CN101545124A - Method for preparing bismuth nano wire array thermoelectric materials - Google Patents
Method for preparing bismuth nano wire array thermoelectric materials Download PDFInfo
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- CN101545124A CN101545124A CN200910050277A CN200910050277A CN101545124A CN 101545124 A CN101545124 A CN 101545124A CN 200910050277 A CN200910050277 A CN 200910050277A CN 200910050277 A CN200910050277 A CN 200910050277A CN 101545124 A CN101545124 A CN 101545124A
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Abstract
The invention discloses a method for preparing bismuth nano wire array thermoelectric materials. The method is to take a high-purity BiCl3, glycerol and ammonia water solution as an electrodeposition solution, adopt electrochemical technology and utilize cyclic voltammetry to perform electrodeposition on an alumina template, and finally obtain the one-dimensional orderly Bi nano wire array thermoelectric materials with high thermoelectric conversion efficiency. The invention has simple preparation method and high filling rate; the maximum characteristic of the materials is that the materials can receive various forms of heat energy (including various types of radiant heat, solar energy, body temperature, heat generated in the system operation process, various types of waste heat and the like) from the environment and highly efficiently and directly convert the heat energy into electric energy which is then outputted; and due to the characteristics of the special high-density nano wire array structure, oxidation resistance, high temperature resistance, high field emission current density, low turn-on field, good emission stability and the like, the application of the materials to field emission microelectronic devices as cathode materials can be realized and the materials have wide commercial application prospect.
Description
Technical field
The present invention relates to the preparation of thermoelectric material, semiconductor material, specifically a kind of preparation has the thermoelectric material method of periodic arrangement Bi nano wire.
Technical background
Bismuth is typical semi-metallic, owing to have the Fermi surface of each diversity of height, very little electron effective mass, big carrier mean free path and semi-metal-characteristics such as semi-conductor transformation, thereby extremely application prospects arranged in fields such as thermoelectricity, transmitter and huge magnetic impedances.Theoretical investigation shows: because the quantum confined effect effect, along with the reduction of material dimension, the thermoelectricity capability of bismuth can increase significantly.In addition, along with the change of nanowire diameter and orientation, the electronic transport and the thermoelectricity capability of bismuth have evident difference.Therefore, the controllable growth of exploring the diameter of bismuth nanometer and orientation is extremely important, simultaneously, controllable growth itself also be the new challenge that current nano materials research faced.It is current that to prepare the bismuth nano-wire array by alumina formwork mainly be by pulsed current deposition or dc electrodeposition mode.The filling ratio that nano wire is filled in the direct current preparation is low, and nanowire size is various, can not control the big area single size.The pulse electrodeposition method is then inaccurate to depositing time control, and sedimentary current potential can only arrive two current potential depositions.
Summary of the invention
A kind of method for preparing bismuth nano wire array thermoelectric materials of providing at the deficiencies in the prior art is provided, and its step is simple, and controllability is strong, and cost is low, and the gained thermoelectric material has the bismuth nano wire array structure.
The object of the present invention is achieved like this:
A kind of method for preparing bismuth nano wire array thermoelectric materials, this method comprises following concrete steps:
A), aluminum oxide (AAO) template is cut into the sheet of 1cm * 2cm, ultrasonic cleaning cleaning in spirituous solution.
B), the preparation electric depositing solution, this solution is by 8g/l～12g/l BiCl
3, 40g/l～55g/l tartrate, 90g/l～100g/l glycerine and 45g/l～55g/lNaCl solution composition, the pH value of solution is adjusted to 0.8～1.2 with dilute hydrochloric acid.
C), adopt many potential steps to carry out galvanic deposit, step one to above-mentioned alumina formwork :-1～-1.5v step time 20ms～60ms; Step two: 0V step time 10～20ms; Three: 1～1.5V of step step time 20ms～60ms is an one-period, and in the cycle step cycle, depositing time was controlled at 100～140 minutes.
D), after galvanic deposit finishes, template is taken out, place in the deionized water, carry out ultrasonic cleaning after, be positioned over again in the NaOH solution of 0.5mol/l, leave standstill and removed pellumina in 30～50 minutes.
E), with d step solution distillation, the white powder bismuth nano wire array thermoelectric materials.
Described alumina formwork can adopt homemade, also can adopt commercial template, and its pore size of template is 50～200nm, porosity at least 50%, and thickness is 60um at least.
The invention has the beneficial effects as follows: (1) step is extremely simple, and controllability is strong, and cost is low, and good reproducibility can big area deposit; (2) B of the periodic array format filling of synthetic
iNano wire, periodically good, the filling ratio height, the spacing between line and the line is 10～20nm, the longest nano wire can reach tens microns; (3) be reflected under the normal pressure and carry out, need not to vacuumize.
The maximum characteristics of gained material of the present invention are that it can accept various forms of heat energy from environment, comprise the heating of various radiant heat, sun power, body temperature, system's operational process and various used heat etc., and directly it are changed into electric energy output expeditiously; Its unique high density nanowire arrays structure and anti-oxidant, high temperature resistant, an emission height, it is lower to open electric field, characteristics such as launch stability is good can realize it as the application in the cathode material emission microelectronics on the scene, have wide commercial application prospect.
