CN102557116B - Method for preparing CuInS2 hollow solar absorbing material - Google Patents
Method for preparing CuInS2 hollow solar absorbing material Download PDFInfo
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- CN102557116B CN102557116B CN201110397191.6A CN201110397191A CN102557116B CN 102557116 B CN102557116 B CN 102557116B CN 201110397191 A CN201110397191 A CN 201110397191A CN 102557116 B CN102557116 B CN 102557116B
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Abstract
The invention relates to a method for preparing a CuInS2 hollow solar absorbing material. According to the method, an indium source, a sulfur source and the like are taken as precursors, cuprous oxide with a specific morphology is taken as a self-sacrifice template and a copper source, and a CuInS2 hollow nanomaterial can be prepared through selecting appropriate solvents and surfactants and controlling a certain reacting temperature and reacting time. Compared with the prior art, the invention has the advantages that: the method is simple in operating steps, rapid in reaction, and low in cost and can meet the industrial requirements, and the prepared CuInS2 hollow nanomaterial can have good application on photocatalytic and solar photovoltaic cells.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, especially relate to a kind of by template synthesis hollow solar absorptive material CuInS
2method.
Background technology
Sun power, as inexhaustible, the nexhaustible renewable and clean energy of a kind of mankind, is paid attention to day by day.And development and the exploitation of solar cell based on photovoltaic effect are one of research fields that development in recent years is fast, the most most active.Solar cell is mainly to take semiconductor material as basis, utilize photoelectric material to absorb the photoelectron shift reaction occurring after luminous energy and realize, therefore in photovoltaic system, catching with the photoabsorption converting material development of conversion solar energy is one of crucial technical problem.Although have the silicon of high conversion efficiency of solar cell, be solar cell dominate in large-scale application and industrial production, its high cost and corresponding loaded down with trivial details battery process have affected its further widespread use.Therefore, the photovoltaic solar cell material of development of new and technique have caused various countries scholar's extensive concern.Although the photovoltaic effect of the II-VI family semiconductor materials such as CdSe is studied widely, because the heavy metal elements such as Cd, Hg and Pb are unfriendly to environment, Europe etc. clearly forbids them to be applied to electronic devices and components, and its application is also restricted.Er Yu II-VI family semiconductor material is similar, CuInS
2also be a class direct band-gap semicondictor material and there are regulatable photoelectric properties.Because of such absorbed spectrum and solar spectrum matching high, there are high assimilated efficiency (α=5 * 10
5cm
-1), without photic attenuating effect with compared with features such as low preparation costs, become the novel solar battery material that has at present potentiality.
Photochemical catalysis is the another kind of important approach that utilizes sun power except the photoelectric conversion by solar cell.Photochemical catalysis mainly comprise photochemical catalysis synthetic (as, photolysis water hydrogen, photochemical catalysis CO
2methyl alcohol processed etc.), the large class of photodegradation two.And the size of light abstraction width and specific surface area is the important factor that affects photocatalysis effect.CuInS
2class material is due to absorption spectrum and solar spectrum matching is high, assimilated efficiency is high very applicable as light absorbing material in photochemical catalysis system.
Hollow and porous structure material have attracted the very large concern of various countries scholar as micro porous molecular sieve, mesoporous silicon oxide, soccerballene C60 and other inorganic hollow nano structural material, this be because its specific surface area is large, hollow and the characteristic of porous and the physics and chemistry character that itself has, make it in fields such as catalysis, medicament transport, light filler, photonic crystal, biomarker and sound-proof materials, have potential application widely.Template method has been widely used in the synthetic of micropore, mesoporous and hollow material at present, and these templates comprise tensio-active agent liquid crystal material, polymer microballoon, inorganic microspheres etc.The structure of using template can make hollow or vesicular structure have from template directly copies.In addition, template can utilize physics and chemistry method to remove from hybrid material as organic amine, PS or PMMA polymer microsphere and inorganic silicon oxide and carbosphere etc. easily.Although the material of hollow is current by a large amount of preparations, yet, to compare with binary compound with simple substance, the research that adopts template to sacrifice method synthesis of ternary sulfide there is not yet report.Adopting template sacrifice legal system for Cu
7s
4ten octahedra hollow semiconductor materials, hollow Cu
2-xse crystal binary chalcogen compound and solvent thermal are prepared CuInS
2basis on, successfully synthesized the CuInS of hollow
2nano material.This material can be widely used in solar cell and photocatalytic system as light absorbing material.
