CN103771495B - Prepare Shi Mo Xi the method of copper-zinc-tin-sulfur nanocrystalline composite material - Google Patents
Prepare Shi Mo Xi the method of copper-zinc-tin-sulfur nanocrystalline composite material Download PDFInfo
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- CN103771495B CN103771495B CN201310723967.8A CN201310723967A CN103771495B CN 103771495 B CN103771495 B CN 103771495B CN 201310723967 A CN201310723967 A CN 201310723967A CN 103771495 B CN103771495 B CN 103771495B
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Abstract
The method preparing Graphene-copper-zinc-tin-sulfur nanocrystalline composite material of technical field of nano material, by graphene oxide water solution being scattered in copper-zinc-tin-sulfur precursor sol, adopts hydrothermal method within 12 hours, to prepare 180 DEG C of reactions; Copper-zinc-tin-sulfur precursor sol by being dissolved in alcohol, water or its mixed solvent and making containing copper source, zinc source, Xi Yuan, sulphur source, wherein: the mol ratio in copper source, zinc source, Xi Yuan, sulphur source is 2: (1 ~ 1.5): (1 ~ 1.5): (4 ~ 8).The present invention is without the need to tensio-active agent, and adopt hydro-thermal in situ synthesis, copper-zinc-tin-sulfur is nanocrystalline to be grown on Graphene uniformly, and method is simple, and cost is low, and the copper-zinc-tin-sulfur of preparation is nanocrystalline is of a size of 3 ~ 5nm.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically a kind of prepare Shi Mo Xi ?the method of copper-zinc-tin-sulfur nanocrystalline composite material.
Background technology
Nano composite material can concentrate the premium properties of independent material, based on the basis of this thinking, for the performance and application of nano material, there is material impact by the structure of appropriate design material, the more important thing is that being uniformly distributed for it of nano material is as significant in fields such as solar cell, photochemical catalysis, ultracapacitors at energy environment, therefore nano composite material control and synthesis more and more come into one's own.
Copper-zinc-tin-sulfur CZTS) be direct band gap p-type semiconductor, energy gap is about 1.5eV, and uptake factor is up to 10
4cm
?1, and CZTS method for manufacturing thin film is simple, and component is rich reserves on earth, and the low and nontoxicity of price, therefore be it is believed that to have great development prospect.Graphene is ultra-thin two-dimension nano material, has strong 200 000cm of electron mobility
2v
-1s
-1), mechanical property and the stability good characteristic such as well.
Through finding the retrieval of prior art, Chinese patent literature 103219066A publication date 2013 ?07 ?24, disclose flexible conductive film of a kind of two-dimensional graphene and one-dimensional nano line compound and preparation method thereof.Graphene, nano wire and dispersing auxiliary are distributed in solvent by this technology, ultrasonic vibration, obtain finely disseminated graphene/nano rice noodles solution, after vacuum filtration, drying, obtain graphene/nano rice noodles laminated film.Described laminated film thickness be 10nm ?1000 μm, have good intensity and flexibility, square resistance 0.001 ?within the scope of 3000 Ω/sq., specific conductivity be 0.01 ?5000S/cm.But this technology preparation process is comparatively complicated, and meets film and cannot reach quantum dot rank.
Summary of the invention
The present invention is directed to prior art above shortcomings, propose a kind of prepare Shi Mo Xi ?the method of copper-zinc-tin-sulfur nanocrystalline composite material, without the need to tensio-active agent, adopt hydro-thermal in situ synthesis, copper-zinc-tin-sulfur is nanocrystalline to be grown on Graphene uniformly.The inventive method is simple, and cost is low, and the copper-zinc-tin-sulfur of preparation is nanocrystalline is of a size of 3 ~ 5nm, and this provides a kind of effective means in the application of photochemical catalysis and solar cell for graphene-based copper-zinc-tin-sulfur nanocrystalline composite material.
The present invention is achieved by the following technical solutions, and the present invention, by graphene oxide water solution being scattered in copper-zinc-tin-sulfur precursor sol, adopts hydrothermal method within 12 ~ 24 hours, to prepare 160 ~ 240 DEG C of reactions.
