CN105776888A - Method for preparing pyrite phase iron disulfide thin film - Google Patents
Method for preparing pyrite phase iron disulfide thin film Download PDFInfo
- Publication number
- CN105776888A CN105776888A CN201610077574.8A CN201610077574A CN105776888A CN 105776888 A CN105776888 A CN 105776888A CN 201610077574 A CN201610077574 A CN 201610077574A CN 105776888 A CN105776888 A CN 105776888A
- Authority
- CN
- China
- Prior art keywords
- ferrous disulfide
- pyrite phase
- powder
- pyrite
- phase ferrous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 63
- 239000011028 pyrite Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 49
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910000339 iron disulfide Inorganic materials 0.000 title abstract description 14
- 239000010409 thin film Substances 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011521 glass Substances 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000007650 screen-printing Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 229940095991 ferrous disulfide Drugs 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000001856 Ethyl cellulose Substances 0.000 claims description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- -1 ferrous chlorides Chemical class 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 24
- 239000002245 particle Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
- C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/119—Deposition methods from solutions or suspensions by printing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a method for preparing a pyrite phase iron disulfide thin film.The method includes the steps that pyrite phase iron disulfide powder is obtained through a hydrothermal method or a thermal injection method; the iron disulfide powder, ethyecellulose and terpilenol are mixed into slurry; a glass or FTO conductive glass substrate is brushed with the iron disulfide slurry through a silk screen printing method; thermal treatment is conducted in the sulfur and nitrogen/argon atmosphere, and the pyrite phase iron disulfide thin film is obtained.The obtained pyrite phase iron disulfide thin film can effectively solve the problem of sulfur omission and can serve as a light absorbing layer or a counter electrode of a solar cell or be used for an electrode.
Description
Technical field
The present invention relates to photoelectric material, new energy materials and technical field, particularly a kind of pyrite phase ferrous disulfide film and preparation method thereof.
Background technology
Pyrite phase ferrous disulfide (FeS2) there are suitable energy gap (0.95eV) and the very big absorption coefficient of light (α >=5 × 105, λ=700nm), and its component is cheap, rich reserves, nontoxic, is a kind of being widely studied and the material of great application potential in the field such as lithium battery and solaode.
At present, there is the multiple method preparing pyrite phase ferrous disulfide film both at home and abroad, such as iron sulfide embrane method, sol-gal process, electrodeposition process, hydro-thermal method, nebulization etc..Existing prepare pyrite phase ferrous disulfide film have drawbacks in that in thin film that ubiquity sulfur is vacant, not easily obtain pyrite phase ferrous disulfide film.
Summary of the invention
The present invention is just for above-mentioned the deficiencies in the prior art, it is provided that the preparation method of a kind of pyrite phase ferrous disulfide film, its objective is to overcome sulfur omission phenomenon, it is thus achieved that pyrite phase ferrous disulfide film.
It is an object of the invention to be achieved through the following technical solutions: as it is shown in figure 1, the preparation method of a kind of pyrite phase ferrous disulfide film, it is characterised in that realize step as follows:
(1) using hydro-thermal method or hot injection method to obtain pyrite phase ferrous disulfide powder, pyrite phase ferrous disulfide powder is cleaned, standby after drying；
(2) by pyrite phase ferrous disulfide powder and ethyl cellulose, terpineol mixing, magnetic agitation is uniform, it is thus achieved that slurry；
(3) FTO electro-conductive glass or glass substrate are cleaned in acetone, dehydrated alcohol, deionized water for ultrasonic successively, blow open standby；
(4) by silk screen print method by pyrite phase ferrous disulfide slurry brush on glass or FTO Conducting Glass；
(5) ferrous disulfide film of Sublimed Sulfur powder and silk screen printing is carried out heat treatment, substrate obtains pyrite phase ferrous disulfide film.
