CN102320647A - Preparation method of copper sulphide nano-powder with different stoichiometric ratios - Google Patents
Preparation method of copper sulphide nano-powder with different stoichiometric ratios Download PDFInfo
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- CN102320647A CN102320647A CN201110236749A CN201110236749A CN102320647A CN 102320647 A CN102320647 A CN 102320647A CN 201110236749 A CN201110236749 A CN 201110236749A CN 201110236749 A CN201110236749 A CN 201110236749A CN 102320647 A CN102320647 A CN 102320647A
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Abstract
The invention discloses a preparation method of copper sulphide nano-powder with different stoichiometric ratios, and belongs to the technical field of nanometer materials. The preparation method is characterized in that elemental copper powder (having a mass fraction above 99.9%) and elemental sulfur power (with a mass fraction above 99.8%) are utilized as raw materials and mixed according to a general chemical formula of Cu2-xS, wherein x is great than or equal to -0.5 and less than or equal to 1.5; and the mixture is subjected to ball-milling at a ball-milling rate of 100 to 425rpm in an argon atmosphere for 5 to 600 minutes to obtain stoichiometric ratio-adjustable single-phase copper sulphide nano-powder with particle sizes of 1 to 500 nanometers. The preparation method has the advantages of cheap and easily available raw materials, simple equipment, good operability of equipment, short process flow, convenience and quickness of large-scale production of copper sulphide nano-powder with different stoichiometric ratios, and wide application prospects.
Description
Technical field
The invention belongs to technical field of nano material, particularly a kind of method for preparing the copper sulphide nano powder of different chemical metering ratio relates to the mechanical alloying technology.
Background technology
Nano material has excellent magnetic, light, electricity, sound and mechanical property than traditional material, more and more receives people's attention.Transient metal sulfide is one type of broad-spectrum functional materials.The cupric sulfide diameter of particle of nano-scale is little, specific surface area is big, because quantum size effect, surface effects and macro quanta tunnel effect, its semiconductor nanocrystal has the instrumentality of conduction electron between molecular entity and crystallite; Have the incomparable photoelectric characteristic of block materials, the copper sulphide nano powder is a kind of important photovaltaic material, at solar cell material; The tectum that photo-thermal changes; The conductive layer of polymer surfaces, optical filter is widely used in the fields such as ammonia gas sensor under the room temperature; At the preparation photodiode, photochemical catalysis and electrochemical cell aspect also have potential and use simultaneously.
The cupric sulfide of different chemical metering ratio is according to general formula Cu
2-xThere are a series of copper sulphur compounds that can stable existence in S (0.5≤x≤1.5), such as: the Cu of rich copper
2S, the increase and decrease vacant along with Cu engenders Cu
1.96S, Cu
1.8S, Cu
1.75S, Cu
1.6S, Cu
1.4A series of compounds such as S and CuS.Because the copper atom occupy-place is different, these compounds can form to have and comprise different cell configurations such as belonging to isometric system, rhombic system, hexagonal system, and its physical properties and chemical property are also different, and energy gap changes according to the x value, such as Cu
2The energy gap of S is 1.2 eV, Cu
1.8The energy gap of S is 1.5 eV, is 2 eV and CuS is an energy gap.Regulatable energy gap has very important meaning for the application of photoelectricity aspect.