Described hydrothermal method is preferred 180 DEG C of reactions 12 hours further.
Described copper-zinc-tin-sulfur precursor sol by being dissolved in alcohol, water or its mixed solvent and making containing copper source, zinc source, Xi Yuan, sulphur source, wherein: the mol ratio in copper source, zinc source, Xi Yuan, sulphur source is 2: (1 ~ 1.5): (1 ~ 1.5): (4 ~ 8).
Further, copper source be in cupric nitrate, cupric chloride, copper sulfate or copper acetate solution any one or its combination; Zinc source be in zinc nitrate, zinc chloride, zinc sulfate or acetic acid zinc solution any one or its combination; Xi Yuan is tin protochloride or stannous sulfate solution or its combination; Sulphur source is thiourea solution.
The volume ratio of described copper source, zinc source, Xi Yuan, sulphur source and graphene oxide water solution is 2: (1 ~ 1.5): (1 ~ 1.5): (4 ~ 8): (10 ?40).
Further, described copper source, zinc source, Xi Yuan, sulphur source adopt concentration be 0.1mmol/L the aqueous solution realize.
The mass concentration of described graphene oxide is 6.5g/L.
The present invention relates to Shi Mo Xi that aforesaid method prepares ?copper-zinc-tin-sulfur nanocrystalline composite material, the copper-zinc-tin-sulfur in this matrix material is nanocrystalline to be grown on Graphene uniformly, and copper-zinc-tin-sulfur is nanocrystalline is of a size of 3 ~ 5nm.
Accompanying drawing explanation
Fig. 1 be preparation in the embodiment of the present invention 1 Shi Mo Xi ?the overall transmission electron microscope figure of copper-zinc-tin-sulfur nanocrystalline composite material.
Fig. 2 be preparation in the embodiment of the present invention 1 Shi Mo Xi ?the graphene edge fractional transmission electron microscope picture of copper-zinc-tin-sulfur nanocrystalline composite material.
Fig. 3 be preparation in the embodiment of the present invention 1 Shi Mo Xi ?the high power transmission electron microscope figure of copper-zinc-tin-sulfur nanocrystalline composite material.
Fig. 4 is Fig. 3 enlarged diagram.
Fig. 5 is the x-ray photoelectron energy spectrogram of the stone ink alkene ?copper-zinc-tin-sulfur nanocrystalline composite material of preparation in the embodiment of the present invention 1.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The present embodiment comprises the following steps:
1) compound concentration is the cupric chloride of 0.1mmol/L, zinc chloride, tin protochloride and thiourea solution, respectively get and be respectively 2,1,1, after the mixing to and dissolve completely of the above-mentioned solution of 6mL, add 10mL graphene aqueous solution again to stir, obtain mixing solutions, finally add water or ethylene glycol, make the ratio of ethylene glycol and water mixed solvent in solution be 1 to 1, and cumulative volume is no more than 80mL;
2) above-mentioned mixing solutions is poured in 100mL hydrothermal reaction kettle, be tamping, in retort furnace, heat 180 DEG C, 12h.
As figure 1 ?shown in Fig. 5, the Shi Mo Xi prepared for embodiment ?the effect schematic diagram of copper-zinc-tin-sulfur nanocrystalline composite material, metal element content is wherein:
Element | Mass ratio % | Atomic ratio % |
Cu | 33.19 | 26.74 |
Zn | 12.95 | 10.15 |
Sn | 25.98 | 11.21 |
S | 24.6 | 39.29 |
The copper-zinc-tin-sulfur of the matrix material that the present embodiment prepares is nanocrystalline to be grown on Graphene uniformly, and copper-zinc-tin-sulfur is nanocrystalline is of a size of 3 ~ 5nm.
Embodiment 2
The present embodiment comprises the following steps:
1) compound concentration is the cupric chloride of 0.1mmol/L, zinc chloride, tin protochloride and thiourea solution, respectively get and be respectively 2,1,1, after the mixing to and dissolve completely of the above-mentioned solution of 4mL, add 10mL graphene aqueous solution again to stir, obtain mixing solutions, finally add water or ethylene glycol, make the ratio of ethylene glycol and water mixed solvent in solution be 1 to 1, and cumulative volume is no more than 80mL;
2) above-mentioned mixing solutions is poured in 100mL hydrothermal reaction kettle, be tamping, in retort furnace, heat 180 DEG C, 12h.
