt/nickel cobalt
Gap, numbering 3 represent electro-conductive glass.
It is as shown in Figure 5 the section for the Ni-based sulfide photonic crystal of cobalt/nickel cobalt being prepared by the respective embodiments described above
Figure, numbering 4 represent the Ni-based sulfide of cobalt/nickel cobalt.
The center of area that Fig. 6 show the Ni-based sulfide photonic crystal of the cobalt/nickel cobalt being prepared by the respective embodiments described above is stood
Square FCC configuration schematic diagram.
It is quick as the dyestuff formed to electrode assembling by the Ni-based sulfide photonic crystal of above-mentioned cobalt/nickel cobalt as shown in Figure 7
Change the cross section structure schematic diagram of solar cell, numbering 5 represents electrolyte, and numbering 6 represents titanium dioxide granule, and numbering 7 represents
Dyestuff N719, numbering 8 represent electro-conductive glass.
The technical concepts and features of above-mentioned embodiment only to illustrate the invention, its object is to allow be familiar with technique
People can understand present disclosure and implement according to this, 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 all be included within the scope of the present invention.
Claims (12)
1. a kind of Ni-based sulfide photonic crystal of cobalt/nickel cobalt for DSSC exists to electrode, its feature
In preparation method is as follows：
S1：Monodisperse polystyrene bead is self-assembled to by constant temperature vertical deposition method colloidal crystal is formed 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：The polystyrene sphere in the composite colloid crystal is removed, obtains cobalt/nickel cobalt nickel photonic crystal；
S4：Sulphur source is introduced in the cobalt/nickel cobalt nickel photonic crystal using hydro-thermal method, obtains the Ni-based sulfide photon of cobalt/nickel cobalt
Crystal.
2. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 1 for DSSC
Electrode, it is characterised in that in the S4, the hydro-thermal method comprises the following steps：
S4-1：The urea liquid configured is transferred in autoclave, and is put into the cobalt/nickel cobalt nickel photonic crystal,
6 ~ 8h is reacted at a temperature of 110 DEG C ~ 130 DEG C, is done respectively with deionized water and washes of absolute alcohol sample, vacuum after natural cooling
Dry sample, obtain basic cobaltous carbonate/nickel cobalt nickel photonic crystal；
S4-2：The nine hydrated sodium sulfide solution configured are transferred in autoclave, and be put into the basic cobaltous carbonate/
Nickel cobalt nickel photonic crystal, 6 ~ 8h is reacted at a temperature of 150 DEG C ~ 170 DEG C, respectively with deionized water and anhydrous after natural cooling
Ethanol cleaning sample, vacuum dried sample, obtain the Ni-based sulfide photonic crystal of the cobalt/nickel cobalt.
3. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 2 for DSSC
Electrode, it is characterised in that in the S4-1, in the urea liquid, the amount of the material of urea is that cobalt/nickel cobalt nickel photon is brilliant
2 ~ 4 times of the amount of the material of body, the volume of the urea liquid are the 70% ~ 80% of autoclave volume.
4. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 2 for DSSC
Electrode, it is characterised in that in the S4-2, in the nine hydrated sodium sulfides solution, the amount of the material of nine hydrated sodium sulfides is
3 ~ 5 times of the amount of the material of the basic cobaltous carbonate/nickel cobalt nickel photonic crystal, the volume of the nine hydrated sodium sulfides solution are
The 70% ~ 80% of autoclave volume.
5. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 1 for DSSC
Electrode, it is characterised in that in the S1, the constant temperature vertical deposition method comprises the following steps：
S1-1：The polystyrene sphere is scattered in formation colloid bead solution in solvent；
S1-2：The colloid bead solution is heated to preset temperature, inserts the electro-conductive glass thereto, and keeping temperature is permanent
It is fixed, treat that solvent slowly volatilizees completely, obtain the colloidal crystal；
S1-3：The colloidal crystal is placed at 30 DEG C ~ 60 DEG C 1 ~ 6h of processing 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. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 5 for DSSC
Electrode, it is characterised 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 absolute ethyl alcohol, in the colloid bead solution, the mass fraction of the polystyrene sphere is
0.5wt%~2.0wt%。
7. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 6 for DSSC
Electrode, it is characterised in that the particle size range of the polystyrene sphere is 200 ~ 800nm.
8. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 7 for DSSC
Electrode, it is characterised in that in the S1-2,
If the particle diameter of the polystyrene sphere is less than 350nm, using Water Tank with Temp.-controlled as firing equipment, if the solvent is deionization
Water, then the preset temperature range is 50 DEG C ~ 60 DEG C, if the solvent is absolute ethyl alcohol, the preset temperature range is 20
℃~35℃；
If the particle diameter of the polystyrene sphere is more than or equal to 350nm, using vacuum drying chamber as firing equipment, if the solvent is
Deionized water, then the preset temperature range is 60 DEG C ~ 70 DEG C, if the solvent is absolute ethyl alcohol, the preset temperature model
Enclose is 35 DEG C ~ 45 DEG C.
9. the Ni-based sulfide photonic crystal pair of cobalt/nickel cobalt according to claim 1 for DSSC
Electrode, it is characterised in that in the S2, the electrochemical deposition method comprises the following steps：
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 is：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 is：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 is：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 that saturation calomel or silver/silver chloride electrode are reference to electrode
Electrode, the composite colloid crystal is prepared using the electrochemical deposition method of potentiostatic mode.
10. the Ni-based sulfide photonic crystal of cobalt/nickel cobalt according to claim 9 for DSSC
To electrode, it is characterised in that in the S2-3, the constant potential is -0.5 ~ -1.0V.
11. cobalt/nickel cobalt Ni-based sulphur according to any one of claim 1 to 10 for DSSC
Compound photonic crystal is to electrode, it is characterised in that in the S3, the composite colloid crystal is put into tetrahydrofuran or toluene
The polystyrene sphere is removed in solution, obtains the cobalt/nickel cobalt nickel photonic crystal.
12. cobalt/nickel cobalt Ni-based sulphur according to any one of claim 1 to 10 for DSSC
Compound photonic crystal is to electrode, it is characterised in that the electro-conductive glass is the tin ash FTO electro-conductive glass of fluorine doped or mixes tin oxygen
Change indium ITO electro-conductive glass.
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