CN105826077A - Composite pair electrode used in quantum-dot sensitized solar cell and preparation method for same - Google Patents
Composite pair electrode used in quantum-dot sensitized solar cell and preparation method for same Download PDFInfo
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- CN105826077A CN105826077A CN201610320360.9A CN201610320360A CN105826077A CN 105826077 A CN105826077 A CN 105826077A CN 201610320360 A CN201610320360 A CN 201610320360A CN 105826077 A CN105826077 A CN 105826077A
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 239000000463 material Substances 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 14
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- 229920000642 polymer Polymers 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 67
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 230000009466 transformation Effects 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical group CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
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- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
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- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000007790 scraping Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
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- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a composite pair electrode used in a quantum-dot sensitized solar cell and a preparation method for the same. The composite pair electrode comprises a base material layer (1) and a composite film layer (2), wherein the composite film layer (2) is located on one panel of the base material layer (1). The base material layer (1) can be made of glass, fabrics or polymers, etc. The composite film layer (2) is made of Cu2S/C or FeS/C or NiS/C. The electrode disclosed by the invention is prepared through combination of a scraping method and chemical conversion technologies. The prepared product has high catalytic activity and high stability in an electrolyte. The assembled quantum-dot sensitized solar cell has high photovoltaic conversion efficiency.
Description
Technical field
The present invention relates to a kind of combined counter electrode, more particularly, refer to a kind of combined counter electrode for quantum dot sensitized solaode and preparation method thereof.
Background technology
" DSSC is applied from theoretical basis to technology " that Chemical Industry Press published in August, 2013, author Ma Tingli and Yun Sining, page 252, disclose " being referred to as quantum dot sensitized solaode (quantumdot-sensitizedsolarcells, QDSC) using quantum dot as the sensitization solar battery of sensitizer ".Page 252, disclose that " QDSC battery is (such as TiO by quantum dot sensitized nano-crystal semiconductor porous film2) be light anode, electrolyte containing oxidation-reduction pair (asElectricity to) and to electrode constitute sandwich structure battery ".The 271-272 page, disclose " electrode being also referred to as photocathode, mainly will be arrived, by external circuit, the oxidation state species that the electronics to electrode is quick, pass in electrolyte to low-loss in the battery ".
Solar energy can effectively solve the energy and the environmental crisis of facing mankind as a kind of cleaning, regenerative resource.Solaode is the very effective mode of one utilizing solar energy, and solar energy is converted directly into electric energy by it.Owing to the energy density of solar energy is relatively low, it is thus achieved that efficient, stable photoelectric transformation efficiency (PCE) is the core objective of solaode research.One of representative as third generation solar cell, quantum dot sensitized solaode (QDSC) is due to the dimensional effect of quantum dot and many exciton effects, and theoretical PCE, up to 44%, is a kind of great Research Significance and the high performance solar batteries of application prospect.
Noble metal with Pt as representative has superperformance to electrode in QDSC, but, withFor Pt electrode in the QDSC of electrolyte because ofReduction overpotential is high, and catalytic performance is very poor.Metal sulfide due toElectrolyte has and is preferably catalyzed activity, be that the QDSC of current most study is to electrode.GaryHode et al. proposes metal sulfide (CoS, NiS, Cu very early2S and PbS) many sulfur electrolyte had higher catalysis activity, and demonstrate metal sulfide catalysis activity in many sulfur electrolyte apparently higher than Pt electrode.
At present, homogenous material to electrode catalyst activity still than in situ preparation Cu2S electrode is less better.Therefore, people attempt integrating the advantage of different materials, make combination electrode and improve the overall performance to electrode, therefore searching cost is relatively low, stability preferable, manyIn electrolyte, catalysis activity is high significant for the photoelectric transformation efficiency (PCE) improving QDSC further to electrode.
Summary of the invention
In order to improve the photoelectric transformation efficiency (PCE) of existing quantum dot sensitization solar battery, and catalysis activity in the electrolyte, the present invention devises a kind of metal sulfide/carbon combined counter electrode and the chemical transformation technique of preparation employing.
A kind of combined counter electrode for quantum dot sensitized solaode of the present invention, this combined counter electrode includes substrate layer (1) and composite film (2), and composite film (2) is positioned on a panel of substrate layer (1)；
The material of described substrate layer (1) can select glass, fabric or polymer；
Described composite film (2) is Cu2S/C or FeS/C or NiS/C.
