CN103420411A - Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles - Google Patents

Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles Download PDF

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CN103420411A
CN103420411A CN2013102899366A CN201310289936A CN103420411A CN 103420411 A CN103420411 A CN 103420411A CN 2013102899366 A CN2013102899366 A CN 2013102899366A CN 201310289936 A CN201310289936 A CN 201310289936A CN 103420411 A CN103420411 A CN 103420411A
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nano particle
zinc
particles
tin
cu2znsns4
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沈鸿烈
王威
金佳乐
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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Abstract

The invention relates to an ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles and belongs to the field of inorganic materials. On the basis of optimizing the formula, the microwave power and the time of a reaction solution, controllable preparation of the Cu2ZnSnS4 nano-particles is realized through adjusting the ultrasonic power. As the performance of the nano-particles is greatly influenced by the shapes and the sizes of the nano-particles, the Cu2ZnSnS4 nano-particles in different shapes and sizes have different application values. The particles with the particle sizes smaller than 10 nm are Cu2ZnSnS4 quantum dots with better luminous performance, the nano-particles with bigger particle sizes can be used for preparing ink, the ink is then used for preparing a Cu2ZnSnS4 film serving as an absorbing layer of a solar cell, and the Cu2ZnSnS4 particles of which the particle sizes reach the quasi micron size can be used as an anode material of a lithium ion battery. Therefore, controllable preparation of the Cu2ZnSnS4 nano-particles is very important. The inexpensive and easy-to-implement method is adopted to successfully prepare the Cu2ZnSnS4 particles in different particle sizes and different shapes.

Description

The controlled preparation Cu of a kind of ultrasonic assisted microwave synthesis 2ZnSnS 4The method of nano particle
Technical field
That the present invention relates to is the controlled preparation Cu of a kind of ultrasonic assisted microwave synthesis 2ZnSnS 4The method of nano particle, be specifically related to field of inorganic nano-material preparation.
Background technology
The exhaustion day by day of traditional fossil energy forces people seeking a kind of reproducible substitute energy.With other energy, compare, sun power is the optimal alternative energy of the mankind.By photovoltaic power generation technology, can directly convert solar energy into electrical energy, to meet the demand of the mankind to the energy.
Through the development of nearly ten years, the research of solar cell obtained many achievements.Yet the cost of solar cell still can be in any more at present, has greatly limited its widespread use.Therefore, people are finding solar cell material and the preparation method of a kind of low cost and environmental protection always.At present, the concern that the sulfide solar cell material is subject to is maximum.Wherein the most representative is Cu (Ga, In) (S, Se) 2(CIGS) thin film solar cell, its highest transformation efficiency has reached 20.3%.But In and Ga are rare elements, price is high, and Se is poisonous, not environmental protection, and this has limited its application to a great extent.Cu 2ZnSnS 4(CZTS) as the same type of material of CIGS, its band gap is about 1.48eV, very approaches the band gap 1.5eV of desirable solar cell absorption layer, and has high uptake factor (>10 4Cm -1).Cu 2ZnSnS 4In each element content in the earth's crust all higher, and be nontoxic, cheap, Cu simultaneously 2ZnSnS 4The solar cell theoretical efficiency is up to 32.4%, so CZTS is a kind of ideal solar cell material.The solar cell efficiency of conversion that the CZTS of take at present is absorption layer reaches 8.4%, and replaces Cu with a part of Se 2ZnSnS 4In the Cu of S 2ZnSn (S, Se) 4(CZTSSe) battery efficiency can reach 11.1%.Therefore this novel solar cell has good application prospect and huge commercial value.
At present, Cu 2ZnSnS 4The preparation method of film is mainly magnetron sputtering sulfuration method and thermal evaporation, and these two kinds of methods all need large-scale vacuum equipment, and preparation condition is required to comparatively harshness, can not fundamentally reduce the preparation cost of material.Yet, use the standby Cu of ink legal system instead 2ZnSnS 4Film can reduce preparation cost greatly.Wherein, the most important step of ink method is prepared uniform nano particle exactly, so just can prepare dispersiveness ink preferably, also just can prepare the Cu with excellent properties 2ZnSnS 4Film.The present invention mainly adopts the quick controlled preparation Cu of ultrasonic assisted microwave synthesis synthesis method 2ZnSnS 4Nano particle.At first, by the regulator solution formula, element ratio, shape and size as the conditions such as different presoma proportionings, different surfaces promoting agent, different sulphur source, different concns regulation and control nano particle, in order to prepare the nano particle with better dispersiveness, lay the first stone for preparing high-quality ink.Simultaneously, also by changing the microwave reaction condition such as reaction times, temperature of reaction, microwave power and increasing the ultrasonic synthetic Cu that further controls such as auxiliary 2ZnSnS 4The size of nano particle.
