CN100491025C

CN100491025C - Process for producing zinc antimonide powder at low temperature

Info

Publication number: CN100491025C
Application number: CNB2007100698757A
Authority: CN
Inventors: 赵士超; 霍德璇; 吕燕飞
Original assignee: Hangzhou Electronic Science and Technology University
Current assignee: Hangzhou Dianzi University; Hangzhou Electronic Science and Technology University
Priority date: 2007-07-03
Filing date: 2007-07-03
Publication date: 2009-05-27
Anticipated expiration: 2027-07-03
Also published as: CN101081436A

Abstract

The process of composing ZnSb powder includes the following steps: dissolving zinc sulfate in water to compound solution and electrolysis to produce metal zinc grain dissolving antimony chloride in water to compound solution and reducing with sodium borohydride to obtain metal antimony grain, compounding metal zinc grain and metal antimony grain in the atom ratio of 1 to 1 to form reactant, and heat treating the reactant in an electric furnace at 150-200 deg.c under the protection of nitrogen to produce ZnSb. The process produces ZnSb powder at relatively low temperature, and Compared with available technology, the present invention has the advantages of simple materials, simple apparatus, simple process and low cost.

Description

A kind of method of producing zinc antimonide powder at low temperature

Technical field

The invention belongs to technical field of material, the method for synthetic zinc antimonide powder under particularly a kind of low-temperature condition condition.

Background technology

Zinc antimonide powder (ZnSb) can become electric energy with thermal power transfer as a kind of thermoelectric material of function admirable.Along with the energy scarcity problem becomes the focus of concern,, the energy savings people come above the heat energy recycle for investing vehicle exhaust, power plant's used heat etc. to sight.So ZnSb more and more obtains paying attention to.In order to obtain the method that the ZnSb material adopts high-temperature heat treatment usually, this method need consume a large amount of energy at present, and equipment and complex process make that the manufacturing cost of ZnSb material is higher simultaneously, and utilization is restricted.This patent both can obtain ZnSb at a lower temperature by new method, and raw materials used, equipment and synthesis technique are simple, and cost is low.

Summary of the invention

Purpose of the present invention is exactly at the deficiencies in the prior art, and the method for the synthetic thermoelectric material zinc antimonide powder of a kind of low temperature is provided.

The present invention adopts following process steps:

(1) with the water-soluble solution that is made into 0.05～0.5mol/L of sulfuric acid zinc salt, as electrolyte;

(2) electrolyte is carried out electrolysis and generate the metallic zinc particle;

(3), obtain the metallic antimony particle with sodium borohydride reduction then with the water-soluble solution that is made into 0.05～0.5mol/L of trichloride antimony;

(4) be that 1: 1 proportioning mix through the washing back according to atomic ratio with metallic zinc particle and metallic antimony particle, as reactant;

(5) reactant is put into the electric furnace of nitrogen protection, under 150～200 ℃ of conditions, heat-treated 1～10h.

The present invention adopts electrolysis to obtain highly active metallic zinc source, and reducing process obtains highly active metallic antimony source, and both can react at low temperatures and generate ZnSb.The present invention compared with the prior art, the outstanding advantage that has is that raw materials used, equipment and synthesis technique are simple, cost is low.

The specific embodiment

Embodiment 1:

A) take by weighing the ZnSO of 14.377g ₄7H ₂The beaker that O puts into 1000ml is mixed with the aqueous solution of 0.05mol/L, with graphite is that electrode electrolysis under the DC voltage of 10V generates the metallic zinc particle, take out the metallic zinc particle then and put into water and clean the zinc salt remove surface absorption, with being placed on dry for standby in 80 ℃ the baking oven;

B) taking by weighing the 11.405g trichloride antimony adds under magnetic agitation and fills in the beaker of 1000ml water, make the aqueous solution of 0.05mol/L, subsequently to wherein slowly adding the excessive borane reducing agent sodium hydride of 4.0g, the reaction back obtains the metallic antimony particle, taking-up metallic antimony particle is put into water and is cleaned the salt of removing surface absorption, places 80 ℃ baking oven dry for standby then;

C) be that the proportioning of 1:1 takes by weighing 1.65g and 3.05g respectively according to atomic ratio, mix that the electric furnace of putting into nitrogen protection then is in 150 ℃ of heat treatment 1h to above-mentioned metallic zinc and antimony particle, cooling naturally obtains the ZnSb powder subsequently.

Embodiment 2:

A) take by weighing the ZnSO of 28.754g ₄7H ₂The beaker that O puts into 1000ml is mixed with the aqueous solution of 0.1mol/L, with graphite is that electrode electrolysis under the DC voltage of 10V generates the metallic zinc particle, take out the metallic zinc particle then and put into water and clean the zinc salt remove surface absorption, with being placed on dry for standby in 80 ℃ the baking oven;

B) taking by weighing the 22.811g trichloride antimony adds under magnetic agitation and fills in the beaker of 1000ml water, be mixed with the aqueous solution of 0.1mol/L, subsequently to wherein slowly adding the excessive borane reducing agent sodium hydride of 8.0g, the reaction back obtains the metallic antimony particle, taking-up metallic antimony particle is put into water and is cleaned the salt of removing surface absorption, places 80 ℃ baking oven dry for standby then;

C) be that the proportioning of 1:1 takes by weighing 3.27g and 6.09g respectively according to atomic ratio, mix that the electric furnace of putting into nitrogen protection then is in 180 ℃ of heat treatment 10h to above-mentioned metallic zinc and antimony particle, cooling naturally obtains the ZnSb powder subsequently.

Embodiment 3:

A) take by weighing the ZnSO of 143.77g ₄7H ₂The beaker that O puts into 1000ml is mixed with the aqueous solution of 0.5mol/L, with graphite is that electrode electrolysis under the DC voltage of 10V generates the metallic zinc particle, take out the metallic zinc particle then and put into water and clean the zinc salt remove surface absorption, with being placed on dry for standby in 80 ℃ the baking oven;

B) taking by weighing the 114.055g trichloride antimony adds under magnetic agitation and fills in the beaker of 1000ml water, be mixed with the aqueous solution of 0.5mol/L, subsequently to wherein slowly adding the excessive borane reducing agent sodium hydride of 12.0g, the reaction back obtains the metallic antimony particle, taking-up metallic antimony particle is put into water and is cleaned the salt of removing surface absorption, places 80 ℃ baking oven dry for standby then;

C) be that the proportioning of 1:1 takes by weighing 3.27g and 6.09g respectively according to atomic ratio, mix that the electric furnace of putting into nitrogen protection then is in 200 ℃ of heat treatment 8h to above-mentioned metallic zinc and antimony particle, cooling naturally obtains the ZnSb powder subsequently.

Claims

1, a kind of method of producing zinc antimonide powder at low temperature is characterized in that may further comprise the steps:

(4) be that the proportioning of 1:1 mix through the washing back according to atomic ratio with metallic zinc particle and metallic antimony particle, as reactant;