CN115458332A - Ag 8 SnS x Se 6-x Preparation method and application of film - Google Patents
Ag 8 SnS x Se 6-x Preparation method and application of film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000004528 spin coating Methods 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
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- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 10
- 239000010409 thin film Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 238000011112 process operation Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 4
- 150000003346 selenoethers Chemical class 0.000 description 4
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- -1 transition metal nitrides Chemical class 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses Ag 8 SnS x Se 6‑x A preparation method and application of a film belong to the technical field of semiconductor material and energy preparation. The method takes oleylamine as a solvent, a silver source, a tin source and a sulfur source as solutes, and the solutes are dissolved in the solvent; stirring and heating for reaction, centrifuging and cleaning after heating, and drying Ag 8 SnS 6 And (3) nanoparticles. Ag 8 SnS 6 Putting the nano particles into a mixed solution of n-butylamine and thioglycollic acid, and then carrying out ultrasonic treatment to obtain ink; putting the cleaned glass on spin coating equipment, performing spin coating by using ink, drying after the spin coating is finished, and annealing to obtain Ag 8 SnS x Se 6‑x A film. The invention prepares Ag by a solvothermal method 8 SnS 6 Nanometer particles, spin coating and selenizing annealing to obtain Ag 8 SnS x Se 6‑x A film; ag 8 SnS x Se 6‑x The film has the advantages of low raw material cost, simple process operation, short preparation period and the like; ag 8 SnS x Se 6‑x The film can be used as a counter electrode material of a dye-sensitized solar cell.
Description
Technical Field
The invention relates to Ag 8 SnS x Se 6-x A preparation method and application of a film belong to the technical field of semiconductor material and energy preparation.
Background
The development of renewable energy sources including wind, solar and tidal energy has become a global trend and common consensus today; the utilization of solar energy is an effective way to relieve the energy crisis and the deterioration of the ecological environment; however, further reduction of the cost of solar cells and improvement of the power generation efficiency remain major challenges facing photovoltaic power generation.
Dye-sensitized solar cells (DSSCs) are considered as a promising alternative to commercial silicon solar cells. DSSCs have irreplaceable advantages in large-scale commercial production due to simple manufacturing process and low cost. DSSCs improve photovoltaic efficiency and reduce manufacturing costs by optimizing photoanodes, counter Electrodes (CEs), photosensitizers, and electrolytes. Wherein CEs is I - /1 3 - The key to the regeneration of the redox couple. For typical DSSCs, pt CEs account for over 50% of the total device cost, and Pt CEs are susceptible to corrosion when in contact with liquid electrolytes. Therefore, research without Pt CEs has attracted great interest in order to reduce costs, improve Power Conversion Efficiency (PCE) and stability of devices.
The performance of DSSCs depends to a large extent on the conductivity and electrocatalytic activity of the CEs. In addition, the grain size, morphology and thickness also have a large impact on the performance of DSSCs. In recent years, carbon-based materials (graphite, graphene, carbon nanofibers), conductive polymers (porous poly (PProDOT), polyaniline (PANI), polypyrrole (PPy)), transition metal nitrides (TiN, crN, fe) 2 N, etc.) and carbides (TiC, ta) 4 C 3 NbC, etc.), metal oxide materials (TaO, mnO) 2 ZnO, etc.), composite materials (MnCo 2 O 4 @NiCo 2 O 4 ， CoSe@NPC/CoSe@CNT，MoIn 2 S 4 @ CNTs, etc.), metal sulfides (NiMoS) 3 ，Cu 2 Cu 1-x Mn x SnS 4 ，Bi 2 S 3 ) And selenide (Cu) 3 SnS X Se 4-X ，NiSe 2 ，Cu 2 ZnSnSe 4 ) Have been intensively studied as alternatives. Among platinum-free materials, selenides have superior catalytic activity, conductivity, and stability. In general, the conductivity of Transition Metal Compounds (TMC) follows that of selenides>Sulfide compound>The order of the oxides. The selenized TMC CEs have good conductivity and electricityCatalytic activity, such as: cu 3 SnS X Se 4-X And Cu 2 ZnSnS 4 After the S in the catalyst is replaced by Se, the charge transfer rate and the catalytic activity are obviously improved. Ag 8 SnS 6 (ATS) is a narrow bandgap (Eg = 1.12-1.57 eV) semiconductor with excellent photovoltaic performance, such as ideal bandgap, suitable band edge, high absorption coefficient and significant carrier mobility. According to the Shockley-Queisser detailed balance model, the optimal band gap of the single junction solar cell is 1.34 eV, and the ultimate Power Conversion Efficiency (PCE) is 33.7%. Therefore, the band gap of the ATS is close to the ideal band gap, and therefore, a preparation method with low cost, simple process operation and short preparation period is urgently needed to be found.