Summary of the invention
The present invention proposes the synthetic controlled preparation Cu of a kind of ultrasonic assisted microwave synthesis 2ZnSnS 4The method of nano particle, the method is without vacuum apparatus, reduce production costs, preparation cycle is short, be applicable to large-scale industrialization production, it is all nontoxic, pollution-free and cheap preparing copper-zinc-tin-sulfur nano particle material used, and the production cost that this has greatly reduced solar cell, have a good application prospect.
Cu involved in the present invention 2ZnSnS 4The preparation method of nano particle is achieved through the following technical solutions, and specifically comprises following step:
(1). be at first the preparation of solution; Cupric salt, stannous salt, divalent zinc salt, sulphur source and tensio-active agent are joined in organic solvent, by magnetic stirrer, evenly make it fully dissolve and obtain settled solution.Wherein said cupric salt concentration is 0.02M-0.08M, and stannous salt concentration is 0.02M-0.04M, and divalent zinc salt concentration is 0.02M-0.04M, and the concentration of sulfonium ion is 0.08M-0.2M, and the concentration of tensio-active agent is 0-1M or 0-0.02g/mL;
(2). the solution that step (1) is obtained is put in microwave oven; Microwave power is 100-800W, and the microwave reaction time is 5-60min, and temperature of reaction is 100-200 ℃, and the assisting ultrasonic output rating is 10-900W, obtains Cu 2ZnSnS 4Nanoparticles solution;
(3). the nano particle that step (2) is obtained is separated from solution with whizzer, and centrifugal speed is 3000-10000r/min, and the time is 5-30min, more repeatedly cleans with ultrapure water and ethanol, finally obtains Cu 2ZnSnS 4Nano particle.
Wherein the described cupric salt of step (1) is a kind of or its combination in cupric chloride, copper sulfate, cupric nitrate or venus crystals.
The described divalent zinc salt of step (1) is a kind of or its combination in zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
The described stannous salt of step (1) is a kind of or its combination in tin protochloride, tin acetate, methyl ethyl diketone tin or methyl ethyl diketone Tin tetrabromide.
The described sulphur of step (1) source is a kind of or its combination in thioacetamide, Sulfothiorine, thiocarbamide, Cys or lauryl mercaptan.
A kind of or its combination that the described tensio-active agent of step (1) is polyvinylpyrrolidone, cetyl trimethylammonium bromide or dodecylbenzene sulphur sodium.
The described organic solvent of step (1) is a kind of in ethylene glycol, polyoxyethylene glycol, glycerol or oleyl amine.
The principle of the invention:
Adopt ultrasonic auxiliary synthesis of nano particle, add ultrasonic vibration in preparation process, can effectively prevent the reunion of nano particle and the appearance of solution superheating phenomenon.This way can effectively limit the size of nano particle.Because every kind of sulphur source is different from the reaction mechanism of source metal, therefore can prepare the Cu of different shapes and size 2ZnSnS 4Nano particle.
Beneficial effect
The present invention and other Cu 2ZnSnS 4The technology of nano particle is compared, and following several beneficial effect is arranged: speed of response at first of the present invention is fast, and solvent-thermal method prepares Cu 2ZnSnS 4Nano particle is wanted tens hours or the longer time, and present technique only needs short several minutes or dozens of minutes just can prepare needed Cu 2ZnSnS 4Nano particle.Secondly, present technique can controlledly be prepared the Cu of different shape and size 2ZnSnS 4Nano particle, to meet different application demands.And the ultrasonic assisted microwave synthesis synthesis method that the present invention adopts belongs to antivacuum chemical synthesis process, avoided adopting the problem of vacuum apparatus costliness.