Summary of the invention
Object of the present invention is exactly in order to overcome the defect of above-mentioned prior art existence, to provide a kind of to take Red copper oxide as sacrificing synthesis method from the template of sacrificing template.The method technique is simple, and production cost is low, the CuInS of the hollow of gained
2nano material can further meet industrial requirement.
Object of the present invention can be achieved through the following technical solutions:
A kind of hollow solar absorptive material CuInS for preparing
2method, it is precursor that the method be take indium source, sulphur source, take the Red copper oxide with specific morphology as from sacrificing template as copper source, by selecting suitable solvent and tensio-active agent, certain temperature of reaction and reaction times of control can prepare CuInS
2hollow nanometer material, specifically comprises the following steps:
(1) indium salt, sulphur source and auxiliary agent are joined in tetrafluoroethylene reactor, then add solvent, be made into the solution that indium salt concn is 0.01-0.5M, stir or ultrasonic dissolution;
(2) take with the Red copper oxide template of indium salt equal molar quantities and join in above-mentioned solution, stirring or ultrasonic even, makes reaction precursor liquid;
(3) by reactor sealing, control temperature 140-200 ℃, reaction times 1-24 hour; After reaction finishes, reactor naturally cools to room temperature, and product is filtered or centrifugation, and with absolute ethanol washing for several times, vacuum is drained, and obtains CuInS
2hollow material.
The mol ratio of the indium salt described in step (1), sulphur source and auxiliary agent is 1: (4-16): (0.5-3).
Indium salt described in step (1) is indium chloride, indium nitrate or indium sulfate.
Sulphur source described in step (1) is the compound that can discharge sulfonium ion or the simple substance of thiocarbamide, dithiocarbonic anhydride or thioacetamide.
Auxiliary agent described in step (1) is soluble high-molecular, comprises polyvinylpyrrolidone or commercially available P123.
Solvent described in step (1) is ethanol, propyl alcohol or butanols.
Compared with prior art, operation steps of the present invention is simple, is swift in response, with low cost, can meet industrial requirement, can be by selecting the pattern of suitable template contral hollow material to meet the different needs, and the CuInS of preparation
2hollow nanometer material can have good application on photochemical catalysis and solar-energy photo-voltaic cell; The method provides thinking for preparing other multi-element compounds hollow material simultaneously.
Accompanying drawing explanation
Fig. 1 is the XRD diffractogram that embodiment 1 makes product;
Fig. 2 is energy-dispersive X-ray fluorescence (EDXRF) (EDX) figure that embodiment 1 makes product;
Fig. 3 is the stereoscan photograph that embodiment 1 makes product;
Fig. 4 is the transmission electron microscope photo that embodiment 1 makes product;
Fig. 5 is the transmission electron microscope photo that embodiment 2 makes product;
Fig. 6 is the transmission electron microscope photo that embodiment 3 makes product;
Fig. 7 is the transmission electron microscope photo that embodiment 4 makes product;
Fig. 8 is the transmission electron microscope photo that embodiment 5 makes product;
Fig. 9 is the transmission electron microscope photo that embodiment 6 makes product.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
(1) by amount of substance part, 4 parts of thiocarbamides, the indium salt of 1 part and 0.68 part of polyvinylpyrrolidone and ethanol are joined in tetrafluoroethylene reactor, then, by reactor sealing, put into the baking oven of 180 ℃, 12 hours reaction times.
(2) after reaction finishes, reactor naturally cools to room temperature, and product is filtered, and with absolute ethanol washing for several times, vacuum is drained, and obtains hollow solar absorptive material CuInS
2.
Fig. 1-2 is the hollow solar absorptive material CuInS obtaining
2x-ray diffraction (XRD) collection of illustrative plates, be shown as the CuInS of pure phase
2.Fig. 3-4th, scanning electron microscope (SEM) and the transmission electron microscope photo (TEM) of sample.As seen from the figure, hollow solar absorptive material CuInS
2the cubes that is hollow.
Embodiment 2
Step is with embodiment 1, and difference is to be thiocarbamide by the sulphur source in embodiment 1, and temperature of reaction is 140 ℃, and the reaction times is within 48 hours, to obtain hollow solar absorptive material CuInS
2nano material, Fig. 5 is the CuInS making
2the transmission electron microscope photo of nano material, can find out that from photo the material preparing is hollow material.
Embodiment 3
Step is with embodiment 1, and difference is to be propyl alcohol by the alcohols in embodiment 1, and sulphur source is dithiocarbonic anhydride, obtains hollow solar absorptive material CuInS
2nano material, Fig. 6 is the CuInS making
2the transmission electron microscope photo of nano material, can find out that from photo the material preparing is square hollow material.