The invention uses the ATS film to carry out selenizing annealing to prepare the Ag8SnSxSe6-x (ATSSe) film. Ag 8 SnS x Se 6-x The film has the advantages of low raw material cost, simple process operation, short preparation period and the like. Ag 8 SnS x Se 6-x The film can be used as a counter electrode material of a dye-sensitized solar cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Ag 8 SnS x Se 6-x A method for preparing the film; preparation of Ag by Solvothermal method, spin coating method and annealing 8 SnS x Se 6-x A film; the method has the advantages of low raw material cost, simple process operation, safe experimental process, low medicine cost and short preparation period.
Ag 8 SnS x Se 6-x The preparation method of the film comprises the following specific steps:
(1) Dissolving a silver source in an organic solvent oleylamine, adding a tin source and a sulfur source into the oleylamine, and dissolving to obtain a precursor solution; heating the precursor solution to 150-190 deg.C under stirring for 30-60min, heating to 200-250 deg.C for 30-60min, cooling to 60-90 deg.C, cleaning, and centrifuging to obtain black precipitate; washing and centrifuging for 3-5 times, and drying to obtain Ag 8 SnS 6 A nanoparticle powder.
(2) Will be provided with30mg of Ag 8 SnS 6 Putting black powder of nano particles into a mixed solution of n-butylamine and thioglycollic acid, and then carrying out ultrasonic treatment to obtain ink; putting the cleaned glass on spin coating equipment, sucking ink by using a liquid-moving gun for spin coating, and drying after the spin coating is finished to obtain Ag 8 SnS 6 A film; then Ag is added 8 SnS 6 Putting the film into a tube furnace, putting 5-20mg of the film into the tube furnace at the same time, annealing together, and obtaining Ag after annealing 8 SnS x Se 6-x A film.
Preferably, the silver source in step (1) of the present invention is any one of silver nitrate, silver acetate and silver sulfate; the tin source is any one of stannous chloride dihydrate, stannic chloride and stannous acetate; the sulfur source is any one of thiourea, n-dodecyl mercaptan, ethanethiol, carbon disulfide and potassium sulfide.
Preferably, in step (1) of the present invention, the molar ratio of the silver source to the tin source to the sulfur source is 8.
Preferably, the stirring speed in step (1) of the present invention is 400 to 600rpm; the centrifugation speed is 8000-10000rpm, and the centrifugation time is 3-10min; the drying temperature is 60-80 ℃, and the drying time is 2-24h; washing with a mixed solution of n-hexane and absolute ethyl alcohol at a volume ratio of (1-3): 1.
Preferably, the volume ratio of n-butylamine to thioglycolic acid in the mixed solution in step (2) of the present invention is 1 (0.1-0.3).
Preferably, the time of the ultrasonic treatment in the step (2) of the invention is 30-60min, and the drying conditions are as follows: drying at 100-200 deg.C for 1-5min.
Preferably, the annealing conditions in step (2) of the present invention are: annealing at 400 deg.C for 30-120min, with the temperature rise rate of the tubular annealing furnace being 10-15 deg.C/min, and annealing in nitrogen environment.
Preferably, the glass is cleaned by adopting absolute ethyl alcohol and acetone for three times, the rotating speed is 500-5000rpm for 10-20s, and a liquid transfer gun sucks 10-20uL.
Another object of the present invention is to provide Ag prepared by the method 8 SnS x Se 6-x Film(s)The application of the compound is taken as a counter electrode material of a dye-sensitized solar cell.
The preparation principle of the invention is as follows: organic solvent oleylamine is used as solvent, silver acetate, tin chloride dihydrate and thiourea are used as solute, and at low temperature, the silver source and the silver sulfide react to generate Ag 2 S species, ag with increasing temperature 2 S and tin source are combined to generate Ag 8 SnS 6 A substance; making into Ag 8 SnS 6 After the film is formed, selenizing annealing is carried out to generate Ag 8 SnS x Se 6-x A film; in the selenizing annealing process, selenium is melted at high temperature and volatilized, and the atomic radius is larger than S 2- Se of (1.84 a) 2- (1.98 a) substitution of S 2- Into Ag 8 SnS 6 In the crystal lattice of (1), form Ag 8 SnS x Se 6-x A substance; the position of S is easily substituted by Se under the same conditions.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention prepares a new Ag 8 SnS x Se 6-x A film.