The accompanying drawing explanation
Fig. 1 is Cu prepared in embodiment 1,2 2ZnSnS 4The stereoscan photograph of nano particle.Ultrasonic assisted microwave synthesis prepares Cu 2ZnSnS 4The SEM photo of nano particle: (a) ultrasonic power 900W, (b) ultrasonic power 10W
Fig. 2 is embodiment 3,4, prepared Cu in 5 2ZnSnS 4The stereoscan photograph of nano particle.The Cu made under different microwave 2ZnSnS 4The SEM photo of nano particle: (a) microwave power 200W, (b) microwave power 400W, (c) microwave power 800W
Fig. 3 is embodiment 6,7, prepared Cu in 8 2ZnSnS 4The stereoscan photograph of nano particle.The Cu that the different surfaces promoting agent makes 2ZnSnS 4The SEM photo of nano particle: (a) dodecylbenzene sulphur sodium, (b) cetyl trimethylammonium bromide, (c) polyvinylpyrrolidone
Fig. 4 is embodiment 6,7, prepared Cu in 8 2ZnSnS 4The X ray diffracting spectrum of nano particle.The Cu that the different surfaces promoting agent makes 2ZnSnS 4The XRD figure spectrum of nano particle: (a) dodecylbenzene sulphur sodium, (b) cetyl trimethylammonium bromide, (c) polyvinylpyrrolidone
Fig. 5 is embodiment 6,7, prepared Cu in 8 2ZnSnS 4The Raman spectrum of nano particle.The Cu that the different surfaces promoting agent makes 2ZnSnS 4The Raman spectrum of nano particle: (a) dodecylbenzene sulphur sodium, (b) cetyl trimethylammonium bromide, (c) polyvinylpyrrolidone
Fig. 6 is Cu prepared in embodiment 9,10 2ZnSnS 4The stereoscan photograph of nano particle.The Cu made under different polyvinylpyrrolidone content 2ZnSnS 4The SEM photo of nano particle: (a) 0g, (b) 0.2g
Fig. 7 is Cu prepared in embodiment 11 2ZnSnS 4The scanning electron microscope of nano particle and transmission electron microscope photo.The L-cysteine prepares Cu as the sulphur source 2ZnSnS 4The SEM of nano particle and TEM photo
Fig. 8 is Cu prepared in embodiment 12 2ZnSnS 4The transmission electron microscope photo of nano particle.Thioacetamide prepares Cu as the sulphur source 2ZnSnS 4The TEM photo of nano particle
Embodiment
Below in conjunction with embodiment, the invention will be further described, but should not limit the scope of the invention with this.
Embodiment 1
Take 0.02M zinc chloride, 0.02M tin protochloride, 0.02M cupric chloride, 0.08M thiocarbamide and 0.6g polyvinylpyrrolidone and be dissolved in the ethylene glycol of 50mL, after stirring, put in microwave oven and heat, microwave power is 800W, and ultrasonic power is 900W.Temperature of reaction is 120 ℃, and the reaction times is 30min, centrifugation, and the ultrapure water washing, obtain Cu 2ZnSnS 4Nano particle.The preparation-obtained Cu of Fig. 1 (a) 2ZnSnS 4The SEM photo of nano particle, prepared nano particle mean sizes is 200nm, flower-like structure.
Embodiment 2
Adopt the 10W ultrasonic power, other parameters are identical with embodiment 1.Fig. 1 (b) is prepared Cu 2ZnSnS 4The SEM photo of nano particle, the nano particle size obtained is about 500nm, flower-like structure.Fig. 1 (a) compares with Fig. 1 (b), in two under different ultrasonic power the shape of prepared nano particle identical, but under the large condition of ultrasonic power, the size of resulting nano particle is less.
Embodiment 3
Taking 0.04M zinc acetate, 0.04M tin acetate, 0.0SM venus crystals, 0.2M thiocarbamide and 0.6g polyvinylpyrrolidone is dissolved in the ethylene glycol of 50mL, put in microwave oven and heat after stirring, the adjusting microwave power is 200W, add ultrasonic assisting, ultrasonic power is 450W simultaneously, and temperature of reaction is 120 ℃, reaction times is 30min, centrifugation, the ultrapure water washing, obtain Cu 2ZnSnS 4Nano particle, the stereoscan photograph of nano particle is as shown in Fig. 2 (a).Have the rod-shpaed particle that is about 7.5 μ m in prepared particle, and size is about the flower-shaped particle of 300nm.
Embodiment 4
Adopt the 400W microwave power, other parameter is identical with embodiment 3, and the existing rod-shpaed particle of prepared nano particle has again flower-shaped particle, the stereoscan photograph that Fig. 2 (b) is prepared nano particle, the flower-shaped particle that nano particle is 300nm left and right size.
Embodiment 5
Adopt the 800W microwave power, other parameter is identical with embodiment 3, and the stereoscan photograph of prepared nano particle is as shown in Fig. 2 (c), and the nano particle mean sizes made is 400nm, flower-like structure.