The method for preparing at present the copper sulphide nano powder has the precipitator method, solid reaction process, hydrothermal method, emulsion method, template etc.People such as Chang Xinhong (patent publication No.: CN101798104A) prepare copper source dispersion soln and sulphur source dispersion soln earlier; Sulphur source dispersion soln that makes and copper source dispersion soln uniform mixing are generated black precipitate; Behind reaction 10～60min reactant is sent into whizzer; Isolated throw out passes through and zero(ppm) water, aqueous ethanolic solution and absolute ethyl alcohol elder generation mixing again after the step such as spinning successively, makes the copper sulphide nano powder after sending into the loft drier drying.This arts demand prepares forerunner's dispersion liquid, and separating step is loaded down with trivial details.People such as Ma Guangyue (patent publication No.: CN101367541) with the ionic liquid be solvent, with low-temperature solvent by the use of thermal means synthesis of nano cupric sulfide, at [BMIM] [BF
4] or 1-normal-butyl-3-Methylimidazole hexafluorophosphate in, add thiocarbamide and neutralized verdigris according to mol ratio, reaction 24 hours under the temperature of 120 degree in reaction kettle then obtains the bar-shaped cupric sulfide of nano-scale.This method long reaction time, and the raw material that uses is complicated, expensive.In a word, at present there is following shortcoming in the method for existing synthetic copper sulphide nano powder: expensive raw materials, and technology is loaded down with trivial details, length consuming time, product is difficult to separate, and productive rate is not high, and these preparing methods only are suitable for preparing a certain stoichiometric ratio, such as, CuS or Cu
2The S nano-powder is difficult to a kind of method and can prepares simultaneously and adhere to a series of copper sulphide nano powders different crystal type, different chemical metering ratio separately.
Summary of the invention
A kind of method for preparing the different chemical metering than copper sulphide nano powder provided by the invention, the mechanical alloying method of employing nonequilibrium state is a raw material with simple substance Cu powder and S powder; Control the stoichiometric ratio of products obtained therefrom through the different proportionings of raw material, required equipment is simple, and the time is short; Product need not to separate; Purity is high, and productive rate is high, is fit to large-scale commercial prodn.
A kind of preparation method of copper sulphide nano powder of different chemical metering ratio, it is characterized in that: with metal simple-substance copper powder (massfraction is greater than 99.9%) and elemental sulfur powder (massfraction is greater than 99.8%) is raw material, according to Cu
2-xS (0.5≤x≤1.5) proportioning, in argon gas atmosphere protection down, rotational speed of ball-mill 100 ~ 425 rpm ball millings 5 ~ 600 min, the different chemical that can obtain to be of a size of 1 ~ 500 nm measures the single-phase cupric sulfide even powder of ratio.
The present invention adopts mechanical alloying method, the Cu of preparation different chemical metering ratio
2-xS, nano-powder, it is controlled to have stoichiometric ratio, and raw material is easy to get, and equipment is simple, and technical process is short, and is consuming time few, the advantage that productive rate is high.
Technical characterictic of the present invention is: mechanical alloying nonequilibrium state, the copper sulphide nano powder of synthetic different chemical metering ratio fast, and no wet-milling process need not to separate, and directly gets material, and product purity is high, the productive rate height.This method can be prepared the copper sulphide nano powder of the different chemical metering ratio with 1 ~ 500 nm simply, quickly and easily.
Description of drawings
Fig. 1: the XRD figure spectrum of prepared a kind of copper sulphide nano powder.
Embodiment
Instance 1
According to mol ratio: elemental copper: elemental sulfur=2.5:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 450 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 400 ~ 500 nm behind ball milling 5 min
2.5S) nano-powder.
Instance 2
According to mol ratio: elemental copper: elemental sulfur=2.2:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 420 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 200 ~ 400 nm behind ball milling 30 min
2.2S) nano-powder.
Instance 3
According to mol ratio: elemental copper: elemental sulfur=2:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 450 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 200 ~ 300 nm behind ball milling 100 min
2S) nano-powder.
Instance 4
According to mol ratio: elemental copper: elemental sulfur=1.8:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 300 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 150 ~ 300 nm behind ball milling 200 min
1.8S) nano-powder.
Instance 5
According to mol ratio: elemental copper: elemental sulfur=1.75:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 350 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 100 ~ 300 nm behind ball milling 300 min
1.75S) nano-powder.
Instance 6
According to mol ratio: elemental copper: elemental sulfur=1.6:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 400 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 40 ~ 250 nm behind ball milling 400 min
1.6S) nano-powder.
Instance 7
According to mol ratio: elemental copper: elemental sulfur=1:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 425 rpm on the planetary ball mill device can get cupric sulfide (CuS) nano-powder of particle diameter 20 ~ 160 nm behind ball milling 500 min.