(2) The invention has the advantages of low cost of raw materials, simple process operation, short preparation period and the like. By adding relatively pure Ag 8 SnS 6 Nanoparticles of Ag 8 SnS 6 The nano particles are selenized and annealed to obtain a selenide.
(3) Ag prepared by the invention 8 SnS x Se 6-x The film material can be used as a counter electrode material of a dye-sensitized solar cell.
Drawings
FIG. 1 is sample Ag prepared in example 1 8 SnS 6 X-ray diffraction pattern of the nanoparticles.
FIG. 2 is sample Ag prepared in example 1 8 SnS x Se 6-x X-ray diffraction pattern of the film.
FIG. 3 is sample Ag prepared in example 2 8 SnS x Se 6-x X-ray diffraction pattern of the film.
FIG. 4 is a schematic view ofEXAMPLE 2 preparation of sample Ag 8 SnS x Se 6-x Scanning electron micrographs of the films.
FIG. 5 is sample Ag prepared in example 3 8 SnS x Se 6-x X-ray diffraction pattern of the film.
Detailed Description
The invention relates to Ag 8 SnS x Se 6-x The present invention will be further described with reference to the following embodiments, but the scope of the present invention is not limited to the above description.
The medicines used in the embodiment of the invention are all analytical pure products purchased from the market and are not further purified.
Example 1
Ag 8 SnS x Se 6-x The preparation method of the film comprises the following specific steps:
(1) Dissolving 8mmol of silver source (silver acetate) in 40ml of oleylamine, adding 1mmol of tin source (stannous chloride dihydrate) and 6mmol of sulfur source (thiourea) into the oleylamine, and dissolving by ultrasonic for 30min to obtain precursor solution; the molar ratio of the silver source to the tin source to the sulfur source is 8.
Stirring and heating the precursor solution at 500rpm to 180 ℃ for 30min, heating to 240 ℃ for 40min, naturally cooling to 60 ℃ after heating, performing first-step centrifugation at 9000rpm for 3min to obtain black precipitate, and cleaning with n-hexane: absolute ethanol (volume ratio 1:1); centrifuging and cleaning for 3 times to obtain black precipitate, and drying at 60 deg.C for 24 hr to obtain Ag 8 SnS 6 And (3) nanoparticles.
(2) Weigh 30mg of Ag 8 SnS 6 Putting black powder of the nano particles into 180ul of a mixed solution of n-butylamine and thioglycollic acid (volume ratio of 1; putting the cleaned glass on spin-coating equipment, and sucking 10ul of printing ink for multiple times by using a liquid-moving gun for spin-coating at the rotating speed of 600rpm for 20s; drying at 150 deg.C for 3min to obtain Ag 8 SnS 6 A film; then Ag is added 8 SnS 6 Placing the film into a tube furnace, simultaneously placing 5mg of selenium powder into the tube furnace for annealing together, annealing at 400 ℃ for 80min, wherein the temperature rise speed of the tube annealing furnace is 13 ℃/min, annealing in a nitrogen environment, and obtaining Ag after the annealing is finished 8 SnS x Se 6-x A film.
Ag prepared in this example 8 SnS 6 The XRD pattern of the nanoparticles is shown in FIG. 1, and it can be seen from FIG. 1 that the diffraction peaks at diffraction angles of 27.43 °, 28.95 °, 36.07 °, 38.16 °, 43.60 °, 47.96 ° and 49.90 ° respectively and Ag 8 SnS 6 The (411), (022), (313), (114), (331), (603), (424) and (532) crystal faces of the standard card (PDF # 38-0434) of (1) correspond to each other; the prepared material is Ag 8 SnS 6 And (3) nanoparticles.
