CN101077525A - Surfactants auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material - Google Patents
Surfactants auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material Download PDFInfo
- Publication number
- CN101077525A CN101077525A CNA2006100821314A CN200610082131A CN101077525A CN 101077525 A CN101077525 A CN 101077525A CN A2006100821314 A CNA2006100821314 A CN A2006100821314A CN 200610082131 A CN200610082131 A CN 200610082131A CN 101077525 A CN101077525 A CN 101077525A
- Authority
- CN
- China
- Prior art keywords
- cis
- surfactant
- preparation
- energy ball
- solar cell
- 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.)
- Pending
Links
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Powder Metallurgy (AREA)
Abstract
The present invention is surfactant aided high energy ball milling process for preparing nanometer Cu-In-Se (CIS) material for solar cell. The high energy ball milling process includes preparation of micron level CIS phase with three kinds simple substance material, Cu, In and Se; and the preparation of nanometer CIS material while adding pyridine surfactant. Thus prepared nanometer CIS material for solar cell has stable structure, single composition and homogeneous granularity.
Description
Technical field:
The present invention relates to the new method of a kind of preparation nanometer CIS (CIS) solar cell material.
Background technology:
CIS (CIS) material is one of solar cell new material that has potentiality, traditional energy band can become discrete, quasi-molecule energy state after particularly material reached nano-scale, the band gap of material increases, the conducting path of exciton separates, and these character all help to improve the electricity conversion of material.In the document there be much the method for making of report CIS material now, as solvent heat, heat injection (TOPO) method, high temperature pyrolysis precursor process, back selenizing method, sputter, evaporation, lay-up method (SEL), molecular beam epitaxy, chemical deposition, electrodeposition process and traditional solid phase, liquid phase synthesizing method, but wherein the CIS preparation of nanomaterials is less relatively, so the new method of a kind of CIS nano material preparation that we will introduce in this patent---and the high-energy ball milling method that surfactant is auxiliary." high-energy ball milling method " preparation CIS material also has report in the literature, but this result of study can only obtain size at micron order, the random CIS material of shape, can't obtain uniform particles, the nanoscale CIS material of regular shape.Surfactant has a wide range of applications improving nano-particle surface performance, control nanoparticle size, vpg connection, pyridine is as a kind of traditional surfactant, be usually used in solvent hot preparation nano material, Qian Yitai etc. once used copper chloride, inidum chloride, selenium powder, pyridine, successfully synthesized nanometer CIS material in reactor.We are introduced in the high-energy ball milling now, and the advantage of mating surface activating agent and high-energy ball milling makes those can't obtain nano level material with direct ball milling, successful nanometer.
Summary of the invention:
The purpose of this invention is to provide a kind of new nano material synthetic method, i.e. the auxiliary high-energy ball milling method of surfactant, and adopt this method can access Stability Analysis of Structures, component is single, evengranular chalcopyrite nanometer CIS material.
It is raw material that the present invention adopts copper, indium and three kinds of simple substance of selenium, adopts the high-energy ball milling method preparation, comprises the preparation of micron order CIS pure phase and two processes of preparation of nanoscale CIS material, adds surfactant in the preparation process of nanoscale CIS material.
Surfactant is preferably the pyridines surfactant, such as pyridine; 2,2 bipyridyls; 4,4 bipyridyls etc.
Surfactant is preferably pyridine.
The advantage of this process is: equipment and technology are simple, and is easy to operate, with low cost; Raw material are simple, and environmental pollution is little; By changing the Cu/In ratio that adds, can effectively control the conduction type of material, and can effectively control the pattern and the size of nano particle by the kind that changes process conditions and surfactant.
The specific embodiment:
1) preparation of micron order CIS material
During the preparation pure phase, drum's speed of rotation is 300-600rpm, and the time is 0.5-15 hour, and the best is 600rpm, 2 hours.
With the CIS pure phase that does not contain other impurity that obtains, analyze as can be seen by X-ray powder diffraction (XRD), 2 θ have very strong diffraction maximum in the time of 26.7 °, 44.2 °, 52.4 °, the XRD simulation drawing comparison with the CIS mono-crystalline structures shows that gains are chalcopyrite CIS mutually.
The rotating speed for preparing CIS thing and ball mill with the method for ball milling has very big relation.Rotating speed is too low, can't form the CIS pure phase at short notice, and rotating speed is too high, and the general milling machine can't reach, and instrument is had relatively high expectations.Except that rotating speed, the time is also bigger to the influence of thing phase.Time is too short, and that mainly form is Cu
xThe binary thing phase of Se; Time is oversize, and indium is oxidized gradually in mechanical milling process, and the CIS thing easily is decomposed mutually, CuSe finally occurs
2, In
2O
3Deng the thing phase.
2) preparation of nanometer CIS material
In the preparation process of nano material, drum's speed of rotation is 600rpm, and the time is 40 hours.
Add pyridine as surfactant at the pure micron order CIS thing for preparing in mutually, carry out ball milling again, can obtain single, the evengranular CIS nano material of component by control ball milling speed and time.By Electronic Speculum as can be seen, do at pyridine under the booster action of surfactant, along with the growth of ball milling time, the pattern of CIS is by random flat sheet, mix with graininess to sheet, reach regular shape, uniform graininess at last, the diameter of particle is 60-70nm.
Aspect the thing phase; by X-ray powder diffraction as can be seen; ball milling in the time of 40 hours thing phase peak and the CIS monocrystalline XRD fitted figure of standard coupling better; the just appearance of the oxide of a little indium; the faint enhancings of locating the peak such as 29.2 °, 32.7 °, 35.9 °, 56.2 ° have been promoted; but do not influence overall CIS thing phase, the instruction card surface-active agent can shield to the CIS thing effectively mutually.
Simple dry grinding can't make the CIS thing reach nanometer mutually, because under the mutual powerful extruding of agate ball, material is easy to bonding, finally forms coarse multilayer chip structure.Surfactant not only plays in mechanical milling process and guarantees that thing is stable mutually, is difficult for oxidized effect, can effectively stop the reunion of the bonding and nano particle between the material simultaneously, thereby play the effect of stable nanoparticles.
About preparating mechanism, we think that CIS is dispersed in wherein, during ball milling after adding surfactant, mutual extrusion friction between agate jar and ball, ball and ball and ball and the surfactant, make further tinyization of CIS, regular shapeization, the subtitle substance of generation is wrapped up by surfactant simultaneously, stop and reunite or bonding generation, such process continues carrying out, and is final, makes micron-sized CIS be converted into nanoscale CIS material.
Claims (4)
1. the auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material of surfactant, employing is a raw material with copper, indium and three kinds of simple substance of selenium, the preparation of employing high-energy ball milling method, comprise the preparation of micron order CIS pure phase and two processes of preparation of nanoscale CIS material, it is characterized in that: in the preparation process of nanoscale CIS material, add surfactant.
2. preparation method as claimed in claim 1 is characterized in that: described surfactant is the pyridines surfactant.
3. preparation method as claimed in claim 2 is characterized in that: described pyridines surfactant is pyridine or 2,2 bipyridyls or 4,4 bipyridyls.
4. preparation method as claimed in claim 3 is characterized in that: described pyridines surfactant is a pyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100821314A CN101077525A (en) | 2006-05-26 | 2006-05-26 | Surfactants auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100821314A CN101077525A (en) | 2006-05-26 | 2006-05-26 | Surfactants auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101077525A true CN101077525A (en) | 2007-11-28 |
Family
ID=38905282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100821314A Pending CN101077525A (en) | 2006-05-26 | 2006-05-26 | Surfactants auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101077525A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818375A (en) * | 2010-02-11 | 2010-09-01 | 昆山正富机械工业有限公司 | Method for preparing copper-indium-gallium-selenium(sulfur) light absorption layer by adopting non-vacuum process |
| CN101927983A (en) * | 2010-07-26 | 2010-12-29 | 中国科学院化学研究所 | CuInSe2 nano material and preparation method and application thereof |
| CN101525126B (en) * | 2009-03-16 | 2011-04-20 | 大连交通大学 | Preparation process of CuInSe2 solar battery material |
| CN102041555A (en) * | 2011-01-14 | 2011-05-04 | 南开大学 | Preparation method of CuInS2 nanocrystalline material |
| CN102070121A (en) * | 2009-11-20 | 2011-05-25 | 正峰新能源股份有限公司 | Method for preparing copper-indium-gallium-selenium nanoparticles |
| CN101700871B (en) * | 2009-10-26 | 2012-07-18 | 中国科学技术大学 | Copper-indium-selenium nanowire array and preparation method and application thereof |
| CN101700872B (en) * | 2009-10-26 | 2012-07-18 | 中国科学技术大学 | Copper-indium-gallium-selenium nanowire array and preparation method and application thereof |
| CN105405744A (en) * | 2010-12-07 | 2016-03-16 | 同和控股（集团）有限公司 | Chalcogen compound powder, chalcogen compound paste and preparation methods of chalcogen compound powder and chalcogen compound paste |
| CN106191986A (en) * | 2016-07-13 | 2016-12-07 | 中国科学技术大学 | The controlled method preparing orthorhombic phase silver gallium selenium and silver indium gallium selenium nanometer monocrystalline granule of liquid-phase reflux one-step method |
| CN111230098A (en) * | 2020-03-18 | 2020-06-05 | 北京大学 | Metal-based nano composite powder material, preparation method and application thereof |
-
2006
- 2006-05-26 CN CNA2006100821314A patent/CN101077525A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525126B (en) * | 2009-03-16 | 2011-04-20 | 大连交通大学 | Preparation process of CuInSe2 solar battery material |
| CN101700871B (en) * | 2009-10-26 | 2012-07-18 | 中国科学技术大学 | Copper-indium-selenium nanowire array and preparation method and application thereof |
| CN101700872B (en) * | 2009-10-26 | 2012-07-18 | 中国科学技术大学 | Copper-indium-gallium-selenium nanowire array and preparation method and application thereof |
| CN102070121A (en) * | 2009-11-20 | 2011-05-25 | 正峰新能源股份有限公司 | Method for preparing copper-indium-gallium-selenium nanoparticles |
| CN101818375A (en) * | 2010-02-11 | 2010-09-01 | 昆山正富机械工业有限公司 | Method for preparing copper-indium-gallium-selenium(sulfur) light absorption layer by adopting non-vacuum process |
| CN101927983A (en) * | 2010-07-26 | 2010-12-29 | 中国科学院化学研究所 | CuInSe2 nano material and preparation method and application thereof |
| CN101927983B (en) * | 2010-07-26 | 2012-12-05 | 中国科学院化学研究所 | CuInSe2 nano material and preparation method and application thereof |
| CN105405744A (en) * | 2010-12-07 | 2016-03-16 | 同和控股（集团）有限公司 | Chalcogen compound powder, chalcogen compound paste and preparation methods of chalcogen compound powder and chalcogen compound paste |
| CN102041555A (en) * | 2011-01-14 | 2011-05-04 | 南开大学 | Preparation method of CuInS2 nanocrystalline material |
| CN106191986A (en) * | 2016-07-13 | 2016-12-07 | 中国科学技术大学 | The controlled method preparing orthorhombic phase silver gallium selenium and silver indium gallium selenium nanometer monocrystalline granule of liquid-phase reflux one-step method |
| CN106191986B (en) * | 2016-07-13 | 2018-09-07 | 中国科学技术大学 | Liquid-phase reflux one-step method controllable preparation orthorhombic phase AgIn1-xGaxSe2The method of nanometer monocrystalline particle |
| CN111230098A (en) * | 2020-03-18 | 2020-06-05 | 北京大学 | Metal-based nano composite powder material, preparation method and application thereof |
| CN111230098B (en) * | 2020-03-18 | 2021-07-13 | 北京大学 | Metal-based nano composite powder material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101077525A (en) | Surfactants auxiliary high-energy ball-mill method for preparing nano cuprum indium selenium solar cell material | |
| Wang et al. | Polymer-based nanocomposites: Role of interface for effective microwave absorption | |
| CN103359777B (en) | A kind of Cu 2znSnS 4hydrothermal preparation method and Cu 2znSnS 4material and purposes | |
| Wang et al. | Preparation and properties of Cu2FeSnS4 nanocrystals by ultrasound-assisted microwave irradiation | |
| KR20120015367A (en) | Preparation method for cis-based compound thin film with high density and preparation method for thin film solarcell manufactured by using the cis-based compound thin film | |
| CN102897724A (en) | Tin selenide nano-flowers and preparation method thereof | |
| Vidhya et al. | Structural studies of mechano-chemically synthesized CuIn1− xGaxSe2 nanoparticles | |
| CN104658771B (en) | A kind of preparation method and application of sea urchin shape vanadium base nano-electrode material | |
| CN108675339B (en) | Preparation method of rodlike self-assembled spherical zinc-cadmium-sulfur solid solution material | |
| CN103042230A (en) | Preparation method for micron spherical silver powder for electronic paste | |
| Tanveer et al. | Atypical BiOCl/Bi2S3 hetero-structures exhibiting remarkable photo-catalyst response | |
| CN103887373B (en) | Antivacuum legal system is for the production technology of gradient band gap CIGS solar cell light absorption layer | |
| Li et al. | Research progress of SiOx-based anode materials for lithium-ion batteries | |
| Su et al. | Synthesis of heteroarchitectures of PbS nanostructures well-erected on electrospun TiO2 nanofibers | |
| CN110482594B (en) | Cu 2 CdSnS 4 Micro-nano material and preparation method thereof | |
| Chang et al. | Rapid preparation and photocatalytic properties of octahedral Cu2O@ Cu powders | |
| CN106277040B (en) | Controllable stannic oxide microballoon of a kind of crystallite dimension and preparation method and application | |
| CN102897722B (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
| CN105562711B (en) | A kind of preparation method of nano silver wire | |
| CN111362316B (en) | Amorphous cobalt sulfide nanowire and preparation method thereof | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN103101964A (en) | Preparation method of zinc oxide nanoflower of spiauterite structure | |
| Pei et al. | Shape-controlled synthesis of LiMnPO4 porous nanowires | |
| CN105858727B (en) | A kind of 2H-MoS2The preparation method of nanometer sheet | |
| CN102126708B (en) | Preparation method of Cu-In-Ga-Se-S nano powder material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20071128 |