Description of drawings
Fig. 1 is the SEM photo of embodiment 1
Fig. 2 is the backscattered electron image of embodiment 1
Fig. 3 is the secondary electron image of embodiment 1
Embodiment
A), alumina formwork is cut into the small pieces of 1cm * 2cm, ultrasonic cleaning is clean in spirituous solution then.
B), the preparation electric depositing solution, this solution is by 10g/l BiCl
3, 50g/l tartrate, 95g/l glycerine and 50g/lNaCl solution composition, the pH value of solution is adjusted to 0.9 with dilute hydrochloric acid.
C), adopt the CHl660C electrochemical workstation that alumina formwork is carried out galvanic deposit, and selected cyclic voltammetry, step one :-1v step time 20ms; Step two: 0V step time 10ms; Step three: 1V step time 30ms is an one-period; In the cycle step cycle, electrochemical deposition software is closed in depositing time control 120 minutes, finishes deposition.
D), after galvanic deposit finishes, template is taken out, place in the deionized water, carry out ultrasonic cleaning after, be positioned over again in NaOH (0.5mol/l) solution, leave standstill and removed pellumina in 30 minutes.
E), with d step solution distillation, the white powder bismuth nano wire array thermoelectric materials.
Claims (2)
1, a kind of method for preparing bismuth nano wire array thermoelectric materials is characterized in that this method comprises following concrete steps:
A), aluminum oxide (AAO) template is cut into the sheet of 1cm * 2cm, ultrasonic cleaning cleaning in spirituous solution;
B), the preparation electric depositing solution, this solution is by 8g/l～12g/l BiCl
3, 40g/l～55g/l tartrate, 90g/l～100g/l glycerine and 45g/l～55g/lNaCl solution composition, the pH value of solution is adjusted to 0.8～1.2 with dilute hydrochloric acid;
C), adopt many potential steps to carry out galvanic deposit, step one to above-mentioned alumina formwork :-1～-1.5v step time 20ms～60ms; Step two: 0V step time 10～20ms; Three: 1～1.5V of step step time 20ms～60ms is an one-period, and in the cycle step cycle, depositing time was controlled at 100～140 minutes;
D), after galvanic deposit finishes, template is taken out, place in the deionized water, carry out ultrasonic cleaning after, be positioned over again in the NaOH solution of 0.5mol/l, leave standstill and removed pellumina in 30～50 minutes;
E), with d step solution distillation, the white powder bismuth nano wire array thermoelectric materials.
2, preparation method according to claim 1 is characterized in that described alumina formwork aperture is 50～200nm, porosity at least 50%, and thickness is 60um at least.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942683A (en) * | 2010-09-19 | 2011-01-12 | 西南科技大学 | Method for preparing bismuth film by pulse plating process |
| CN102220609A (en) * | 2010-04-16 | 2011-10-19 | 华东师范大学 | Method for preparing bunchy bismuth nanostructure material |
| CN102263198A (en) * | 2010-05-26 | 2011-11-30 | 苏州汉申温差电科技有限公司 | Method for preparing thermoelectric material in low-dimension structure |
| CN102672162A (en) * | 2012-06-04 | 2012-09-19 | 中山大学 | Bismuth nanofiber three-dimensional structural material and preparation method thereof |
| CN106082120A (en) * | 2016-07-11 | 2016-11-09 | 西安交通大学 | A kind of method preparing Ag nano wire based on ZnO nanotube/template |
| CN111250076A (en) * | 2020-03-25 | 2020-06-09 | 电子科技大学 | Nano bismuth catalyst and preparation method and application thereof |
-
2009
- 2009-04-30 CN CN2009100502774A patent/CN101545124B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220609A (en) * | 2010-04-16 | 2011-10-19 | 华东师范大学 | Method for preparing bunchy bismuth nanostructure material |
| CN102263198A (en) * | 2010-05-26 | 2011-11-30 | 苏州汉申温差电科技有限公司 | Method for preparing thermoelectric material in low-dimension structure |
| CN101942683A (en) * | 2010-09-19 | 2011-01-12 | 西南科技大学 | Method for preparing bismuth film by pulse plating process |
| CN102672162A (en) * | 2012-06-04 | 2012-09-19 | 中山大学 | Bismuth nanofiber three-dimensional structural material and preparation method thereof |
| CN106082120A (en) * | 2016-07-11 | 2016-11-09 | 西安交通大学 | A kind of method preparing Ag nano wire based on ZnO nanotube/template |
| CN111250076A (en) * | 2020-03-25 | 2020-06-09 | 电子科技大学 | Nano bismuth catalyst and preparation method and application thereof |
| CN111250076B (en) * | 2020-03-25 | 2022-08-02 | 电子科技大学 | Nano bismuth catalyst and preparation method and application thereof |
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