The present invention prepares a kind of method of combined counter electrode for quantum dot sensitized solaode, and it includes the following step:
The first step, prepared by slurry；
By the metal powder of carbon source, 50～500nm, binding agent and solvent mix homogeneously, obtain slurry；
Consumption: the slurry of 100g processed needs the binding agent of the metal powder of carbon source, 5～15g, 15～the 20g of 5～15g, the solvent of surplus.
Described carbon source includes active material and conductive agent, and active material has graphite, CNT, Graphene, activated carbon etc., and conductive agent has white carbon black, acetylene black etc..
Described metal powder is copper, ferrum or nickel etc., and metal powder particle size can be adjustable to tens micrometer ranges in tens nanometers.
Described binding agent is acrylic resin or Kynoar.
Described solvent is N-methyl pyrrole network alkanone or dipropylene glycol methyl ether.
Second step, prepares metal/carbon laminated film；
Choosing glass, fabric or polymer is base material, and base material is cleaned, dried, obtain cleaning base material；
The slurry first step obtained uniformly scratches at clean substrate surface, and blade coating thickness is 30～70 microns, obtains the first pre-adult；
3rd step, heat treatment removes solvent；
It is 50 DEG C～70 DEG C that the first pre-adult obtained by second step is placed in temperature, heat treatment 25～after 40 minutes, obtains the second pre-adult；
In the present invention, the second pre-adult does not contains solvent.The the second pre-adult prepared is that a kind of metal/carbon composite membrane is at base material.
4th step, chemical conversion metal sulfide/carbon combined counter electrode；
The the second pre-adult 3rd step obtained is dipped in many sulfur electrolyte that temperature is 20 DEG C～35 DEG C 6～8 hours, obtains metal sulfide/carbon combined counter electrode.
Many sulfur electrolyte is Na2The mixed aqueous solution of S Yu S, Na2The concentration of S be the concentration of 2mol/L, S be 3mol/L, preparation method be 60 DEG C stir 30 minutes.
The advantage of the combined counter electrode that the present invention prepares is:
1. being prepared on inorganic non-metallic base material by composite film, selection is with low cost, and good film-forming property.
2. composite film is the root that autgmentability dendritic morphology is similar to plant, shows that metal sulfide contacts with carbon fully so that composite film catalysis activity in the electrolyte is high, good stability.
3. the combined counter electrode that the present invention prepares being assembled into quantum dot sensitized solaode, the photoelectric transformation efficiency of battery system is higher.As a example by the quantum dot sensitized solaode that FeS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.45V, and short-circuit current density is 19.57mA/cm2, fill factor, curve factor is 0.64, and photoelectric transformation efficiency is 5.61%.
The technological advantage preparing combined counter electrode is: uses knife coating to combine with chemical conversion technique and is prepared, and prepared product catalysis activity in the electrolyte is high, and good stability, the photoelectric transformation efficiency of the quantum dot sensitized solaode assembled is higher.As a example by the quantum dot sensitized solaode that FeS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.45V, and short-circuit current density is 19.57mA/cm2, fill factor, curve factor is 0.64, and photoelectric transformation efficiency is 5.61%.
Accompanying drawing explanation
Fig. 1 is the present invention combined counter electrode structural representation for quantum dot sensitized solaode.
Fig. 2 is the J-V curve of the quantum dot sensitized solaode that FeS/C combined counter electrode assembles in embodiment 1.
Fig. 3 is the surface scan Electronic Speculum figure of the FeS/C film that embodiment 1 prepares.
Fig. 4 is the EDS collection of illustrative plates of the Fe/C film that embodiment 1 prepares.
Fig. 5 is the EDS collection of illustrative plates of the FeS/C film that embodiment 1 prepares.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Shown in Figure 1, a kind of combined counter electrode for quantum dot sensitized solaode disclosed by the invention, combined counter electrode includes substrate layer 1 and composite film 2, and composite film 2 is positioned on a panel of substrate layer 1.The material of described substrate layer 1 can select glass, fabric or polymer etc..Described composite film 2 is Cu2S/C or FeS/C or NiS/C.
In the present invention, preparing a kind of combined counter electrode for quantum dot sensitized solaode, it includes the following step:
The first step, prepared by slurry；
By the metal powder of carbon source, 50～500nm, binding agent and solvent mix homogeneously, obtain slurry；
Consumption: the slurry of 100g processed needs the binding agent of the metal powder of carbon source, 5～15g, 15～the 20g of 5～15g, the solvent of surplus.