Mixing Ag with water 8 SnS 6 Dispersing the powder into a mixed solution of n-butylamine and thioglycollic acid (volume ratio of 1 8 SnS x Se 6-x A film. Ag prepared in example 1 8 SnS x Se 6-x The XRD pattern of the film is shown in FIG. 2, and it can be seen from FIG. 2 that the diffraction peaks at diffraction angles of 26.58 °, 27.76 °, 34.46 °, 35.31 °, 39.91 °, 42.40 °, 46.408 ° and 48.71 ° are respectively associated with Ag 8 SnSe 6 The (311), (222), (330), (331), (422), (511), (440) and (531) crystal faces of the standard cards (PDF # 19-1163) correspond to each other; in FIG. 2, mainly Ag 8 SnSe 6 But contains a small amount of Ag therein 8 SnS 6 The diffraction peak of (4); mainly, se2- (1.98 a) with the atomic radius larger than that of S2- (1.84 a) replaces S2 to enter Ag during high-temperature selenization annealing 8 SnS 6 In the crystal lattice of (a); meanwhile, S is not completely substituted by Se, and a small amount of S still exists in the selenized film; preparing to obtain Ag 8 SnS x Se 6-x A film.
Example 2
Ag 8 SnS x Se 6-x The preparation method of the film comprises the following specific steps:
(1) Dissolving 8mmol of silver source (silver nitrate) in 40ml of oleylamine, adding 1mmol of tin source (tin chloride) and 6mmol of sulfur source (ethanethiol) into the oleylamine, and dissolving for 30min by ultrasonic treatment to obtain a precursor solution; the molar ratio of the silver source to the tin source to the sulfur source is 8.
Stirring and heating the precursor solution at 500rpm to 150 ℃ for 60min, heating to 200 ℃ for 60min, naturally cooling to 70 ℃ after heating, performing first-step centrifugation at 8000rpm for 8min to obtain black precipitate, and cleaning with n-hexane: absolute ethanol (volume ratio 2:1); centrifuging and cleaning for 3 times to obtain black precipitate, and drying at 80 deg.C for 12 hr to obtain Ag 8 SnS 6 And (3) nanoparticles.
(2) Weigh 30mg of Ag 8 SnS 6 Putting black powder of the nano particles into 180uL of a mixed solution of n-butylamine and thioglycollic acid (the volume ratio is 1; putting the cleaned glass on spin coating equipment, absorbing 10ul of printing ink for multiple times by using a liquid-moving gun for spin coating, rotating at 5000rpm for 10s, and drying at 200 ℃ for 1min after the spin coating is finished to obtain Ag preliminarily 8 SnS 6 A film; then Ag is added 8 SnS 6 Placing the film into a tube furnace, simultaneously placing 10mg of selenium powder into the tube furnace for annealing together, annealing at 400 ℃ for 120min, wherein the temperature rise speed of the tube annealing furnace is 15 ℃/min, annealing is carried out in a nitrogen environment, and Ag is obtained after the annealing is finished 8 SnS x Se 6-x A film.
From the XRD pattern in FIG. 3, the material was Ag 8 SnS x Se 6-x (ii) a While Ag can be seen from FIG. 4 8 SnS x Se 6-x The film surface was dense but some larger particles appeared.
Example 3
Ag 8 SnS x Se 6-x The preparation method of the film comprises the following specific steps:
(1) Dissolving 8mmol of silver source (silver sulfate) in 40ml of oleylamine, adding 1mmol of tin source (stannous acetate) and 6mmol of sulfur source (n-dodecyl mercaptan) into the oleylamine, and dissolving for 30min by ultrasonic treatment to obtain precursor solution; the molar ratio of the silver source to the tin source to the sulfur source is 8.
Stirring and heating the precursor solution at 500rpm to 190 ℃ for 40min, heating to 250 ℃ for 30min, naturally cooling to 90 ℃ after heating, centrifuging for the first step at a centrifugal speed of 10000rpm for 10min to obtain a black precipitate, and then cleaning by adopting n-hexane: absolute ethanol (volume ratio 3:1); centrifuging and cleaning for 3 times to obtain black precipitate, and drying at 70 deg.C for 12 hr to obtain Ag 8 SnS 6 And (3) nanoparticles.