Embodiment 3
The present embodiment comprises the following steps:
1) compound concentration is the cupric chloride of 0.1mmol/L, zinc chloride, tin protochloride and thiourea solution, respectively get and be respectively 2,1,1, after the mixing to and dissolve completely of the above-mentioned solution of 8mL, add 10mL graphene aqueous solution again to stir, obtain mixing solutions, finally add water or ethylene glycol, make the ratio of ethylene glycol and water mixed solvent in solution be 1 to 1, and cumulative volume is no more than 80mL;
2) above-mentioned mixing solutions is poured in 100mL hydrothermal reaction kettle, be tamping, in retort furnace, heat 180 DEG C, 12h.
Claims (4)
1. prepare a method for Graphene-copper-zinc-tin-sulfur nanocrystalline composite material, it is characterized in that, the copper-zinc-tin-sulfur in described matrix material is nanocrystalline to be grown on Graphene uniformly, and copper-zinc-tin-sulfur is nanocrystalline is of a size of 3 ~ 5 nm;
Described method, by graphene oxide water solution being scattered in copper-zinc-tin-sulfur precursor sol, adopting hydrothermal method to react under 180 DEG C of environment and prepares for 12 hours;
Described copper-zinc-tin-sulfur precursor sol by being dissolved in alcohol, water or its mixed solvent and making containing copper source, zinc source, Xi Yuan, sulphur source, wherein: the mol ratio in copper source, zinc source, Xi Yuan, sulphur source is 2: (1 ~ 1.5): (1 ~ 1.5): (4 ~ 8);
Described copper source be in cupric nitrate, cupric chloride, copper sulfate or copper acetate solution any one or its combination; Zinc source be in zinc nitrate, zinc chloride, zinc sulfate or acetic acid zinc solution any one or its combination; Xi Yuan is tin protochloride or stannous sulfate solution or its combination; Sulphur source is thiocarbamide.
2. method according to claim 1, is characterized in that, the volume ratio of described copper source, zinc source, Xi Yuan, sulphur source and graphene oxide water solution is 2: (1 ~ 1.5): (1 ~ 1.5): (4 ~ 8): 10.
3. method according to claim 1, is characterized in that, described copper source, zinc source, Xi Yuan, sulphur source adopt concentration be 0.1mmol/L the aqueous solution realize.
4. method according to claim 1, is characterized in that, the mass concentration of described graphene oxide is 6.5 g/L.
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CN101792175A (en) * | 2010-03-11 | 2010-08-04 | 山东大学 | Cu-Sn-Zn-S semiconductor material with adjustable forbidden band width and preparation method thereof |
CN102107905A (en) * | 2011-01-12 | 2011-06-29 | 东华大学 | Method for preparing Cu2ZnSnS4 solar battery material |
CN102254985A (en) * | 2011-04-14 | 2011-11-23 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
CN102689920A (en) * | 2012-06-20 | 2012-09-26 | 上海大学 | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis |
CN102965105A (en) * | 2012-11-21 | 2013-03-13 | 中国科学院等离子体物理研究所 | Graphene-CuInS2 quantum dot compound and preparation method thereof |
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Patent Citations (5)
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CN101792175A (en) * | 2010-03-11 | 2010-08-04 | 山东大学 | Cu-Sn-Zn-S semiconductor material with adjustable forbidden band width and preparation method thereof |
CN102107905A (en) * | 2011-01-12 | 2011-06-29 | 东华大学 | Method for preparing Cu2ZnSnS4 solar battery material |
CN102254985A (en) * | 2011-04-14 | 2011-11-23 | 山东大学 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
CN102689920A (en) * | 2012-06-20 | 2012-09-26 | 上海大学 | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis |
CN102965105A (en) * | 2012-11-21 | 2013-03-13 | 中国科学院等离子体物理研究所 | Graphene-CuInS2 quantum dot compound and preparation method thereof |
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