Described carbon source includes active material and conductive agent, and active material has graphite, CNT, Graphene, activated carbon etc., and conductive agent has white carbon black, acetylene black etc..
Described metal powder is copper, ferrum or nickel etc., and metal powder particle size can be adjustable to tens micrometer ranges in tens nanometers.
Described binding agent is acrylic resin or Kynoar.
Described solvent is N-methyl pyrrole network alkanone or dipropylene glycol methyl ether.
Second step, prepares metal/carbon laminated film；
Choose glass, fabric or polymer etc. for base material, and base material is cleaned, dried, obtain the base material of cleaning；
The slurry first step obtained uniformly scratches at clean substrate surface, and blade coating thickness is 30～70 microns, obtains the first pre-adult；
3rd step, heat treatment removes solvent；
It is 50 DEG C～70 DEG C that the first pre-adult obtained by second step is placed in temperature, heat treatment 25～after 40 minutes, obtains the second pre-adult；
In the present invention, the second pre-adult does not contains solvent.The the second pre-adult prepared is that a kind of metal/carbon composite membrane is at base material.
4th step, chemical conversion metal sulfide/carbon combined counter electrode；
The the second pre-adult 3rd step obtained is dipped in many sulfur electrolyte that temperature is 20 DEG C～35 DEG C 6～8 hours, obtains metal sulfide/carbon combined counter electrode.
Many sulfur electrolyte is Na2The mixed aqueous solution of S Yu S, Na2The concentration of S be the concentration of 2mol/L, S be 3mol/L, preparation method be 60 DEG C stir 30 minutes.
In the present invention, the second pre-adult is inserted in many sulfur electrolyte, is, by chemical transformation, metal/carbon composite membrane is fully converted to metal sulfide/carbon composite membrane.
Embodiment 1
Preparation FeS/C combined counter electrode:
The first step, prepared by slurry；
By mixture (carbon source), 50～the iron powder of 500nm of graphite and white carbon black, acrylic resin (binding agent) and N-methyl pyrrole network alkanone (solvent) mix homogeneously, obtain slurry；
Graphite and white carbon black mix with mass ratio for 6:4, obtain mixture.
Consumption: the slurry of 100g processed needs graphite and the mixture of white carbon black, the iron powder of 10g, the acrylic resin of 16g of 10g, the N-methyl pyrrole network alkanone of 64g.
Second step, prepares metal/carbon laminated film；
Choosing glass is base material, and glass is cleaned, dried, obtain cleaning glass；
The slurry first step obtained uniformly scratches at clean substrate surface, and blade coating thickness is 50 microns, obtains the first pre-adult；
3rd step, heat treatment removes solvent；
It is 50 DEG C that the first pre-adult obtained by second step is placed in temperature, and heat treatment, after 30 minutes, obtains the second pre-adult；
In the present invention, the second pre-adult does not contains solvent, i.e. N-methyl pyrrole network alkanone.Fe/C composite membrane is attached on glass baseplate.Shown in Figure 4, the EDS collection of illustrative plates of Fe/C composite membrane, figure can be seen that the chemical composition of Fe/C composite membrane.
4th step, chemical conversion FeS/C combined counter electrode；
The the second pre-adult 3rd step obtained is dipped in many sulfur electrolyte that temperature is 25 DEG C 6 hours, obtains FeS/C combined counter electrode.Shown in Figure 5, the EDS collection of illustrative plates of FeS/C composite membrane, figure can be seen that the chemical composition of FeS/C composite membrane.Comparison diagram 4 and Fig. 5, it can be seen that the composition transfer of film layer before and after chemical conversion.
Many sulfur electrolyte is Na2The mixed aqueous solution of S Yu S, Na2The concentration of S be the concentration of 2mol/L, S be 3mol/L, preparation method be 60 DEG C stir 30 minutes.
In the present invention, the second pre-adult is inserted in many sulfur electrolyte, is, by chemical transformation, metal/carbon composite membrane is fully converted to metal sulfide/carbon composite membrane (i.e. FeS/C film).The surface scan Electronic Speculum of the FeS/C film prepared is as shown in Figure 3.The most this autgmentability dendritic morphology is similar to the root of plant, shows that FeS with C contacts fully, and this is conducive to receiving electronics efficiently, carries high catalytic activity.