Embodiment 6
Taking 0.02M zinc nitrate, 0.02M tin protochloride, 0.04M cupric nitrate, 0.08M thiocarbamide and 0.06M dodecylbenzene sulphur sodium is dissolved in the ethylene glycol of 50mL, put in microwave oven and heat after stirring, microwave power is adjusted to 800W, ultrasonic power is 450W, temperature of reaction is 120 ℃, and the reaction times is 30min, centrifugation, the ultrapure water washing, obtain Cu 2ZnSnS 4The film nano particle.Prepared Cu 2ZnSnS 4The stereoscan photograph of nano particle, X ray diffracting spectrum, Raman spectrum is respectively as Fig. 3 (a), and (a) in Fig. 4, shown in (a) in Fig. 5.Prepared nano particle is dumbbell shaped, and size is about 500nm.XRD and Raman result show the Cu prepared 2ZnSnS 4Nano particle is for having the custerite structure of (112) preferred orientation.
Embodiment 7
Adopting the 0.06M cetyl trimethylammonium bromide is tensio-active agent, other parameters are identical with embodiment 6, (b) in Fig. 3 (b), Fig. 4, stereoscan photograph, X ray diffracting spectrum that (b) in Fig. 5 is prepared nano particle, Raman spectrum.From the SEM photo, prepared nano particle is ball-like structure, and size is about 500nm.XRD and Raman result show that the nano particle of preparing is the CZTS that the custerite structure has (112) preferred orientation.
Embodiment 8
Adopting the 1g polyvinylpyrrolidone is tensio-active agent, and other parameters are identical with embodiment 6, (c) in Fig. 3 (c), Fig. 4, stereoscan photograph, X ray diffracting spectrum that (c) in Fig. 5 is prepared nano particle, Raman spectrum.The Cu made 2ZnSnS 4The flower-shaped particle that nano particle is the 450nm left and right, and be the custerite structure with (112) preferred orientation.
Embodiment 9
Do not add any tensio-active agent, other parameters are identical with embodiment 6, and Fig. 6 (a) is prepared nano particle stereoscan photograph.The spherical particle that prepared nano particle is 550nm left and right size.
Embodiment 10
Adopting the 0.2g polyvinylpyrrolidone is tensio-active agent, and other parameters are identical with embodiment 6, and Fig. 6 (b) is prepared nano particle stereoscan photograph.Prepared nano particle mean sizes is 500nm, flower-like structure.
Embodiment 11
Taking 0.02M zinc sulfate, 0.02M methyl ethyl diketone Tin tetrabromide, 0.04M copper sulfate, 0.08M Cys and 0.6g polyvinylpyrrolidone is dissolved in the ethylene glycol of 50mL, put in microwave oven and heat after stirring, microwave power is adjusted to 800W, ultrasonic power is 450W, temperature of reaction is 120 ℃ of C, and the reaction times is 30min, centrifugation, the ultrapure water washing, obtain Cu 2ZnSnS 4Nano particle.Fig. 7 is SEM and the TEM photo of the CZTS nano particle that makes, and nano particle is hollow ball-shape, and particle mean size is about 50nm.
Embodiment 12
Adopt the thioacetamide of 0.08M as the sulphur source, other parameters are identical with embodiment 11, and Fig. 8 is prepared Cu 2ZnSnS 4The transmission electron microscope photo of nano particle.The nanocrystal that the nano particle obtained is the 5nm left and right.
Embodiment 13
Adopt the Sulfothiorine of 0.08M as the sulphur source, other parameters are identical with embodiment 11, the spherical particle that prepared nano particle is the 500nm left and right.
Embodiment 14
Adopt the lauryl mercaptan of 0.08M as the sulphur source, other parameters are identical with embodiment 11, the spherical particle that prepared nano particle is the 300nm left and right.
Embodiment 15
The employing glycerol is solvent, and other parameters are identical with embodiment 11, the flower-shaped particle that prepared nano particle is the 400nm left and right.
Embodiment 16
The employing poly(oxyethylene glycol) 400 is solvent, and other parameters are identical with embodiment 11, the rod-like nano particle that prepared nano particle is the 50nm left and right.
Embodiment 17
The employing oleyl amine is solvent, and other parameters are identical with example 11, the spherical particle that prepared nano particle is the 10nm left and right.
Embodiment 18
Taking 0.02M zinc chloride, 0.02M methyl ethyl diketone tin, 0.04M cupric chloride, 0.08M thiocarbamide and 0.6g polyvinylpyrrolidone is dissolved in the ethylene glycol of 50mL, put in microwave oven and heat after stirring, microwave power is adjusted to 800W, ultrasonic power is 450W, temperature of reaction is 100 ℃, and the reaction times is 30min, centrifugation, the ultrapure water washing, obtain Cu 2ZnSnS 4Nano particle.The spherical particle that prepared nano particle is the 50nm left and right.