Described step (1) uses hydro-thermal method to obtain pyrite phase ferrous disulfide powder method: ferrous sulfate heptahydrate and polyvinylpyrrolidone are added in the aqueous solution of 90-95 °, thiourea is added after dissolving, above-mentioned solution is poured in polytetrafluoroethyllining lining, add sulfur powder and ethanol in proper amount to the 80% of liner volume, it is cooled to room temperature after autoclave being put in baking oven 190-210 DEG C of reaction 4-40 hour to take out, black powder is used ethanol, deionized water, Carbon bisulfide washs, dried for standby.
Described step (1) uses hot injection method to obtain pyrite phase ferrous disulfide powder method: add oleyl amine and four water ferrous chlorides in the three-necked bottle of nitrogen protection, and 110-120 DEG C is reacted 1-1.5 hour, it is thus achieved that solution A；Being dissolved in diphenyl ether by sulfur powder in the container of another nitrogen protection, 70-80 DEG C of reaction obtains solution B in 1-1.5 hour；By needle tubing, B solution is injected in solution A, 210-220 DEG C reaction 5-24 hour after be cooled to room temperature.Black powder is used dehydrated alcohol, chloroform, dried for standby.
The mol ratio of described ferrous sulfate heptahydrate, polyvinylpyrrolidone, thiourea and sulfur powder is 1:1.5-2:2-2.5:4-6.
Described four water ferrous chlorides, sulfur powder mol ratio be 1:5-7, every mM of four water ferrous chlorides use 10 milliliters of oleyl amines to dissolve, and every mM of sulfur powder dissolves with 1 milliliter of diphenyl ether.
When hydro-thermal method or hot injection method obtain different-shape pyrite phase ferrous disulfide powder in described step (1), by adjusting reaction time, obtain the pyrite phase ferrous disulfide powder of variable grain size.
The pyrite phase ferrous disulfide powder of described step (2), ethyl cellulose, terpineol weight ratio be 1:1:4.
Described step (5) heat treatment Sublimed Sulfur powder purity is more than 99%, and heat treatment temperature is 400-550 DEG C, heat treatment 1-3 hour under sulfur and nitrogen/argon gas atmosphere.Heat treatment under sulfur and nitrogen/argon gas atmosphere, can overcome ubiquity sulfur omission problem in ferrous disulfide film preparation process, it is thus achieved that pyrite phase ferrous disulfide film.
The thickness of described pyrite phase ferrous disulfide film is 1-10 micron.The thickness of pyrite phase ferrous disulfide film can be regulated by the number of times of silk screen printing.
The present invention compared with prior art has the advantage that
(1) present invention utilizes hydro-thermal method or hot injection method to obtain pyrite phase ferrous disulfide powder；By ferrous disulfide powder and ethyl cellulose, terpineol furnishing slurry；By silk screen print method by ferrous disulfide slurry brush on glass or FTO Conducting Glass；Heat treatment under sulfur and nitrogen/argon gas atmosphere, it is thus achieved that pyrite phase ferrous disulfide film.The pyrite phase ferrous disulfide film that the present invention obtains can effectively overcome the problem that sulfur is vacant, can as the light absorbing zone of solar cell or to electrode use.
(2) present invention utilizes hydro-thermal method or hot injection method to obtain different-shape pyrite phase ferrous disulfide powder；Pass through adjusting reaction time, it is possible to obtain the pyrite phase ferrous disulfide powder of variable grain size.
(3) present invention utilizes the number of times of silk screen printing to regulate the thickness of pyrite phase ferrous disulfide film.
(4) present invention utilizes hydro-thermal method or hot injection method to prepare pyrite phase ferrous disulfide powder, heat treatment thin film under sulfur and nitrogen/argon gas atmosphere, solves sulfur omission problem, it is thus achieved that pyrite phase.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention；
Fig. 2 is that the present invention utilizes hydro-thermal method to react the stereoscan photograph of the pyrite phase iron disulfide particles prepared for 24 hours；
Fig. 3 is that the present invention utilizes hot injection method to react the stereoscan photograph of the pyrite phase iron disulfide particles prepared for 24 hours；
Fig. 4 is that the present invention utilizes hydro-thermal method to react the stereoscan photograph of the pyrite phase iron disulfide particles prepared for 39 hours；
Fig. 5 is the X-ray diffraction result of pyrite phase iron disulfide particles；
Fig. 6 is the Raman test result of pyrite phase ferrous disulfide film.
