CN105460910A - A constant-temperature large-scale preparing method of belt-shaped black phosphorus - Google Patents
A constant-temperature large-scale preparing method of belt-shaped black phosphorus Download PDFInfo
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- CN105460910A CN105460910A CN201510801468.5A CN201510801468A CN105460910A CN 105460910 A CN105460910 A CN 105460910A CN 201510801468 A CN201510801468 A CN 201510801468A CN 105460910 A CN105460910 A CN 105460910A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a constant-temperature large-scale preparing method of belt-shaped black phosphorus to prepare the black phosphorus in a constant-temperature manner. Cheap red phosphorus, tin and iodine are adopted as raw materials and subjected to a solid-phase reaction at a constant temperature under a low pressure to prepare the pure-phase belt-shaped black phosphorus. The method is simple in steps and high in operability. The method is advantageous in that 1) the adopted raw materials are nontoxic so that the method is clean and environmental friendly, 2) tin tetraiodide is replaced by the iodine, thus greatly reducing a cost, 3) the conversion ratio of the black phosphorus is high, and 4) black phosphorus growth is performed with a muffle furnace in place of a tube furnace, so that the yield of the black phosphorus is greatly increased, a single-pass black phosphorus yield only depends on the volume of the muffle furnace, and the single-pass yield is increased by at least 10 times or above than a single-pass yield when black phosphorus growth is performed in a tube furnace. The prepared belt-shaped black phosphorus is characterized in that crystallinity is good, and thin-layer black phosphorus with a large area can be stripped mechanically more easily. The method provides great convenience for subsequent preparation and applications of photoelectric devices based on the black phosphorus.
Description
Technical field
The present invention relates to the synthesis field of chemical material, be specifically related to a kind of constant temperature and the method for the banded black phosphorus of extensive preparation.
Technical background
Class Graphene two-dimensional semiconductor material is owing to having high conductivity, and high-tenacity and great specific surface area, be considered to be expected to alternative traditional semiconductor silicon, causes new round revolution in electronics technology field.But, because Graphene does not have energy band structure, the Push And Release of logical circuit can not be realized, this strongly limits its application at electron device and field of photoelectric devices, as photodetector, solar cell, field-effect transistor etc.In recent years, New Two Dimensional semiconductor material one of important research field becoming Materials science is found.
Black phosphorus is the common maximum (2.69g/cm of four kinds of allotropic substances (red phosphorus, white phosphorus, violet phosphorus, black phosphorus) Midst density of phosphorus
3), the most stable one, there is the laminate structure of similar graphite, combine by Van der Waals force between layers.But the maximum feature being different from graphite in its structure is, the phosphorus atom in its same layer, not in same plane, is the layered arrangement of fold along b axle, and interlamellar spacing larger than graphite (about 5 dust).In addition, it is direct band-gap semicondictor, has good hole mobility and optical characteristics, and the theoretical cell capacity 2596mAh/g higher than graphite, and these advantages all make it have great application prospect at electronics and field of photoelectric devices.
Traditional method preparing black phosphorus is by heating white phosphorus under high pressure (12000atm), or makees catalyzer with mercury under normal pressure and be prepared.These methods have high toxicity, the feature of unclean environmental protection.Recently, also article report red phosphorus is had, tinization gold, tin tetraiodide is that black phosphorus prepared by raw material, but in raw material used, the cost of gold and tin tetraiodide is high, and tin tetraiodide also needs to prepare in advance, substantially increases preparation cost, technique is loaded down with trivial details, and the black phosphorus unit price of present commercial sale is up to 600 Euros/gram.On the other hand, the preparation method of above report is due to needs thermograde, and Preparation equipment is tube furnace, and the output of black phosphorus is extremely restricted, and cannot realize scale of mass production.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, there is provided a kind of constant temperature and the method for the banded black phosphorus of extensive preparation, the method optimizes the preparation process of black phosphorus, the cheap raw material crystalline flake of iodine is adopted to substitute tin tetraiodide, concrete Cost comparisons: tin tetraiodide 304RMB/g, the crystalline flake of iodine: 12RMB/g, greatly reduce costs (cost reduced 96% than originally), meanwhile, eliminate the step originally preparing tin tetraiodide, save manpower and materials.On the other hand, in order to the practical application of scale operation, the method growth black phosphorus of trial constant temperature, first raw material is put into silica tube tube sealing, put into muffle furnace again, the silica tube quantity put in muffle furnace only depends on the volume of muffle furnace, and therefore the output of black phosphorus prepared by single is relative to the improve obtaining more than at least 10 times with silica tube.Specifically with red phosphorus, tin and iodine are raw material, by solid state reaction, prepare the banded black phosphorus of pure phase in constant temperature muffle furnace.Experiment finds, the black phosphorus of this band shape, relative to the bulk black phosphorus prepared before, has the advantage that easier mechanically peel goes out the black squama of big area thin layer.
