阅读说明：本技术 一种CoSbSe纳米片材料的制备方法及其应用 (A kind of preparation method and applications of CoSbSe nanometer sheet material ) 是由 王先杰 林磊 付强 于 2019-09-25 设计创作，主要内容包括：一种CoSbSe纳米片材料的制备方法及其应用,本发明属于纳米材料制备技术领域,它的目的是针对CoSbSe作为热电材料所存在的制备过程所需温度较高、时间较长、能耗较高的问题。CoSbSe纳米片的制备方法：一、对碳布进行超声清洗；二、按照化学计量比Sb:Se＝1:1的比例将锑粉和硒粉混合；三、将钴盐、尿素和氟化铵加入到超纯水中搅拌溶解；四、碳布浸入步骤三的反应液中水热反应；五、将锑硒粉混合物和前驱体一同放入石英管中,抽真空密封,分两个阶段加热反应,得到CoSbSe纳米片。本发明得到的CoSbSe纳米片所需的制备温度大幅度降低,所需的制备时间大幅度减少,有利于清洁高效制备CoSbSe纳米片。(A kind of preparation method and applications of CoSbSe nanometer sheet material, the invention belongs to technical field of nanometer material preparation, its purpose is for CoSbSe is higher as preparation process required temperature present in thermoelectric material, the time is longer, the higher problem of energy consumption.The preparation method of CoSbSe nanometer sheet: one, carbon cloth is cleaned by ultrasonic；Two, antimony powder and selenium powder are mixed according to the ratio of stoichiometric ratio Sb:Se=1:1；Three, cobalt salt, urea and ammonium fluoride are added to stirring and dissolving in ultrapure water；Four, carbon cloth immerses hydro-thermal reaction in the reaction solution of step 3；Five, antimony selenium powder mixture and presoma are put into quartz ampoule together, vacuumize sealing, heating reaction, obtains CoSbSe nanometer sheet in two stages.Preparation temperature needed for the CoSbSe nanometer sheet that the present invention obtains is greatly lowered, and required preparation time is greatly reduced, and is conducive to clean and effective preparation CoSbSe nanometer sheet.)

1. a kind of preparation method of CoSbSe nanometer sheet material, it is characterised in that this method is to follow these steps to realize:

One, carbon cloth is cleaned by ultrasonic, the carbon cloth after being cleaned；

Two, antimony powder and selenium powder are mixed according to the ratio of stoichiometric ratio Sb:Se=1:1, antimony selenium powder mixture is obtained after grinding；

Three, cobalt salt, urea and ammonium fluoride are added to stirring and dissolving in ultrapure water, obtain reaction solution；

Four, the carbon cloth after cleaning is immersed in the reaction solution of step 3,6~10h of hydro-thermal reaction at 100~160 DEG C, reaction knot Carbon cloth is taken out after beam, obtains presoma after cleaning-drying；

Five, antimony selenium powder mixture is poured into quartz ampoule, presoma is put into quartz ampoule together, cover antimony selenium powder mixture On presoma surface, vacuum degree in quartz ampoule is evacuated to 1 × 10^-5Pa or less is simultaneously sealed, and is put into batch-type furnace, batch-type furnace temperature-rise period It is divided into two stages, the first stage is that furnace temperature is raised to 350~400 DEG C with the heating rate of 3~10 DEG C/min, and keep the temperature 20~ 40min, obtains antimony selenium solid solution, and second stage is to be warming up to 700~800 DEG C with the heating rate of 1~5 DEG C/min, and keep the temperature It handles, takes out carbon cloth after natural cooling, CoSbSe nanometer sheet is obtained after cleaning-drying.

2. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that carbon in step 1 Cloth is cleaned by ultrasonic 15~25min by acetone, ethyl alcohol, ultrapure water respectively.

3. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that institute in step 3 The cobalt salt stated is cobalt nitrate or cobaltous sulfate.

4. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that in step 4 Hydro-thermal reaction 6h at 120 DEG C.

5. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that institute in step 4 The drying stated is to be dried in vacuo 10h under the conditions of 70 DEG C.

6. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that will in step 5 20~150mg antimony selenium powder mixture pours into quartz ampoule.

7. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that in step 5 One stage was furnace temperature to be raised to 400 DEG C with the heating rate of 5 DEG C/min, and keep the temperature 20~40min.

8. a kind of preparation method of CoSbSe nanometer sheet material according to claim 1, it is characterised in that in step 5 Two-stage is 700~800 DEG C to be warming up to the heating rate of 1~5 DEG C/min, and keep the temperature 5~10h.

9. such as the application for the CoSbSe nanometer sheet that claim 1 is prepared, it is characterised in that make CoSbSe nanometer sheet material For thermoelectric material.

Technical field

The invention belongs to nano material preparation and clean energy resource preparation technical fields, and in particular to a kind of CoSbSe nanometer sheet The preparation method and applications of material.