Detailed description of the invention
The present invention is discussed in detail below in conjunction with drawings and the specific embodiments.But below example is only limitted to explain the present invention, and protection scope of the present invention should include the full content of claim, is not limited only to the present embodiment.
Embodiment 1
(1) joining in 20ml deionized water by 1.39g ferrous sulfate heptahydrate and 0.83g polyvinylpyrrolidone, stirring adds 0.76g thiourea after half an hour；Above-mentioned solution is transferred in autoclave liner, adds 0.64g sulfur powder, add ethanol in proper amount and make liquid volume reach about the 80% of autoclave liner volume.Autoclave is put in batch-type furnace 200 DEG C heat 24 hours.Being cooled to after room temperature until temperature, poured out by liquid in autoclave liner, use ethanol successively, deionized water, Carbon bisulfide washs, and is finally placed in baking oven by powder dried for standby.Fig. 2 is the stereoscan photograph of this embodiment product；Fig. 5 is the X-ray diffraction result of this embodiment product；Fig. 6 is the Raman results of this embodiment product.
(2) 0.1g ferrous disulfide powder is joined in 5ml ethanol, add 0.1g terpineol and 0.4g ethyl cellulose, magnetic agitation one day.
(3) FTO electro-conductive glass, glass substrate are cleaned in acetone, dehydrated alcohol, deionized water for ultrasonic successively, blow open standby；
(4) by silk screen print method by ferrous disulfide slurry brush in glass, FTO Conducting Glass；
(5) ferrous disulfide film of Sublimed Sulfur powder and silk screen printing is put in quartz boat, 450 DEG C of heat treatments 1 hour in the tube furnace of nitrogen protection, it is thus achieved that ferrous disulfide film, thickness 1.2 microns.
Embodiment 2
(1) in the three-necked bottle of nitrogen protection, add 10ml oleyl amine, 0.20g tetra-water ferrous chloride is added, keep temperature 120 DEG C to react 1 hour, it is thus achieved that solution A；Being dissolved in 5ml diphenyl ether by 0.19g sulfur powder in the container of another nitrogen protection, 70 DEG C of reactions obtain solution B in 1 hour；By needle tubing, B solution is injected in solution A, 220 DEG C reaction 24 hours after be cooled to room temperature.Use dehydrated alcohol, chloroform repeatedly to rinse, be finally placed in baking oven by powder dried for standby.Fig. 3 is the stereoscan photograph of this embodiment product；Fig. 5 is the X-ray diffraction result of this embodiment product；Fig. 6 is the Raman results of this embodiment product.
(2) 0.1g ferrous disulfide powder is joined in 5ml ethanol, add 0.1g terpineol and 0.4g ethyl cellulose, magnetic agitation one day.
(3) FTO electro-conductive glass, glass substrate are cleaned in acetone, dehydrated alcohol, deionized water for ultrasonic successively, blow open standby；
(4) by silk screen print method by ferrous disulfide slurry brush in glass, FTO Conducting Glass；
(5) ferrous disulfide film of Sublimed Sulfur powder and silk screen printing is put in quartz boat, 450 DEG C of heat treatments 1 hour in the tube furnace of nitrogen protection, it is thus achieved that ferrous disulfide film, thickness 1 microns.