Embodiment 4
Step is with embodiment 1, and difference is to be butanols by the alcohols in embodiment 1, and sulphur source is 16 parts of dithiocarbonic anhydride, obtains hollow solar absorptive material CuInS
2nano material, Fig. 7 is the CuInS making
2the transmission electron microscope photo of nano material, can find out that from photo the material preparing is spherical porous material.
Embodiment 5
Step is with embodiment 1, and difference is to be ethanol by the alcohols in embodiment 1, and sulphur source is thioacetamide, obtains hollow solar absorptive material CuInS
2nano material, Fig. 8 is the CuInS making
2the transmission electron microscope photo of nano material, can find out that from photo the material preparing is hollow material.
Embodiment 6
Step is with embodiment 1, and difference is 3 parts by polyvinylpyrrolidone in embodiment 1, obtains hollow solar absorptive material CuInS
2nano material, Fig. 9 is the CuInS making
2the transmission electron microscope photo of nano material, can find out that from photo the material preparing is hollow material.
Embodiment 7
A kind of hollow solar absorptive material CuInS for preparing
2method, it is precursor that the method be take indium source, sulphur source, take the Red copper oxide with specific morphology as from sacrificing template as copper source, by selecting suitable solvent and tensio-active agent, certain temperature of reaction and reaction times of control can prepare CuInS
2hollow nanometer material, specifically comprises the following steps:
(1) by indium chloride, thiocarbamide and polyvinylpyrrolidone, be to join at 1: 4: 0.5 in tetrafluoroethylene reactor in molar ratio, then add alcohol solvent, be made into the solution that indium salt concn is 0.01M, stirring and dissolving;
(2) take with the Red copper oxide template of indium chloride equal molar quantities and join in above-mentioned solution, stir, make reaction precursor liquid;
(3) by reactor sealing, control 140 ℃ of temperature, 24 hours reaction times; After reaction finishes, reactor naturally cools to room temperature, and product is filtered or centrifugation, and with absolute ethanol washing for several times, vacuum is drained, and obtains CuInS
2hollow material.
Embodiment 8
A kind of hollow solar absorptive material CuInS for preparing
2method, it is precursor that the method be take indium source, sulphur source, take the Red copper oxide with specific morphology as from sacrificing template as copper source, by selecting suitable solvent and tensio-active agent, certain temperature of reaction and reaction times of control can prepare CuInS
2hollow nanometer material, specifically comprises the following steps:
(1) by indium nitrate, dithiocarbonic anhydride and polyvinylpyrrolidone, be to join at 1: 6: 1 in tetrafluoroethylene reactor in molar ratio, then add propyl alcohol solvent, be made into the solution that indium nitrate concentration is 0.2M, ultrasonic dissolution;
(2) take with the Red copper oxide template of indium nitrate equal molar quantities and join in above-mentioned solution, utilize ultrasonic mixing, make reaction precursor liquid;
(3) by reactor sealing, control 160 ℃ of temperature, 12 hours reaction times; After reaction finishes, reactor naturally cools to room temperature, and product is filtered or centrifugation, and with absolute ethanol washing for several times, vacuum is drained, and obtains CuInS
2hollow material.
Embodiment 9
A kind of hollow solar absorptive material CuInS for preparing
2method, it is precursor that the method be take indium source, sulphur source, take the Red copper oxide with specific morphology as from sacrificing template as copper source, by selecting suitable solvent and tensio-active agent, certain temperature of reaction and reaction times of control can prepare CuInS
2hollow nanometer material, specifically comprises the following steps:
(1) indium sulfate, thioacetamide and P123 are joined in tetrafluoroethylene reactor, then add solvent, be made into the solution that indium sulfate concentration is 0.5M, ultrasonic dissolution;
(2) take with the Red copper oxide template of indium sulfate equal molar quantities and join in above-mentioned solution, utilize ultrasonic mixing, make reaction precursor liquid;
(3) by reactor sealing, control 200 ℃ of temperature, 1 hour reaction times; After reaction finishes, reactor naturally cools to room temperature, and product is filtered or centrifugation, and with absolute ethanol washing for several times, vacuum is drained, and obtains CuInS
2hollow material.