FeS/C combined counter electrode performance characterization in QDSC:
The preparation of the light anode of QDSC:
Knife coating is utilized to prepare TiO2Light anode.Take P25TiO2Powder 0.6g, add 0.6ml deionized water, 2 acetylacetone,2,4-pentanediones, 1 OP-10,1ml polyglycol solution (take 1g PEG 20000 and be dissolved in 10ml deionized water and by magnetic stirrer to being completely dissolved) joins in agate mortar, grinds about 40min and must can be used for the nano-TiO of blade coating2Slurry.
Take the ITO electro-conductive glass being about 25mm × 20mm successively by the size of acetone, ethanol and deionized water ultrasonic cleaning, test its conducting surface with circuit tester.Nonconductive surface is placed downwards sheet glass (double faced adhesive tape is fixed), puts special silk screen above, take a small amount of nano-TiO prepared2Slurry, scratches from left to right with scraper, is repeated 15 times.Take off sheet glass, sinter 30min at 450 DEG C, be cooled to room temperature.
Above-mentioned base material is immersed 0.5MCd (NO3)2Ethanol solution in 5min, taking-up deionized water rinsing, dry up；Immerse 0.5MNa again25min in S solution, taking-up deionized water rinsing, dries up, and is repeated 3 times.By TiO2/ CdS electrode immerses 0.5MCd (NO3)2Ethanol solution in 5min, taking-up alcohol flushing, dry up；Immerse 50 DEG C of Na again2SeSO3Aqueous solution (23.7g/LSe, 75.6g/LNaSO3Be dissolved in the deionized water of respective amount, at 90 DEG C, stir 7h formulated) in 1h, taking-up deionized water rinsing, dry up.The TiO that will obtain2/ CdS/CdSe electrode immerses 0.5MZn (NO3) ethanol solution in 5min, taking-up deionized water rinsing dries up；Immerse 0.5MNa again25min in S solution, taking-up deionized water rinsing dries up i.e. makes TiO2/ CdS/CdSe/ZnS light anode.
The preparation of the electrolyte solution of QDSC:
It is Na by solution concentration2S2M and 3M weighs Na2S and simple substance S, the deionized water adding respective amount stirs 1h at 50 DEG C, is cooled to room temperature.
QDSC performance test:
According to the structure of QDSC, the FeS/C combined counter electrode that embodiment 1 prepares is assembled with light anode.The surface topography to electrode is observed, the J-V curve of the QDSC after using the test of CHI600A electrochemical analyser to assemble by scanning electron microscope (JSM-6010LA).
Photoelectric properties test condition: intensity of illumination is 100mWcm-2, wave-length coverage be 380～700nm xenon lamp (500W).
Performance characterization: see the J-V curve of the quantum dot sensitized solaode that Fig. 2 illustrates that FeS/C combined counter electrode assembles.As can be seen from the figure the open-circuit voltage of battery is 0.45V, and short-circuit current density is 19.57mA/cm2, fill factor, curve factor is 0.64, and photoelectric transformation efficiency is 5.61%.
Embodiment 2
Preparation Cu2S/C combined counter electrode:
The first step, prepared by slurry；
By mixture (carbon source), 50～the copper powder of 500nm of graphite and acetylene black, Kynoar (binding agent) and N-methyl pyrrole network alkanone (solvent) mix homogeneously, obtain slurry；
Graphite and acetylene black mix with mass ratio for 1:1, obtain mixture.
Consumption: the slurry of 100g processed needs graphite and the mixture of acetylene black, the copper powder of 10g, the Kynoar of 15g of 15g, the N-methyl pyrrole network alkanone of 60g.
Second step, prepares metal/carbon laminated film；
Choosing glass is base material, and glass is cleaned, dried, obtain cleaning glass；
The slurry first step obtained uniformly scratches at clean substrate surface, and blade coating thickness is 60 microns, obtains the first pre-adult；
3rd step, heat treatment removes solvent；
It is 60 DEG C that the first pre-adult obtained by second step is placed in temperature, and heat treatment, after 25 minutes, obtains the second pre-adult；
In the present invention, the second pre-adult does not contains solvent, i.e. N-methyl pyrrole network alkanone.Cu/C composite membrane is attached on glass baseplate.
4th step, chemical conversion Cu2S/C combined counter electrode；
The the second pre-adult 3rd step obtained is dipped in many sulfur electrolyte that temperature is 30 DEG C 6 hours, obtains Cu2S/C combined counter electrode.