Embodiment 3
(1) joining in 20ml deionized water by 1.39g ferrous sulfate heptahydrate and 0.83g polyvinylpyrrolidone, stirring adds 0.76g thiourea after half an hour；Above-mentioned solution is transferred in autoclave liner, adds 0.64g sulfur powder, add ethanol in proper amount and make liquid volume reach about the 80% of autoclave liner volume.Autoclave is put in batch-type furnace 200 DEG C heat 39 hours.Being cooled to after room temperature until temperature, poured out by liquid in autoclave liner, use ethanol successively, deionized water, Carbon bisulfide washs, and is finally placed in baking oven by powder dried for standby.Fig. 4 is the stereoscan photograph of this embodiment product；Fig. 5 is the X-ray diffraction result of this embodiment product；Fig. 6 is the Raman results of this embodiment product.
(2) 0.1g ferrous disulfide powder is joined in 5ml ethanol, add 0.1g terpineol and 0.4g ethyl cellulose, magnetic agitation one day.
(3) FTO electro-conductive glass, glass substrate are cleaned in acetone, dehydrated alcohol, deionized water for ultrasonic successively, blow open standby；
(4) by silk screen print method by ferrous disulfide slurry brush in glass, FTO Conducting Glass；
(5) ferrous disulfide film of Sublimed Sulfur powder and silk screen printing is put in quartz boat, 450 DEG C of heat treatments 1 hour in the tube furnace of nitrogen protection, it is thus achieved that ferrous disulfide film, thickness 1.2 microns.
Figure it is seen that it is near octahedra for adopting the iron disulfide particles that hydro-thermal method reacts preparation in 24 hours.
From figure 3, it can be seen that it is spherical for adopting the iron disulfide particles that hot injection method reacts preparation in 24 hours.
From fig. 4, it can be seen that adopting the iron disulfide particles that hydro-thermal method reacts preparation in 39 hours is lamellar.
Fig. 5 is that the ferrous disulfide adopting the inventive method hydro-thermal method to prepare with hot injection method adopts X ' PertPro polycrystal X ray diffractometer to carry out the XRD diffracting spectrum that thing is tested mutually, as can be seen from the figure, each characteristic peak of laboratory sample is stronger, halfwidth is narrower, crystal face is grown better, completely the same with pyritous XRD standard diagram (JCPDF42-1340), it does not have the diffraction maximums such as marcasite occur.
Fig. 6 adopts Kr for adopting the inventive method hydro-thermal method and hot injection method to prepare ferrous disulfide+-Ar+The Raman test collection of illustrative plates that gaseous mixture volumetric laser (λ=514.5nm) carries out, it can be seen that sample comprises 340,377 and 425cm–1Pyrite phase ferrous disulfide Characteristic Raman peak, consistent with the result of bibliographical information, it was demonstrated that adopting the product that the inventive method is prepared is single-phase pyrite phase ferrous disulfide.
It should be noted that according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claims of the present invention and appurtenance completely, it is achieved process and the same the various embodiments described above of method；And non-elaborated part of the present invention belongs to techniques well known.
The above; being only part detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art are in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should be encompassed within protection scope of the present invention.
Claims (9)
1. the method preparing pyrite phase ferrous disulfide film, it is characterised in that realize step as follows:
(1) using hydro-thermal method or hot injection method to obtain pyrite phase ferrous disulfide powder, pyrite phase ferrous disulfide powder is cleaned, standby after drying；
(2) by pyrite phase ferrous disulfide powder and ethyl cellulose, terpineol mixing, magnetic agitation is uniform, it is thus achieved that slurry；
(3) FTO electro-conductive glass or glass substrate are cleaned in acetone, dehydrated alcohol, deionized water for ultrasonic successively, blow open standby；
(4) by silk screen print method by pyrite phase ferrous disulfide slurry brush on glass or FTO Conducting Glass；
(5) ferrous disulfide film of Sublimed Sulfur powder and silk screen printing is carried out heat treatment, substrate obtains pyrite phase ferrous disulfide film.