Background technique

With the development and progress of human society, the consumption of fossil energy and the problem of environmental pollution thus caused become day It is beneficial serious.In order to solve the energy and environmental problem of facing mankind, energy waste is reduced, energy use efficiency, sufficiently benefit are improved Work with renewable energy and research and development novel environmental friendly materials is extremely urgent.Among these, thermoelectric material is made For a kind of new energy material, has and generate electricity and two big major functions of refrigeration, it can be with using the nature temperature difference and industrial waste heat Achieve the purpose that thermoelectric power generation, to improve energy use efficiency, energy shortage problem is effectively relieved, reduces making for fossil energy With, reduce the discharge of pernicious gas, for alleviate problem of environmental pollution play the role of it is vital.Therefore, seek in recent years Efficiently, low price, the new thermoelectric materials of rich reserves become the hot spot in the fields such as the energy, material, Condensed Matter Physics, chemistry.

CoSbSe is constituted as a kind of novel two-dimensional layer semiconductor material, with CoPS with similar element, Application prospect in terms of thermoelectric material receives more concern.But preparation method is single at present, and preparation process is multiple Miscellaneous, synthesis temperature and time are higher, and energy consumption is larger.Therefore develop a kind of efficiently feasible CoSbSe nanometer sheet thermoelectric material It is applied to have great importance.

Summary of the invention

The purpose of the present invention is for CoSbSe as preparation process required temperature present in thermoelectric material the higher, time Longer, the higher problem of energy consumption, and a kind of preparation method of relatively simple efficient CoSbSe nanometer sheet is proposed, using the party Method preparation effectively improves problem above.

The preparation method of CoSbSe nanometer sheet of the present invention follows these steps to realize:

One, carbon cloth is cleaned by ultrasonic, the carbon cloth after being cleaned；

Two, antimony powder and selenium powder are mixed according to the ratio of stoichiometric ratio Sb:Se=1:1, it is mixed that antimony selenium powder is obtained after grinding Close object；

Three, cobalt salt, urea and ammonium fluoride are added to stirring and dissolving in ultrapure water, obtain reaction solution；

Four, the carbon cloth after cleaning is immersed in the reaction solution of step 3,6~10h of hydro-thermal reaction at 100~160 DEG C, instead Carbon cloth is taken out after answering, and obtains presoma after cleaning-drying；

Five, antimony selenium powder mixture is poured into quartz ampoule, presoma is put into quartz ampoule together, make antimony selenium powder mixture It is covered on presoma surface, vacuum degree in quartz ampoule is evacuated to 1 × 10^-5Pa or less is simultaneously sealed, and is put into batch-type furnace, batch-type furnace heating Process is divided into two stages, and the first stage is furnace temperature to be raised to 350~400 DEG C with the heating rate of 3~10 DEG C/min, and keep the temperature 20~40min, obtains antimony selenium solid solution, second stage be warming up to 700~800 DEG C with the heating rate of 1~5 DEG C/min, and Isothermal holding takes out carbon cloth after natural cooling, CoSbSe nanometer sheet is obtained after cleaning-drying.

The application of CoSbSe nanometer sheet of the present invention is using CoSbSe nanometer sheet material as thermoelectric material.

The preparation method of CoSbSe material of the present invention is that the method for first passing through hydro-thermal synthesizes Co on conductive carbon cloth Presoma, later heat antimony selenium solid solution, under conditions of vacuum tightness distil after antimony, selenium steam and Co presoma in height It reacts under temperature, obtains final CoSbSe nanometer sheet.Compared with the CoSbSe nanometer sheet of existing high temperature process heat, this hair Preparation temperature needed for bright obtained CoSbSe nanometer sheet is greatly lowered, and required preparation time is greatly reduced, advantageous clear Clean efficient preparation CoSbSe nanometer sheet.

The preparation method of CoSbSe nanometer sheet of the present invention include it is following the utility model has the advantages that

1, the element that CoSbSe nanometer sheet of the present invention includes is the element of rich reserves, cheap, environmental-friendly, former Expect from a wealth of sources, chemical property stabilization；

2, equipment needed for preparing is simple, and synthesis temperature is lower, can significantly save the cost；

3, preparation condition is more wide in range, is relatively easy to that corresponding product is made in actual fabrication process.

Detailed description of the invention

Fig. 1 is the CoSbSe nano material and Sb that embodiment one obtains₂Se₃XRD diagram, wherein ◆ represent CoSbSe, ● generation Table Sb₂Se₃；

Fig. 2 be embodiment two obtain CoSbSe nano material, Sb₂Se₃And CoSb₃XRD diagram, wherein ◆ represent CoSbSe, ● represent Sb₂Se₃,Represent CoSb₃；

Fig. 3 be embodiment three obtain CoSbSe nano material, Sb₂Se₃And CoSb₃XRD diagram, wherein ◆ represent CoSbSe, ● represent Sb₂Se₃,Represent CoSb₃；

Fig. 4 be example IV obtain CoSbSe nano material, Sb₂Se₃And CoSe₃XRD diagram, wherein ◆ represent CoSbSe, ● represent Sb₂Se₃,Represent CoSb₃；

Fig. 5 be embodiment five obtain CoSbSe nano material, Sb₂Se₃And CoSe₃XRD diagram, wherein ◆ represent CoSbSe, ● represent Sb₂Se₃,Represent CoSe₃；

Fig. 6 be embodiment six obtain CoSbSe nano material, Sb₂Se₃And CoSe₃XRD diagram, wherein ◆ represent CoSbSe。

Specific embodiment