CN103011263A - Method for preparing sheet antimony tin oxide (ATO) powder body - Google Patents

Abstract

The invention relates to a method for preparing a sheet antimony tin oxide (ATO) powder body. The method comprises the following steps of: adding stannous oxalate into the water under a stirring condition, and slowly dropwise adding an ammonium polyacrylate solution to obtain a settled solution; dissolving antimonous oxide by using tartaric acid, slowly dropwise adding the dissolved antimonous oxide into the settled solution, and dropwise adding the tartaric acid and ammonia water to ensure that pH of the system is between 2 and 12 to obtain a precursor liquid; stirring the precursor liquid at 40-90 DEG C to heat for 0.5-48 hours, drying the precursor liquid to be at a solid state at 120-200 DEG C, and performing thermal treatment on the dried powder body at 300-800 DEG C for 0.5-12hours to obtain the sheet powder body. The method is simple in process, low in equipment requirement, low in cost and easy to industrialize, and has easily-obtained raw materials and less procedures; chlorine-containing raw materials are not added during the whole process so as to pollute the environment; and meanwhile, the manufactured sheet ATO powder body has the advantages of good conductivity, good transparency and easiness for dispersion, and can be applied to the fields of anti-static fillers, ultraviolet screening films, air-sensitive sensors and the like.

Description

A kind of preparation method of sheet ATO powder

Technical field

The present invention relates to a kind of preparation method of sheet ATO powder, can be to environment in the starting material itself that the method is used and the last handling process, and this powder loose density is low, can be applied to the fields such as anti-electrostatic filler, ultraviolet shielded film and gas sensor.

Background technology

Tindioxide (SnO ₂) be that a kind of energy gap is the N-shaped semiconductor material of 3.6eV.Because its high electron mobility (109.56cm ²/ Vs), high carrier concentration (1.23 * 1O ¹⁹Cm ³), high light transmittance, the physicochemical property such as high refractive index (1.9-2) and stability at elevated temperature are mixed and unadulterated SnO ₂Based transparent film is used widely, as being used for anti-electrostatic filler, transparent conducting coating, ultraviolet shielded film, gas sensor, photo-electric display, solar cell, lithium ion cell electrode, the aspects such as voltage dependent resistor.

SnO ₂The preparation of base transparent conductive material is mainly with SnCl ₂Or SnCl ₄Be raw material, with SbCl ₃Or NH ₄F etc. are donor dopant, adopt the techniques such as magnetron sputtering, chemical vapour deposition, pyrolytic coating, collosol and gel, co-precipitation, hydro-thermal to be prepared.Wherein coprecipitation method is easy to get with raw material, and flow process is few, and technique is simple, and not high to equipment requirements, cost is low, is easy to the advantages such as industrialization, has occupied dominant position in actual production.Because contain chlorion in the raw material, and the later stage to adopt ammoniacal liquor to neutralize because the existence of strong polarity ion chlorion and ammonium radical ion makes nanoparticle produce easily salt bridge in precipitation process, and then cause occurring reuniting, make the pattern of particle become irregular.In order to obtain the nano-powder of regular morphology, must displace chlorion and ammonium radical ion by the suction filtration process, this process will be used a large amount of deionized waters and alcohol, and is not only more time-consuming but also cost is also higher.In addition, the method can only obtain the powder of class sphere.Sheet ATO powder has the specific surface area height, good conductivity, and therefore the advantage such as the transparency is good is necessary to develop the ATO powder of sheet.The SnS that investigator elder generation synthesizing flaky is arranged ₂, at the SnO for preparing sheet by thermal treatment ₂, obtaining the ATO powder by mixing at last, the method technique is more loaded down with trivial details, and the control difficulty is larger, and powder reuniting occurs easily.

Summary of the invention

Technical problem to be solved by this invention provides a kind of preparation method of ATO flaky powder, have simple to operate, raw material is easy to get, the characteristics that flow process is few, and can not produce the toxic and harmfuls such as oxysulfide in starting material itself and the last handling process, and can be to environment, not high to equipment requirements, cost is low, is easy to industrialization.