(2) Weigh 30mg of Ag 8 SnS 6 Putting black powder of the nano particles into 180ul of a mixed solution of n-butylamine and thioglycollic acid (volume ratio of 1; putting the cleaned glass on spin-coating equipment, and sucking 10ul of printing ink for multiple times by using a liquid-moving gun for spin-coating, wherein the rotating speed is 2500rpm and the rotating speed is 15s; drying at 100 deg.C for 5min to obtain Ag 8 SnS 6 A film; then Ag is added 8 SnS 6 Putting the film into a tube furnace, simultaneously putting 5mg of selenium powder into the tube furnace for annealing together, annealing at 400 ℃ for 50min, wherein the temperature rise speed of the tube annealing furnace is 10 ℃/min, annealing is carried out in a nitrogen environment, and Ag is obtained after the annealing is finished 8 SnS x Se 6-x A film. From the XRD pattern in FIG. 5, the material was Ag 8 SnS x Se 6-x 。
Ag prepared in examples 1-3 8 SnS x Se 6-x XRD and SEM test analysis are carried out on the film, and Ag with better crystallinity is obtained 8 SnS x Se 6-x . It can be seen from the XRD patterns of fig. 2, 3 and 5 that the content of selenium powder does not change the Ag formed to some extent 8 SnS x Se 6-x The diffraction peak of (2) shows that in the high-temperature selenization process, the position of S is replaced once Se is added, so that the diffraction angle of the peak and the diffraction peak are directly converted into a new substance, but the S is not completely replaced by Se, and a small amount of S still exists in the selenized film; ag 8 SnS x Se 6-x The film tool has ultraviolet and visible light regionsHas better photocatalytic activity and electrochemical performance, and is more suitable to be used as a counter electrode material of a dye-sensitized solar cell.
Claims (9)
1. Ag 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps:
(1) Dissolving a silver source in an organic solvent oleylamine, adding a tin source and a sulfur source into the oleylamine, and dissolving to obtain a precursor solution; heating the precursor solution to 150-190 ℃ under stirring for reaction for 30-60min, then continuously heating to 200-250 ℃ for reaction for 30-60min, cooling to 60-90 ℃, washing the solvent, and centrifuging to obtain black precipitate; washing and centrifuging for 3-5 times, and drying to obtain Ag 8 SnS 6 A nanoparticle powder;
(2) Mixing 30mgAg 8 SnS 6 Putting black powder of nano particles into a mixed solution of n-butylamine and thioglycollic acid, and then carrying out ultrasonic treatment to obtain ink; putting the cleaned glass on spin coating equipment, sucking ink by using a liquid-moving gun for spin coating, and drying after the spin coating is finished to obtain Ag 8 SnS 6 A film; then Ag is added 8 SnS 6 Putting the film into a tube furnace, simultaneously putting 5-20mg of selenium powder into the tube furnace for annealing together, and obtaining Ag after annealing 8 SnS x Se 6-x A film.
2. Ag according to claim 1 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps: the silver source in the step (1) is any one of silver nitrate, silver acetate and silver sulfate;
the tin source is any one of stannous chloride dihydrate, stannic chloride and stannous acetate;
the sulfur source is any one of thiourea, n-dodecyl mercaptan, ethanethiol, carbon disulfide and potassium sulfide.
3. Ag according to claim 2 8 SnS x Se 6-x Production of filmsThe preparation method is characterized by comprising the following steps: the molar ratio of the silver source to the tin source to the sulfur source in the step (1) is 8.
4. Ag according to claim 1 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps: the stirring speed in the step (1) is 400-600rpm; the centrifugation speed is 8000-10000rpm, and the centrifugation time is 3-10min; the drying temperature is 60-80 ℃, and the drying time is 2-24h; washing with a mixed solution of n-hexane and absolute ethyl alcohol at a volume ratio of (1-3): 1.
5. Ag according to claim 1 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps: the volume ratio of n-butylamine to thioglycollic acid in the mixed solution in the step (2) is 1 (0.1-0.3).
6. Ag according to claim 1 or 5 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps: the ultrasonic treatment time in the step (2) is 30-60min, and the drying conditions are as follows: drying at 100-200 deg.C for 1-5min.
7. Ag according to claim 6 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps: the annealing conditions in the step (2) are as follows: annealing at 400 deg.C for 30-120min, with the temperature rise rate of the tubular annealing furnace being 10-15 deg.C/min, and annealing in nitrogen environment.
8. Ag according to claim 1 8 SnS x Se 6-x The preparation method of the film is characterized by comprising the following steps: the glass is cleaned for three times by adopting absolute ethyl alcohol and acetone, the rotating speed is 500-5000rpm for 10-20s, and a liquid transfer gun sucks 10-20ul.
9. Ag prepared by the process of any one of claims 1~8 8 SnS x Se 6-x The thin film is applied to being used as a counter electrode material of a dye-sensitized solar cell.
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