Many sulfur electrolyte is Na2The mixed aqueous solution of S Yu S, Na2The concentration of S be the concentration of 2mol/L, S be 3mol/L, preparation method be 60 DEG C stir 30 minutes.
In the present invention, the second pre-adult is inserted in many sulfur electrolyte, is, by chemical transformation, metal/carbon composite membrane is fully converted to metal sulfide/carbon composite membrane (i.e. Cu2S/C film).
With Cu2As a example by the quantum dot sensitized solaode that S/C combined counter electrode assembles, the open-circuit voltage of battery is 0.43V, and short-circuit current density is 19.49mA/cm2, fill factor, curve factor is 0.57, and photoelectric transformation efficiency is 4.75%.
Embodiment 3
Preparation NiS/C combined counter electrode:
The first step, prepared by slurry；
By mixture (carbon source), 50～the nikel powder of 500nm of activated carbon and white carbon black, acrylic resin (binding agent) and dipropylene glycol methyl ether (solvent) mix homogeneously, obtain slurry；
Activated carbon and white carbon black mix with mass ratio for 4:6, obtain mixture.
Consumption: the slurry of 100g processed needs activated carbon and the mixture of white carbon black, the nikel powder of 12g, the acrylic resin of 14g of 18g, the N-methyl pyrrole network alkanone of 56g.
Second step, prepares metal/carbon laminated film；
Choosing glass is base material, and glass is cleaned, dried, obtain cleaning glass；
The slurry first step obtained uniformly scratches at clean substrate surface, and blade coating thickness is 50 microns, obtains the first pre-adult；
3rd step, heat treatment removes solvent；
It is 55 DEG C that the first pre-adult obtained by second step is placed in temperature, and heat treatment, after 30 minutes, obtains the second pre-adult；
In the present invention, the second pre-adult does not contains solvent, i.e. dipropylene glycol methyl ether.Ni/C composite membrane is attached on glass baseplate.
4th step, chemical conversion NiS/C combined counter electrode；
The the second pre-adult 3rd step obtained is dipped in many sulfur electrolyte that temperature is 25 DEG C 7 hours, obtains NiS/C combined counter electrode.
Many sulfur electrolyte is Na2The mixed aqueous solution of S Yu S, Na2The concentration of S be the concentration of 2mol/L, S be 3mol/L, preparation method be 60 DEG C stir 30 minutes.
In the present invention, the second pre-adult is inserted in many sulfur electrolyte, is, by chemical transformation, metal/carbon composite membrane is fully converted to metal sulfide/carbon composite membrane (i.e. NiS/C film).
As a example by the quantum dot sensitized solaode that NiS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.44V, and short-circuit current density is 19.46mA/cm2, fill factor, curve factor is 0.51, and photoelectric transformation efficiency is 4.34%.
The present invention propose use knife coating combine with chemical conversion technique to electrode preparation method, to be solved is how to improve the technical problem that the photoelectric transformation efficiency of existing quantum dot sensitization solar battery is relatively low, present invention employs composite film processed on inorganic non-metallic base material, then the technological means of chemical conversion is carried out, thus realize metal sulfide and be fully contacted with carbon, make composite film catalysis activity in the electrolyte high, good stability.The combined counter electrode present invention prepared is assembled into quantum dot sensitized solaode, and the photoelectric transformation efficiency of battery system is higher.
Claims (9)
1. the combined counter electrode for quantum dot sensitized solaode, it is characterized in that: this combined counter electrode includes substrate layer (1) and composite film (2), composite film (2) is positioned on a panel of substrate layer (1)；
The material of described substrate layer (1) can select glass, fabric or polymer；
Described composite film (2) is Cu2S/C or FeS/C or NiS/C.
A kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 1, it is characterized in that: as a example by the quantum dot sensitized solaode that FeS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.45V, and short-circuit current density is 19.57mA/cm2, fill factor, curve factor is 0.64, and photoelectric transformation efficiency is 5.61%.
A kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 1, it is characterised in that: with Cu2As a example by the quantum dot sensitized solaode that S/C combined counter electrode assembles, the open-circuit voltage of battery is 0.43V, and short-circuit current density is 19.49mA/cm2, fill factor, curve factor is 0.57, and photoelectric transformation efficiency is 4.75%.
A kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 1, it is characterized in that: as a example by the quantum dot sensitized solaode that NiS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.44V, and short-circuit current density is 19.46mA/cm2, fill factor, curve factor is 0.51, and photoelectric transformation efficiency is 4.34%.