The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of preparation method of ATO flaky powder is characterized in that may further comprise the steps:

1) under agitation condition, stannous oxalate is added to the water, slowly drips the polyacrylic acid ammonium solution to obtaining settled solution; The concentration of stannous oxalate is 0.01～1mol/L, and the mol ratio of ammonium polyacrylate and stannous oxalate is between 1: 1～1: 20;

2) with the antimonous oxide solution of antimonous oxide with the rear acquisition of tartrate dissolving concentration 0.01～1mol/L, slowly drop in the above-mentioned settled solution, dripping tartrate makes the pH value of system between 2～5, obtain precursor liquid, perhaps drip ammoniacal liquor, make the pH value of system between 8～12, remove by filter transparent throw out, the mol ratio of antimonous oxide and stannous oxalate is between 1: 100～20: 100 at this moment;

3) with above-mentioned precursor liquid at 40～90 ℃ of stirring heating 0.5～48h, then be dried to solid-stately at 120～200 ℃, dried powder had both been obtained flaky powder at 300～800 ℃ of thermal treatment 0.5～12h.

As preferably, described step 2) when adopting tartrate, the pH value of solution is 3; When adopting ammoniacal liquor, the pH value of solution is 10 and will removes by filter transparent throw out.

As preferably, described polyacrylic acid ammonium solution adopts 40 (wt) % concentration.

Compared with prior art, the invention has the advantages that: technique of the present invention is simple, easy to operate, does not add chloride raw material in whole process, can be to environment, and raw material is easy to get, and flow process is few, not high to equipment requirements, cost is low, is easy to industrialization; The sheet ATO powder that makes simultaneously has good conductivity, and the advantage that the transparency is got well and is easy to disperse can be applied to the fields such as anti-electrostatic filler, ultraviolet shielded film and gas sensor.

Description of drawings

Fig. 1 a-1b: the electromicroscopic photograph of product;

Fig. 2 a-2b: the X-ray diffractogram of product.

Embodiment

Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.

Embodiment 1

Under agitation condition, in the stannous oxalate adding 40ml water with 0.01mol, slowly dripping concentration is that 40wt% polyacrylic acid ammonium solution 5～10ml is to obtaining settled solution.After the tartrate dissolving of antimonous oxide with 0.005mol with 0.001mol, slowly drop in the stannous oxalate solution, dropping concentration is that the tartaric acid solution of 5mol/L maintains about 3 the PH of system, obtains transparent, stable precursor liquid.With precursor liquid at 60 ℃ of stirring heating 12h, then be dried at 150 ℃ solid-state, with dried powder at 500 ℃ of thermal treatment 2h, the pattern of products therefrom such as Fig. 1 a, XRD is shown in Fig. 2 a.

Embodiment 2

Under agitation condition, in the stannous oxalate adding 40ml water with 0.01mol, slowly dripping concentration is that 40wt% polyacrylic acid ammonium solution 5～10ml is to obtaining settled solution.After the tartrate dissolving of antimonous oxide with 0.005mol with 0.001mol, slowly drop in the stannous oxalate solution, dropping concentration is that the ammoniacal liquor of 75wt% maintains about 10 the PH of system, obtains the emulsion of white, and will remove by filter transparent throw out.Emulsion at 40 ℃ of stirring heating 24h, is obtained settled solution, then be dried at 150 ℃ solid-state, with dried powder at 500 ℃ of thermal treatment 2h, the pattern of products therefrom such as Fig. 1 b, XRD is shown in Fig. 2 b.

Claims (2)

1. the preparation method of a sheet ATO powder is characterized in that may further comprise the steps:

1) under agitation condition, stannous oxalate is added to the water, slowly drips the polyacrylic acid ammonium solution to obtaining settled solution; The concentration of stannous oxalate is 0.01～1mol/L, and the mol ratio of ammonium polyacrylate and stannous oxalate is between 1: 1～1: 20;

2) with the antimonous oxide solution of antimonous oxide with the rear acquisition of tartrate dissolving concentration 0.01～1mol/L, slowly drop in the above-mentioned settled solution, dripping tartrate makes the pH value of system between 2～5, obtain precursor liquid, perhaps drip ammoniacal liquor, make the pH value of system between 8～12, remove by filter transparent throw out, the mol ratio of antimonous oxide and stannous oxalate is between 1: 100～20: 100 at this moment;

3) with above-mentioned precursor liquid at 40～90 ℃ of stirring heating 0.5～48h, then be dried to solid-stately at 120～200 ℃, dried powder had both been obtained flaky powder at 300～800 ℃ of thermal treatment 0.5～12h.

2. preparation method according to claim 1 is characterized in that described step 2) when adopting tartrate, the pH value of solution is 3; When adopting ammoniacal liquor, the pH value of solution is 10 and will removes by filter transparent throw out.

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