Instance 8
According to mol ratio: elemental copper: elemental sulfur=0.8:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 100 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 1 ~ 100 nm behind ball milling 600 min
0.8S) nano-powder.
Instance 9
According to mol ratio: elemental copper: elemental sulfur=0.5:1 configuration, the copper powder of weighing respective quality and sulphur powder place ball grinder; Put into the Stainless Steel Ball of ball-to-powder weight ratio 20:1; The sealing, after vacuumizing, charge into argon shield gas after; 200 rpm on the planetary ball mill device can get the cupric sulfide (Cu of particle diameter 250 ~ 400 nm behind ball milling 80 min
0.5S) nano-powder.
Claims (2)
1. the preparation method of the copper sulphide nano powder of a different chemical metering ratio is characterized in that: according to chemical general formula Cu
2-xThe S configuration, x is a mole number, its span is-0.5≤x≤1.5; Is raw material greater than 99.9% metal simple-substance copper powder and massfraction greater than 99.8% elemental sulfur powder with massfraction, and in the argon gas atmosphere protection down, rotational speed of ball-mill is 100 ~ 425 rpm ball millings, 5 ~ 600 min, and the preparation different chemical measures the copper sulphide nano powder of ratio.
2. the preparation method of the copper sulphide nano powder of different chemical metering ratio as claimed in claim 1, it is characterized in that: the stoichiometric ratio of the single-phase copper sulphide nano powder that is obtained is controlled, and it is of a size of 1 ~ 500 nm uniform particles.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616753A (en) * | 2012-04-11 | 2012-08-01 | 桂林理工大学 | Low-temperature mechanical alloying method for preparing sulphur selenide submicro powder material |
| CN102774871A (en) * | 2012-07-19 | 2012-11-14 | 北京理工大学 | P-type CuxSy semiconductor nanocrystalline, preparation method and application thereof |
| CN102817081A (en) * | 2012-08-22 | 2012-12-12 | 兰州大学 | Preparation method of flaky iron sulfide single crystal nano-material |
| CN103936054A (en) * | 2014-04-22 | 2014-07-23 | 天津大学 | Synthesis method for copper sulphide powder with bicontinuous nano porous structure |
| CN104628028A (en) * | 2014-12-19 | 2015-05-20 | 天津大学 | Method for preparing nanosheet cluster-structure cupric sulfide from titanium-copper amorphous alloy and application thereof |
| CN104817103A (en) * | 2015-03-27 | 2015-08-05 | 淮北师范大学 | Solid phase reaction preparation method of cuprous sulfide nanopowder |
| CN104925849A (en) * | 2015-06-08 | 2015-09-23 | 辽宁石油化工大学 | Synthetic method of flower shaped microsphere CuS crystalline powder |
| CN105414554A (en) * | 2015-11-06 | 2016-03-23 | 浙江工业大学 | Preparation method for iron-ferrous sulfide composite |
| CN106536097A (en) * | 2015-11-06 | 2017-03-22 | 浙江工业大学 | Preparation method for iron-ferrous sulfide composite |
| CN108217713A (en) * | 2018-01-25 | 2018-06-29 | 北京化工大学 | A kind of method that polishing prepares Nano slices of copper sulphide |
| CN108383526A (en) * | 2018-02-28 | 2018-08-10 | 昆明理工大学 | A kind of Cu1.8The Quito S crystalline substance block thermoelectric material and preparation method thereof |
| CN111689512A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海高等研究院 | In-doped Cu-S-based thermoelectric material and preparation method thereof |