Above-mentioned constant temperature and the method for the banded black phosphorus of extensive preparation are realized by following steps; By high-purity red phosphorus, the 10-40:0.2-3:0.05-0.4 mixing in mass ratio of tin and iodine, load in silica tube, the muffle furnace of constant temperature is put into after direct tube sealing, setting in-furnace temperature 500 ~ 650 DEG C, insulation 2-5h, 5 to 10h cools to 300 to 480 DEG C more afterwards, insulation 2-5h, then cool to room temperature after 3 to 10h.The banded black phosphorus of gained is evenly distributed in silica tube.
The form of described high-purity red phosphorus is powder or particle, and purity is not less than 99.99%, and the form of described tin is fragment or powder, and the form of described iodine is sheet.The form obtaining black phosphorus is banded (strip).
With the method high toxicity of current existing synthesis black phosphorus, yield poorly, the feature that high pressure preparation cost is higher is compared, and the step that the present invention prepares black phosphorus is simple, and strong operability, has following significant technical superiority: one, adopt nontoxic raw material, clean environment firendly; Two, adopt iodo for tin tetraiodide, significantly reduce costs; Three, black phosphorus turnover ratio reaches 97%; Four, adopt muffle furnace to replace tube furnace and prepare black phosphorus, black phosphorus productive rate can be increased substantially, make single black phosphorus productive rate only depend on the volume of muffle furnace, improve more than at least 10 times relative to the single productive rate of tube furnace growth black phosphorus.The more important thing is, prepared black phosphorus has the pattern of strip, smooth surface, and be beneficial to mechanically peel and go out the thinner black phosphorus of big area, this is significant to the application of black phosphorus on photoelectric device.
Accompanying drawing explanation
Fig. 1 is the outside drawing that embodiment 1 obtains black phosphorus product in silica tube, and (a) is overall appearance, and (b) is for amplifying outward appearance, the outside drawing that (c) is black phosphorus in silica tube end.
Fig. 2 is the XRD figure of black phosphorus prepared by embodiment 1.
Fig. 3 is the SEM figure of black phosphorus prepared by embodiment 1; A black phosphorus SEM that (), (b) are respectively under different angles schemes.。
Fig. 4 is the light microscopic figure after the banded black phosphorus mechanically peel of embodiment 1 preparation; A (), (b), (c) are respectively the light microscopic figure under different angles.
Embodiment
Below in conjunction with drawings and the specific embodiments, the invention will be further described.
Embodiment 1
By tin, high-purity red phosphorus, iodine is according to tin: red phosphorus: ratio (mass ratio) mixing of iodine=0.6:20:0.1, then loads direct tube sealing in silica tube; Subsequently the silica tube after tube sealing is put into muffle furnace, the silica tube quantity put into depends on muffle furnace volume; Set the reaction times, be then warming up to 650 DEG C, insulation 2h, cools to 300 DEG C afterwards, continues insulation 2h, finally progressively cools to room temperature (10h).The strip black phosphorus of gained is evenly distributed in silica tube, as shown in Figure 1.