5. the preparation method of combined counter electrode for quantum dot sensitized solaode, it is characterised in that include the following step:
The first step, prepared by slurry；
By the metal powder of carbon source, 50～500nm, binding agent and solvent mix homogeneously, obtain slurry；
Consumption: the slurry of 100g processed needs the binding agent of the metal powder of carbon source, 5～15g, 15～the 20g of 5～15g, the solvent of surplus；
Described carbon source includes active material and conductive agent, and active material has graphite, CNT, Graphene, activated carbon etc., and conductive agent has white carbon black, acetylene black etc.；
Described metal powder is copper, ferrum or nickel etc., and metal powder particle size can be adjustable to tens micrometer ranges in tens nanometers；
Described binding agent is acrylic resin or Kynoar；
Described solvent is N-methyl pyrrole network alkanone or dipropylene glycol methyl ether；
Second step, prepares metal/carbon laminated film；
Choosing glass, fabric or polymer is base material, and base material is cleaned, dried, obtain cleaning base material；
The slurry first step obtained uniformly scratches at clean substrate surface, and blade coating thickness is 30～70 microns, obtains the first pre-adult；
3rd step, heat treatment removes solvent；
It is 50 DEG C～70 DEG C that the first pre-adult obtained by second step is placed in temperature, heat treatment 25～after 40 minutes, obtains the second pre-adult；
4th step, chemical conversion metal sulfide/carbon combined counter electrode；
The the second pre-adult 3rd step obtained is dipped in many sulfur electrolyte that temperature is 20 DEG C～35 DEG C 6～8 hours, obtains metal sulfide/carbon combined counter electrode；
Many sulfur electrolyte is Na2The mixed aqueous solution of S Yu S, Na2The concentration of S be the concentration of 2mol/L, S be 3mol/L, preparation method be 60 DEG C stir 30 minutes.
The preparation method of a kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 5, it is characterized in that: the combined counter electrode prepared includes substrate layer (1) and composite film (2), and composite film (2) is positioned on a panel of substrate layer (1)；
The material of described substrate layer (1) can select glass, fabric or polymer；
Described composite film (2) is Cu2S/C or FeS/C or NiS/C.
The preparation method of a kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 5, it is characterized in that: as a example by the quantum dot sensitized solaode that FeS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.45V, and short-circuit current density is 19.57mA/cm2, fill factor, curve factor is 0.64, and photoelectric transformation efficiency is 5.61%.
The preparation method of a kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 5, it is characterised in that: with Cu2As a example by the quantum dot sensitized solaode that S/C combined counter electrode assembles, the open-circuit voltage of battery is 0.43V, and short-circuit current density is 19.49mA/cm2, fill factor, curve factor is 0.57, and photoelectric transformation efficiency is 4.75%.
The preparation method of a kind of combined counter electrode for quantum dot sensitized solaode the most according to claim 5, it is characterized in that: as a example by the quantum dot sensitized solaode that NiS/C combined counter electrode assembles, the open-circuit voltage of battery is 0.44V, and short-circuit current density is 19.46mA/cm2, fill factor, curve factor is 0.51, and photoelectric transformation efficiency is 4.34%.
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| CN107946078A (en) * | 2017-11-15 | 2018-04-20 | 青岛大学 | Preparation method for quantum dot sensitized solar cell compound material flexible to electrode |
| CN111243869A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院福建物质结构研究所 | Composite material, preparation method and application thereof |
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| CN106328379A (en) * | 2016-09-18 | 2017-01-11 | 河南师范大学 | Preparation method of quantum dot sensitized solar cell graphene composite counter electrode |
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| CN107230551A (en) * | 2017-05-26 | 2017-10-03 | 桂林理工大学 | A kind of TiO2/ GQDs/NiS hetero-junctions light anodes and preparation method thereof |
| CN107230551B (en) * | 2017-05-26 | 2019-10-11 | 桂林理工大学 | A kind of TiO2/ GQDs/NiS hetero-junctions light anode and preparation method thereof |
| CN107946078A (en) * | 2017-11-15 | 2018-04-20 | 青岛大学 | Preparation method for quantum dot sensitized solar cell compound material flexible to electrode |
| CN111243869A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院福建物质结构研究所 | Composite material, preparation method and application thereof |
| CN111243869B (en) * | 2018-11-29 | 2022-06-10 | 中国科学院福建物质结构研究所 | Composite material, preparation method and application thereof |
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