| KR20210084153A (en) * | 2019-12-27 | 2021-07-07 | 한국과학기술연구원 | METHOD FOR SYNTHESIZING Cu1.81S WHICH ONE KIND OF COPPER SULFIDE |
| CN113509944A (en) * | 2020-03-25 | 2021-10-19 | 韩国科学技术研究院 | Cu for ammonia synthesis1.81S catalyst and ammonia synthesis method using same |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616753A (en) * | 2012-04-11 | 2012-08-01 | 桂林理工大学 | Low-temperature mechanical alloying method for preparing sulphur selenide submicro powder material |
| CN102774871A (en) * | 2012-07-19 | 2012-11-14 | 北京理工大学 | P-type CuxSy semiconductor nanocrystalline, preparation method and application thereof |
| CN102817081A (en) * | 2012-08-22 | 2012-12-12 | 兰州大学 | Preparation method of flaky iron sulfide single crystal nano-material |
| CN102817081B (en) * | 2012-08-22 | 2015-04-08 | 兰州大学 | Preparation method of flaky iron sulfide single crystal nano-material |
| CN103936054B (en) * | 2014-04-22 | 2015-08-26 | 天津大学 | A kind of synthetic method with the cupric sulfide powder of co-continuous nano-porous structure |
| CN103936054A (en) * | 2014-04-22 | 2014-07-23 | 天津大学 | Synthesis method for copper sulphide powder with bicontinuous nano porous structure |
| CN104628028A (en) * | 2014-12-19 | 2015-05-20 | 天津大学 | Method for preparing nanosheet cluster-structure cupric sulfide from titanium-copper amorphous alloy and application thereof |
| CN104817103B (en) * | 2015-03-27 | 2016-04-27 | 淮北师范大学 | A kind of solid state reaction preparation method of cuprous sulfide nano-powder |
| CN104817103A (en) * | 2015-03-27 | 2015-08-05 | 淮北师范大学 | Solid phase reaction preparation method of cuprous sulfide nanopowder |
| CN104925849B (en) * | 2015-06-08 | 2017-03-15 | 辽宁石油化工大学 | A kind of synthetic method of flower-like microsphere CuS crystal powder |
| CN104925849A (en) * | 2015-06-08 | 2015-09-23 | 辽宁石油化工大学 | Synthetic method of flower shaped microsphere CuS crystalline powder |
| CN106536097B (en) * | 2015-11-06 | 2020-05-29 | 浙江工业大学 | Preparation method of iron-ferrous sulfide complex |
| CN105414554A (en) * | 2015-11-06 | 2016-03-23 | 浙江工业大学 | Preparation method for iron-ferrous sulfide composite |
| CN106536097A (en) * | 2015-11-06 | 2017-03-22 | 浙江工业大学 | Preparation method for iron-ferrous sulfide composite |
| CN108217713A (en) * | 2018-01-25 | 2018-06-29 | 北京化工大学 | A kind of method that polishing prepares Nano slices of copper sulphide |
| CN108383526A (en) * | 2018-02-28 | 2018-08-10 | 昆明理工大学 | A kind of Cu1.8The Quito S crystalline substance block thermoelectric material and preparation method thereof |
| CN108383526B (en) * | 2018-02-28 | 2021-08-03 | 昆明理工大学 | Cu1.8S-based polycrystalline bulk thermoelectric material and preparation method thereof |
| CN111689512A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海高等研究院 | In-doped Cu-S-based thermoelectric material and preparation method thereof |
| KR20210084153A (en) * | 2019-12-27 | 2021-07-07 | 한국과학기술연구원 | METHOD FOR SYNTHESIZING Cu1.81S WHICH ONE KIND OF COPPER SULFIDE |
| KR102328299B1 (en) * | 2019-12-27 | 2021-11-19 | 한국과학기술연구원 | METHOD FOR SYNTHESIZING Cu1.81S WHICH ONE KIND OF COPPER SULFIDE |
| CN113509944A (en) * | 2020-03-25 | 2021-10-19 | 韩国科学技术研究院 | Cu for ammonia synthesis1.81S catalyst and ammonia synthesis method using same |
| CN113509944B (en) * | 2020-03-25 | 2024-03-15 | 韩国科学技术研究院 | Cu for ammonia synthesis 1.81 S catalyst and ammonia synthesis method using same |
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Application publication date: 20120118 |