Products therefrom is black ribbon block, and Fig. 2 is its XRD figure, and its SEM as shown in Figure 3, can find out that products therefrom is black phosphorus.And through measuring, gained black phosphorus quality is about 97% of red phosphorus quality in raw material.
Choose the black phosphorus of gained strip, constantly carry out mechanically peel with adhesive tape, be finally bonded on silicon/silicon dioxide substrate, use light microscopic microscopic examination, the thinner black phosphorus of more large-area strip can be found as shown in Figure 4.Embodiment 2
By tin, high-purity red phosphorus, iodine is according to tin: red phosphorus: the ratio mixing of iodine=1:18:0.4, then loads direct tube sealing in silica tube; Subsequently the silica tube after tube sealing is put into muffle furnace, silica tube quantity depends on muffle furnace volume; Set the reaction times, be then warming up to 750 DEG C, insulation 5h, cools to 400 DEG C afterwards, continues insulation 5h, finally progressively cools to room temperature (15h).The strip black phosphorus of gained is evenly distributed in silica tube.
Embodiment 3
By tin, high-purity red phosphorus, iodine is according to tin: red phosphorus: the ratio mixing of iodine=3:40:0.5, then loads direct tube sealing in silica tube; Subsequently the silica tube after tube sealing is put into muffle furnace, silica tube quantity depends on muffle furnace volume; Set the reaction times, be then warming up to 500 DEG C, insulation 10h, cools to 200 DEG C afterwards, continues insulation 8h, finally progressively cools to room temperature (20h).The strip black phosphorus of gained is evenly distributed in silica tube.
Embodiment 4
By tin, high-purity red phosphorus, iodine is according to tin: red phosphorus: the ratio mixing of iodine=0.2:10:0.05, then loads direct tube sealing in silica tube; Subsequently the silica tube after tube sealing is put into muffle furnace, silica tube quantity depends on muffle furnace volume; Set the reaction times, be then warming up to 600 DEG C, insulation 1h, cools to 350 DEG C afterwards, continues insulation 5h, finally progressively cools to room temperature (6h).The strip black phosphorus of gained is evenly distributed in silica tube.
Claims (2)
1. constant temperature and a method for the banded black phosphorus of extensive preparation, it is characterized in that, the method comprises the steps:
High-purity red phosphorus, tin and iodine are mixed according to mass ratio 10-40:0.2-3:0.05-0.4, load in silica tube, the muffle furnace of constant temperature is put into after direct tube sealing, setting in-furnace temperature 500 ~ 650 DEG C, insulation 2-5h, cools to 300 ~ 480 DEG C with 5 to 10h afterwards again, insulation 2-5h, use 3 to 10h cool to room temperature again, in silica tube, obtain banded black phosphorus.
2. constant temperature according to claim 1 and the method for the banded black phosphorus of extensive preparation, it is characterized in that, described high-purity red phosphorus purity is not less than 99.99%.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498492A (en) * | 2016-11-01 | 2017-03-15 | 南京工业大学 | A kind of method for preparing rhombic system black phosphorus monocrystalline |
| CN106711408A (en) * | 2015-11-13 | 2017-05-24 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanosheet-graphene composite film anode, and preparation thereof |
| CN106744754A (en) * | 2016-11-14 | 2017-05-31 | 深圳大学 | A kind of red phosphorus preprocess method prepared for black phosphorus |
| CN108059137A (en) * | 2017-12-04 | 2018-05-22 | 中国科学院电工研究所 | A kind of preparation method of black phosphorus nano material |
| CN108128761A (en) * | 2018-01-30 | 2018-06-08 | 昆明理工大学 | A kind of continuous preparation method of black phosphorus |
| CN108408703A (en) * | 2018-06-15 | 2018-08-17 | 广西越洋科技股份有限公司 | A kind of production method of black phosphorus |