2. the method preparing pyrite phase ferrous disulfide film according to claim 1, it is characterized in that: described step (1) use hydro-thermal method obtains pyrite phase ferrous disulfide powder method and is: ferrous sulfate heptahydrate and polyvinylpyrrolidone are added in the aqueous solution of 90-95 °, thiourea is added after dissolving, above-mentioned solution is poured in polytetrafluoroethyllining lining, add sulfur powder and ethanol in proper amount to the 80% of liner volume, it is cooled to room temperature after autoclave being put in baking oven 190-210 DEG C of reaction 4-40 hour to take out, black powder is used ethanol, deionized water, Carbon bisulfide washs, dried for standby.
3. the method preparing pyrite phase ferrous disulfide film according to claim 1; it is characterized in that: described step (1) uses hot injection method to obtain pyrite phase ferrous disulfide powder method to be: add oleyl amine and four water ferrous chlorides in the three-necked bottle of nitrogen protection; 110-120 DEG C is reacted 1-1.5 hour, it is thus achieved that solution A；Being dissolved in diphenyl ether by sulfur powder in the container of another nitrogen protection, 70-80 DEG C of reaction obtains solution B in 1-1.5 hour；By needle tubing, B solution is injected in solution A, 210-220 DEG C reaction 5-24 hour after be cooled to room temperature.Black powder is used dehydrated alcohol, chloroform, dried for standby.
4. the method preparing pyrite phase ferrous disulfide film according to claim 2, it is characterised in that: the mol ratio of described ferrous sulfate heptahydrate, polyvinylpyrrolidone, thiourea and sulfur powder is 1:1.5-2:2-2.5:4-6.
5. the method preparing pyrite phase ferrous disulfide film according to claim 3, it is characterized in that: described four water ferrous chlorides, sulfur powder mol ratio be 1:5-7, every mM of four water ferrous chlorides use 10 milliliters of oleyl amines to dissolve, and every mM of sulfur powder dissolves with 1 milliliter of diphenyl ether.
6. the method preparing pyrite phase ferrous disulfide film according to claim 1, it is characterized in that: when in described step (1), hydro-thermal method or hot injection method obtain different-shape pyrite phase ferrous disulfide powder, by adjusting reaction time, obtain the pyrite phase ferrous disulfide powder of variable grain size.
7. the method preparing pyrite phase ferrous disulfide film according to claim 1, it is characterised in that: the pyrite phase ferrous disulfide powder of described step (2), ethyl cellulose, terpineol weight ratio be 1:1:4.
8. the method preparing pyrite phase ferrous disulfide film according to claim 1, it is characterized in that: described step (5) heat treatment Sublimed Sulfur powder purity is more than 99%, heat treatment temperature is 400-550 DEG C, heat treatment 1-3 hour under sulfur and nitrogen/argon gas atmosphere.
9. the method preparing pyrite phase ferrous disulfide film according to claim 1, it is characterised in that: the thickness of described pyrite phase ferrous disulfide film is 1-10 micron.The thickness of pyrite phase ferrous disulfide film can be regulated by the number of times of silk screen printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610077574.8A CN105776888B (en) | 2016-02-02 | 2016-02-02 | A method of preparing pyrite phase ferrous disulfide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610077574.8A CN105776888B (en) | 2016-02-02 | 2016-02-02 | A method of preparing pyrite phase ferrous disulfide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105776888A true CN105776888A (en) | 2016-07-20 |
| CN105776888B CN105776888B (en) | 2019-01-29 |
Family
ID=56403385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610077574.8A Expired - Fee Related CN105776888B (en) | 2016-02-02 | 2016-02-02 | A method of preparing pyrite phase ferrous disulfide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776888B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745322A (en) * | 2016-11-18 | 2017-05-31 | 上海交通大学 | A kind of iron disulfide microspheres and preparation method thereof |