Claims (1)
1. prepare hollow solar absorptive material CuInS for one kind
2method, it is characterized in that, the method comprises the following steps:
(1) indium salt, sulphur source and auxiliary agent are joined in tetrafluoroethylene reactor, then add solvent, be made into the solution that indium salt concn is 0.01-0.5M, stir or ultrasonic dissolution;
(2) take with the Red copper oxide template of indium salt equal molar quantities and join in above-mentioned solution, stirring or ultrasonic even, makes reaction precursor liquid;
(3) by reactor sealing, control temperature 140-200 ℃, reaction times 1-24 hour; After reaction finishes, reactor naturally cools to room temperature, and product is filtered or centrifugation, and with absolute ethanol washing for several times, vacuum is drained, and obtains CuInS
2hollow material;
The mol ratio of the indium salt described in step (1), sulphur source and auxiliary agent is 1:(4-16): (0.5-3), described indium salt is indium chloride, indium nitrate or indium sulfate, described sulphur source is thiocarbamide, dithiocarbonic anhydride or thioacetamide, described auxiliary agent is polyvinylpyrrolidone or commercially available P123, and described solvent is ethanol, propyl alcohol or butanols.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188758A (en) * | 2016-07-25 | 2016-12-07 | 广西南宁胜祺安科技开发有限公司 | A kind of solar energy thermal-power-generating heat-absorbing material |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887538B (en) * | 2012-10-15 | 2014-08-06 | 江苏科技大学 | Preparation method of surfactant-modified CuInS2 nanocrystal |
| CN103214029A (en) * | 2013-04-25 | 2013-07-24 | 上海理工大学 | Preparation method of wurtzite CuInS2 nanodisk |
| CN103253714A (en) * | 2013-05-28 | 2013-08-21 | 江苏科技大学 | Method for preparing chalcopyrite type CuInxFe(1-x)S2 nano crystals through Fe doping |
| CN104493194B (en) * | 2014-12-01 | 2016-11-23 | 上海交通大学 | Ag-Ag8snS6the preparation method of heterodimer nano material |
| CN105084416B (en) * | 2015-09-09 | 2017-01-11 | 上海交通大学 | Preparation method of three-dimensional honeycomb CuInS2 nanowire array solar absorbing material |
| CN106531845B (en) * | 2016-12-08 | 2018-02-06 | 福建师范大学 | Chemical bath prepares solar battery obsorbing layer CuInS2The method of film |
| CN109589991B (en) * | 2018-08-14 | 2021-07-13 | 河南大学 | Zinc indium sulfide/copper indium sulfide two-dimensional heterojunction photocatalyst, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559978A (en) * | 2009-05-31 | 2009-10-21 | 淮北煤炭师范学院 | Solvent thermal synthesis method of Wurtzite structure CuInS* |
| CN102070184A (en) * | 2010-12-01 | 2011-05-25 | 同济大学 | Preparation method of CuInS2 nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100789064B1 (en) * | 2006-07-14 | 2007-12-26 | 중앙대학교 산학협력단 | Manufacturing method of cuins2 thin film using metal organic chemical vapor deposition, cuins2 thin film thereby and manufacturing method of in2s3 thin film using thereof |
-
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- 2011-12-02 CN CN201110397191.6A patent/CN102557116B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559978A (en) * | 2009-05-31 | 2009-10-21 | 淮北煤炭师范学院 | Solvent thermal synthesis method of Wurtzite structure CuInS* |
| CN102070184A (en) * | 2010-12-01 | 2011-05-25 | 同济大学 | Preparation method of CuInS2 nanoparticles |
Non-Patent Citations (4)
| Title |
|---|
| Jinning Gao et al..One-Pot Synthesis of Uniform Cu2O and CuS Hollow Spheres and Their Optical Limiting Properties.《Chem. Mater》.2008,第20卷第6263-6269页. |
| Jun Xu et al..Large-Scale Synthesis and Phase Transformation of CuSe, CuInSe2, and CuInSe2/CuInS2 Core/Shell Nanowire Bundles.《ACS NANO》.2010,第4卷(第4期),第1845-1850页. |
| Large-Scale Synthesis and Phase Transformation of CuSe, CuInSe2, and CuInSe2/CuInS2 Core/Shell Nanowire Bundles;Jun Xu et al.;《ACS NANO》;20100308;第4卷(第4期);第1845-1850页 * |
| One-Pot Synthesis of Uniform Cu2O and CuS Hollow Spheres and Their Optical Limiting Properties;Jinning Gao et al.;《Chem. Mater》;20080913;第20卷;第6263-6269页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188758A (en) * | 2016-07-25 | 2016-12-07 | 广西南宁胜祺安科技开发有限公司 | A kind of solar energy thermal-power-generating heat-absorbing material |
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