| CN110498404A (en) * | 2019-07-22 | 2019-11-26 | 山东玥能新材料科技有限公司 | A method of black phosphorus-carbon nano tube compound material is prepared in situ |
| CN111170291A (en) * | 2020-01-21 | 2020-05-19 | 上海交通大学 | Method for quickly preparing black phosphorus at low cost |
| WO2021025318A1 (en) * | 2019-08-07 | 2021-02-11 | 한국표준과학연구원 | Method for forming black phosphorous |
| CN112645295A (en) * | 2021-01-05 | 2021-04-13 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN112830462A (en) * | 2021-02-03 | 2021-05-25 | 陕西科技大学 | Method for safely and efficiently synthesizing high-purity black phosphorus |
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113620264A (en) * | 2021-08-27 | 2021-11-09 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| CN114772564A (en) * | 2022-04-27 | 2022-07-22 | 中南大学 | Black phosphorus arsenic quantum dot and preparation method thereof |
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| CN104310326A (en) * | 2014-10-29 | 2015-01-28 | 浙江大学 | Black phosphorus preparation method with high conversion rate |
| CN104630879A (en) * | 2015-02-28 | 2015-05-20 | 安庆美晶新材料有限公司 | Method for preparing black phosphorus monocrystal from high-purity red phosphorus under atmospheric pressure |
| CN104787736A (en) * | 2015-04-04 | 2015-07-22 | 成都育芽科技有限公司 | Method for large-scale preparation of black phosphorus with bilayer structure |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106711408A (en) * | 2015-11-13 | 2017-05-24 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanosheet-graphene composite film anode, and preparation thereof |
| CN106711408B (en) * | 2015-11-13 | 2019-05-10 | 中国科学院金属研究所 | Flexible lithium ion battery black phosphorus nanometer sheet-graphene composite film cathode and preparation |
| CN106498492A (en) * | 2016-11-01 | 2017-03-15 | 南京工业大学 | A kind of method for preparing rhombic system black phosphorus monocrystalline |
| CN106744754A (en) * | 2016-11-14 | 2017-05-31 | 深圳大学 | A kind of red phosphorus preprocess method prepared for black phosphorus |
| CN108059137A (en) * | 2017-12-04 | 2018-05-22 | 中国科学院电工研究所 | A kind of preparation method of black phosphorus nano material |
| CN108128761A (en) * | 2018-01-30 | 2018-06-08 | 昆明理工大学 | A kind of continuous preparation method of black phosphorus |
| CN108408703A (en) * | 2018-06-15 | 2018-08-17 | 广西越洋科技股份有限公司 | A kind of production method of black phosphorus |
| US10968102B2 (en) * | 2018-06-15 | 2021-04-06 | Black P2 (USA) INC. | Method for producing black phosphorus |
| CN110498404A (en) * | 2019-07-22 | 2019-11-26 | 山东玥能新材料科技有限公司 | A method of black phosphorus-carbon nano tube compound material is prepared in situ |
| KR20210017205A (en) * | 2019-08-07 | 2021-02-17 | 한국표준과학연구원 | Methods of forming black phosphorous |
| WO2021025318A1 (en) * | 2019-08-07 | 2021-02-11 | 한국표준과학연구원 | Method for forming black phosphorous |
| KR102255946B1 (en) | 2019-08-07 | 2021-05-25 | 한국표준과학연구원 | Methods of forming black phosphorous |
| CN111170291A (en) * | 2020-01-21 | 2020-05-19 | 上海交通大学 | Method for quickly preparing black phosphorus at low cost |
| CN112645295A (en) * | 2021-01-05 | 2021-04-13 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN112830462A (en) * | 2021-02-03 | 2021-05-25 | 陕西科技大学 | Method for safely and efficiently synthesizing high-purity black phosphorus |
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113620264A (en) * | 2021-08-27 | 2021-11-09 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| CN113620264B (en) * | 2021-08-27 | 2023-03-17 | 昆明理工大学 | Preparation method of nano black phosphorus/graphene |
| CN114772564A (en) * | 2022-04-27 | 2022-07-22 | 中南大学 | Black phosphorus arsenic quantum dot and preparation method thereof |
| CN114772564B (en) * | 2022-04-27 | 2023-04-07 | 中南大学 | Black phosphorus arsenic quantum dot and preparation method thereof |
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