| CN107879643A (en) * | 2017-10-25 | 2018-04-06 | 中国石油大学(北京) | A kind of sulphur iron compound film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424429A (en) * | 2011-08-25 | 2012-04-25 | 重庆大学 | Method for preparing iron sulfide thin film from natural pyrite |
| CN102642874A (en) * | 2012-04-27 | 2012-08-22 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
| CN103950989A (en) * | 2014-05-07 | 2014-07-30 | 安徽师范大学 | FeS nano-material and preparation method thereof |
-
2016
- 2016-02-02 CN CN201610077574.8A patent/CN105776888B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424429A (en) * | 2011-08-25 | 2012-04-25 | 重庆大学 | Method for preparing iron sulfide thin film from natural pyrite |
| CN102642874A (en) * | 2012-04-27 | 2012-08-22 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
| CN103950989A (en) * | 2014-05-07 | 2014-07-30 | 安徽师范大学 | FeS nano-material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745322A (en) * | 2016-11-18 | 2017-05-31 | 上海交通大学 | A kind of iron disulfide microspheres and preparation method thereof |
| CN106745322B (en) * | 2016-11-18 | 2018-06-22 | 上海交通大学 | A kind of iron disulfide microspheres and preparation method thereof |
| CN107879643A (en) * | 2017-10-25 | 2018-04-06 | 中国石油大学(北京) | A kind of sulphur iron compound film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105776888B (en) | 2019-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106952743B (en) | The preparation and its application of a kind of cobaltosic oxide/carbon@molybdenum disulfide core-shell materials | |
| Gao et al. | Improved high rate capacity and lithium diffusion ability of LiNi1/3Co1/3Mn1/3O2 with ordered crystal structure | |
| CN105498773A (en) | Preparation method for doped iron oxide nanorod catalyst | |
| CN102167397B (en) | Methods for preparing porous spherical titanium dioxide and light positive pole | |
| CN104192900B (en) | A kind of TiO2Nanocrystalline synthetic method | |
| Hu et al. | SnO2 nanoparticle films prepared by pulse current deposition for photocathodic protection of stainless steel | |
| Hosono et al. | Fabrication of Nano/Micro Hierarchical Fe2O3∕ Ni Micrometer-Wire Structure and Characteristics for High Rate Li Rechargeable Battery | |
| CN109896547A (en) | Manganese dioxide composite material and preparation method thereof and capacitor | |
| CN110182856A (en) | A kind of preparation method of double shells hollow ball-shape nickel cobaltate nano particles | |
| CN102874874A (en) | Preparation method and application of multistage-structured flower-shaped molybdenum trioxide | |
| Hosono et al. | Crystal-growth process of single-crystal-like mesoporous ZnO through a competitive reaction in solution | |
| Karim et al. | Solvothermal synthesis of flower-flakes like nano composites of Ni-Co metal organic frameworks and graphene nanoplatelets for energy storage applications | |
| CN105776888A (en) | Method for preparing pyrite phase iron disulfide thin film | |
| CN104192896B (en) | A kind of TiO 2nanocrystalline and synthetic method | |
| CN104952626B (en) | It is a kind of nanocrystalline to electrode and preparation method thereof | |
| CN106629830B (en) | A kind of zinc titanate nano-material and its application in perovskite solar cell | |
| CN102897722B (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
| CN106207174B (en) | Cu2SnS3Nano material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery | |
| Li et al. | Synthesis of TiO2-SrTiO3 hetero-structured nanorod arrays and their photoelectrical performance in all-solid-state dye-sensitized solar cells | |
| Su et al. | The mechanism of aluminum vanadate in aqueous zinc ion batteries with ultra-long cycle life | |
| CN106449099B (en) | A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film | |
| Reddy et al. | Vanadium oxide nanorods for Li-ion battery applications | |
| CN109133158A (en) | The SnS of selective oxidation2Preparation of sections method and products thereof and purposes | |
| Wu et al. | Aspect ratio controlled growth of MnOOH in mixtures of Mn3O4 and MnOOH single crystals for supercapacitors | |
| Cui et al. | Synthesis and supercapacitance of Co3O4 supported on porous carbon derived from wheat flour |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190129 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |