CN103215466A - Method for one-step preparation of single-phase BiCuSeO thermoelectric material powder by mechanical alloying - Google Patents
Method for one-step preparation of single-phase BiCuSeO thermoelectric material powder by mechanical alloying Download PDFInfo
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- CN103215466A CN103215466A CN2013101260919A CN201310126091A CN103215466A CN 103215466 A CN103215466 A CN 103215466A CN 2013101260919 A CN2013101260919 A CN 2013101260919A CN 201310126091 A CN201310126091 A CN 201310126091A CN 103215466 A CN103215466 A CN 103215466A
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Abstract
The invention relates to a method for preparing BiCuSeO thermoelectric material powder. The method for one-step preparation of single-phase BiCuSeO thermoelectric material powder by mechanical alloying is characterized by comprising the following steps of: (1) weighing simple-substance Bi, simple-substance Cu, simple-substance Se and Bi2O3 powder in the molar ratio of 1:3:3:1 as raw materials; and (2) putting the powder into a high-energy ball mill for ball-milling to obtain the single-phase BiCuSeO thermoelectric material powder, wherein in the ball-milling process, the mass ratio of ball-milling media to the material is 20:1 to 60:1, the rotation speed of the ball mill is 350-800 r/min, and the ball-milling time is 8-24 hours. The method has the advantages that the energy source is saved, the technological parameters are simple and controllable, the repeatability is good and the like.
Description
Technical field
The invention belongs to the new energy materials field, be specifically related to a kind of preparation method of BiCuSeO thermoelectric material powder.
Background technology
In recent ten years, the population rapid expansion, industrial fast development, the energy and environmental problem highlight gradually, with crude oil price rise suddenly and sharply, greenhouse gas emission is excessive and ozone hole is that the energy dilemma and the ecocrisis of sign causes concern day by day.At present, traditional energies such as oil, coal, Sweet natural gas can't satisfy the social and economic development requirement.Under this background, seek and tap a new source of energy and new energy materials becomes the focus of global scientific worker research.Thermoelectric material can directly become electric energy with thermal power transfer, it is utilizing industrial exhaust heat and used heat as a kind of environmentally friendly material, there is important application prospects automobile exhaust gas, underground heat, sun power and ocean thermal gradients homenergic aspect, so thermoelectric material gets more and more people's extensive concerning.
The BiCuSeO compound has electrical property and complicated crystalline structure preferably, and the raw material reserves enrich, advantages such as value is cheap, thermoelectricity capability excellence because it has again simultaneously, are subjected to people's attention.
The synthetic main employing mechanical ball milling of BiCuSeO thermoelectric material is in conjunction with the method for two single-step solid phase reactions at present, wherein mechanical ball milling technology generally as batch mixing or control powder granularity method, and there is bibliographical information to show, when adopting a step mechanical ball milling method or mechanical ball milling to prepare the BiCuSeO thermoelectric material powder in conjunction with the method for a solid state reaction, the second phase Bi appears in the building-up process easily
2O
3Powder or Bi powder, can't obtain monophasic BiCuSeO thermoelectric material powder, so mechanical ball milling is the common methods of preparation BiCuSeO in this area in conjunction with two single-step solid phase reactions, but solid state reaction process very complicated, need the energy of consumption more, therefore find a kind of simple and fast, less energy consumption, the synthetic method of good reproducibility to seem very important.
Summary of the invention
The object of the present invention is to provide the method for the single-phase BiCuSeO thermoelectric material powder of a kind of mechanical alloying one step preparation, this method technology is simple, and good reproducibility.
To achieve these goals, technical scheme of the present invention is: the method for the single-phase BiCuSeO thermoelectric material powder of a kind of mechanical alloying one step preparation is characterized in that it comprises the steps:
1) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is a raw material, presses simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3The powder mol ratio is the ratio of 1:3:3:1, takes by weighing simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder;
2) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is packed in the high energy ball mill, carries out ball milling and obtains single-phase BiCuSeO thermoelectric material powder.
The quality purity of above-mentioned simple substance Bi is greater than 99.9%;
The quality purity of above-mentioned simple substance Cu is greater than 99.9%;
The quality purity of above-mentioned simple substance Se is greater than 99.9%;
Above-mentioned Bi
2O
3The quality purity of powder is greater than 99.9%;
The mass ratio of ball material is 20:1 ~ 60:1 in the above-mentioned mechanical milling process, and drum's speed of rotation is 350 ~ 800r/min, and the ball milling time is 8 ~ 24 hours.
The present invention has overcome habitual thinking and the technology prejudice of prior art at preparation BiCuSeO powder, report according to existing document shows, can have the second phase Bi in the BiCuSeO powder that utilizes a step mechanical ball milling method or mechanical ball milling to prepare in conjunction with the method for a single-step solid phase reaction
2O
3Powder or Bi powder can't obtain single-phase BiCuSeO powder.The present invention prolongs the ball milling time by improving rotational speed of ball-mill, has realized utilizing at normal temperatures a step Prepared by Ball Milling to obtain single-phase BiCuSeO powder.
The invention has the beneficial effects as follows:
1. material cost is cheap.The present invention mainly adopts Bi powder, Cu powder, Se powder and Bi
2O
3Powder is as raw material, and the source is abundant, cheap.
2. utilize a step mechanical ball milling method directly to prepare single-phase BiCuSeO thermoelectric material powder, this method technology is simple, be easy to control; Compared with prior art, reduced the solid state reaction process, and ma process carries out under normal temperature condition, so the energy consumption in the whole process of preparation will significantly reduce, the preparation cost of BiCuSeO thermoelectric material powder can reduce significantly.
Description of drawings
The BiCuSeO powder XRD figure spectrum that Fig. 1 obtains for embodiment 1.
The BiCuSeO powder XRD figure spectrum that Fig. 2 obtains for embodiment 2.
The BiCuSeO powder XRD figure spectrum that Fig. 3 obtains for embodiment 3.
BiCuSeO powder and Bi that Fig. 4 obtains for Comparative Examples
2O
3The XRD figure spectrum of powder.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention is not limited only to the following examples below in conjunction with embodiment.
Embodiment 1:
The method of the single-phase BiCuSeO thermoelectric material powder of a kind of mechanical alloying one step preparation, its step is as follows:
1) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is a raw material, presses simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3The powder mol ratio is the ratio of 1:3:3:1, takes by weighing simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder;
2) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is packed into and is carried out ball milling in the high energy ball mill, and ratio of grinding media to material is 40:1, and drum's speed of rotation is 350r/min, and the ball milling time is 24h, obtains the powder of BiCuSeO.
The BiCuSe powder XRD figure spectrum that present embodiment obtains is seen Fig. 1, and what obtain behind the mechanical ball milling as shown in Figure 1 is the single-phase powder of BiCuSeO.
Embodiment 2:
The method of the single-phase BiCuSeO thermoelectric material powder of a kind of mechanical alloying one step preparation, its step is as follows:
1) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is a raw material, presses simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3The powder mol ratio is the ratio of 1:3:3:1, takes by weighing simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder;
2) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is packed into and is carried out ball milling in the high energy ball mill, ball material mass ratio 60:1, and drum's speed of rotation 450r/min, ball milling time 15h obtains the BiCuSeO powder.
The BiCuSeO powder XRD figure spectrum that present embodiment obtains is seen Fig. 2, and what obtain behind the mechanical ball milling as shown in Figure 2 is the single-phase powder of BiCuSeO.
Embodiment 3:
The method of the single-phase BiCuSeO thermoelectric material powder of a kind of mechanical alloying one step preparation, its step is as follows:
1) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is a raw material, presses simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3The powder mol ratio is the ratio of 1:3:3:1, takes by weighing simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder;
2) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is packed into and is carried out ball milling in the high energy ball mill, ball material mass ratio 20:1, and drum's speed of rotation 800r/min, ball milling time 8h obtains the BiCuSeO powder.
The BiCuSeO powder XRD figure spectrum that present embodiment obtains is seen Fig. 3, and what obtain behind the mechanical ball milling as shown in Figure 3 is the single-phase powder of BiCuSeO.
Comparative Examples
A kind of mechanical ball milling prepares the method for BiCuSeO thermoelectric material powder in conjunction with a single-step solid phase reaction, and it comprises the steps:
1) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is a raw material, presses simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3The powder mol ratio is the ratio of 1:3:3:1, takes by weighing simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder;
2) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is packed into and is carried out ball milling, ratio of grinding media to material 40:1, rotating speed 200r/min, ball milling time 8h in the high energy ball mill; After ball milling finished, with the powder plumbago crucible of packing into, at vacuum atmosphere, 300 ℃ of following solid state reaction 10h obtained the BiCuSeO powder.
BiCuSeO powder XRD figure that Comparative Examples obtains spectrum is seen Fig. 4, has the second phase Bi in the BiCuSeO powder that mechanical ball milling obtains in conjunction with a single-step solid phase reaction as shown in Figure 4
2O
3Powder.
Obviously, the foregoing description only is to be the example done of explanation clearly, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of therefore being amplified or change still are within the protection domain of the invention.
Claims (6)
1. the method for the single-phase BiCuSeO thermoelectric material powder of mechanical alloying one step preparation is characterized in that it
Comprise the steps:
1) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is a raw material, presses simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3The powder mol ratio is the ratio of 1:3:3:1, takes by weighing simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder;
2) with simple substance Bi, simple substance Cu, simple substance Se and Bi
2O
3Powder is packed in the high energy ball mill, carries out ball milling and obtains single-phase BiCuSeO thermoelectric material powder.
2. method according to claim 1, the quality purity that it is characterized in that described simple substance Bi is greater than 99.9%.
3. method according to claim 1, the quality purity that it is characterized in that described simple substance Cu is greater than 99.9%.
4. method according to claim 1, the quality purity that it is characterized in that described simple substance Se is greater than 99.9%.
5. method according to claim 1 is characterized in that described Bi
2O
3The quality purity of powder is greater than 99.9%.
6. method according to claim 1 is characterized in that the ball material mass ratio of described ball milling is 20:1 ~ 60:1, drum's speed of rotation 350 ~ 800r/min, ball milling time 8 ~ 24h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591103A (en) * | 2014-12-30 | 2015-05-06 | 华中科技大学 | Bi2Te3-xSx thermoelectric material and preparation method thereof |
| CN104674046A (en) * | 2015-02-03 | 2015-06-03 | 河南理工大学 | Preparation method of BiCuZetaO thermoelectric material |
| WO2015126817A1 (en) * | 2014-02-18 | 2015-08-27 | University Of Houston System | THERMOELECTRIC COMPOSITIONS AND METHODS OF FABRICATING HIGH THERMOELECTRIC PERFORMANCE MgAgSb-BASED MATERIALS |
| CN105152143A (en) * | 2015-07-22 | 2015-12-16 | 武汉理工大学 | Combustion synthesis method of Bi2SeO2-based thermoelectric material and combustion improver for Bi2SeO2-based thermoelectric material |
| CN106744726A (en) * | 2017-01-05 | 2017-05-31 | 上海应用技术大学 | A kind of preparation method with layer structure BiOCuSe nanometer sheets |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0955542A (en) * | 1995-08-11 | 1997-02-25 | Daikin Ind Ltd | Production of thermoelectric conversion material |
| CN101704672A (en) * | 2009-11-13 | 2010-05-12 | 北京科技大学 | Cu-Cr-S ternary thermoelectric material and preparation method thereof |
| CN103011838A (en) * | 2012-10-24 | 2013-04-03 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of BiCuSeO-based pyroelectric oxide powder |
-
2013
- 2013-04-12 CN CN2013101260919A patent/CN103215466A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0955542A (en) * | 1995-08-11 | 1997-02-25 | Daikin Ind Ltd | Production of thermoelectric conversion material |
| CN101704672A (en) * | 2009-11-13 | 2010-05-12 | 北京科技大学 | Cu-Cr-S ternary thermoelectric material and preparation method thereof |
| CN103011838A (en) * | 2012-10-24 | 2013-04-03 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of BiCuSeO-based pyroelectric oxide powder |
Non-Patent Citations (3)
| Title |
|---|
| CÉLINE BARRETEAU等: "Structural and Electronic Transport Properties in Sr-Doped BiCuSeO", 《CHEMISTRY OF MATERIALS》 * |
| JING LI等: "A high thermoelectric figure of merit ZT > 1 in Ba heavily doped BiCuSeO oxyselenides", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
| WILLIAM C. SHEETS等: "Facile Synthesis of BiCuOS by Hydrothermal Methods", 《INORGANIC CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015126817A1 (en) * | 2014-02-18 | 2015-08-27 | University Of Houston System | THERMOELECTRIC COMPOSITIONS AND METHODS OF FABRICATING HIGH THERMOELECTRIC PERFORMANCE MgAgSb-BASED MATERIALS |
| US10323305B2 (en) | 2014-02-18 | 2019-06-18 | University Of Houston System | Thermoelectric compositions and methods of fabricating high thermoelectric performance MgAgSb-based materials |
| CN104591103A (en) * | 2014-12-30 | 2015-05-06 | 华中科技大学 | Bi2Te3-xSx thermoelectric material and preparation method thereof |
| CN104674046A (en) * | 2015-02-03 | 2015-06-03 | 河南理工大学 | Preparation method of BiCuZetaO thermoelectric material |
| CN105152143A (en) * | 2015-07-22 | 2015-12-16 | 武汉理工大学 | Combustion synthesis method of Bi2SeO2-based thermoelectric material and combustion improver for Bi2SeO2-based thermoelectric material |
| CN105152143B (en) * | 2015-07-22 | 2018-08-07 | 武汉理工大学 | A kind of Bi2SeO2The burning synthesis method and its combustion adjuvant of base thermoelectricity material |
| CN106744726A (en) * | 2017-01-05 | 2017-05-31 | 上海应用技术大学 | A kind of preparation method with layer structure BiOCuSe nanometer sheets |
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Application publication date: 20130724 |