Embodiment 19
Adopting temperature of reaction is 200 ℃, and other parameters are identical with embodiment 18, the spherical particle that prepared nano particle is the 200nm left and right.
Embodiment 20
The employing reaction times is 5min, and other parameters are identical with embodiment 18, the platy shaped particle that prepared nano particle is the 200nm left and right.
Embodiment 21
The employing reaction times is 60min, and other parameters are identical with embodiment 18, the flower-shaped particle that prepared nano particle is the 800nm left and right.

Claims (7)

1. the controllable method for preparing of copper-zinc-tin-sulfur particle, is characterized in that, comprises the steps:
(1). be at first the preparation of solution; The mantoquita of different concns, pink salt, zinc salt, sulphur source and tensio-active agent are joined in organic solvent, by magnetic stirrer, evenly make it fully dissolve and obtain settled solution.
Wherein said cupric salt concentration is 0.02M-0.08M, and stannous salt concentration is 0.02M-0.04M, and divalent zinc salt concentration is 0.02M-0.04M, and the concentration of sulfonium ion is 0.08M-0.2M, and the concentration of tensio-active agent is 0-1M or 0-0.02g/mL;
(2). the solution that step (1) is obtained is put in microwave oven; Microwave power is 100-800W, and the microwave reaction time is 5-60min, and temperature of reaction is 100-200 ℃, and the assisting ultrasonic output rating is 10-900W, obtains Cu 2ZnSnS 4Nanoparticles solution;
(3). the nano particle that step (2) is obtained is separated from solution with whizzer, and centrifugal speed is 3000-10000r/min, and the time is 5-30min, more repeatedly cleans with ultrapure water and ethanol, finally obtains Cu 2ZnSnS 4Nano particle.
2. the controlled method for preparing the copper-zinc-tin-sulfur nano particle of a kind of ultrasonic assisted microwave synthesis according to claim 1, is characterized in that, the described cupric salt of step (1) is a kind of or its combination in cupric chloride, copper sulfate, cupric nitrate or venus crystals.
3. the controlled method for preparing the copper-zinc-tin-sulfur nano particle of a kind of ultrasonic assisted microwave synthesis according to claim 1, is characterized in that, the described divalent zinc salt of step (1) is a kind of or its combination in zinc chloride, zinc sulfate, zinc nitrate or zinc acetate.
4. the controlled method for preparing the copper-zinc-tin-sulfur nano particle of a kind of ultrasonic assisted microwave synthesis according to claim 1, it is characterized in that, the described stannous salt of step (1) is a kind of or its combination in tin protochloride, tin acetate, methyl ethyl diketone tin or methyl ethyl diketone Tin tetrabromide.
5. the controlled method for preparing the copper-zinc-tin-sulfur nano particle of a kind of ultrasonic assisted microwave synthesis according to claim 1, is characterized in that, the sulphur source is a kind of or its combination in thioacetamide, Sulfothiorine, thiocarbamide, Cys or lauryl mercaptan.
6. the controlled method for preparing the copper-zinc-tin-sulfur nano particle of a kind of ultrasonic assisted microwave synthesis according to claim 1, is characterized in that a kind of or its combination that tensio-active agent is polyvinylpyrrolidone, cetyl trimethylammonium bromide or dodecylbenzene sulphur sodium.
7. the controlled method for preparing the copper-zinc-tin-sulfur nano particle of a kind of ultrasonic assisted microwave synthesis according to claim 1, is characterized in that, organic solvent is a kind of in ethylene glycol, polyoxyethylene glycol, glycerol or oleyl amine.
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CN105161572A (en) * 2015-08-31 2015-12-16 南京航空航天大学 Ink multi-layer coating preparation method of Cu2ZnSnS4 solar cell absorption layer
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CN106848289A (en) * 2017-02-26 2017-06-13 桂林理工大学 One species lotus root sheet spinel-type ZnMn2O4Raw powder's production technology
CN107827158A (en) * 2017-10-08 2018-03-23 南京邮电大学 A kind of controllable preparation small size Cu2WS4The method of nanocube
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CN104261461A (en) * 2014-09-17 2015-01-07 重庆大学 Method for preparing Cu-Zn-Sn-S nano hollow spheres
CN104261461B (en) * 2014-09-17 2016-04-06 重庆大学 A kind of method preparing Cu-Zn-Sn-S nano-hollow ball
CN105161572A (en) * 2015-08-31 2015-12-16 南京航空航天大学 Ink multi-layer coating preparation method of Cu2ZnSnS4 solar cell absorption layer
CN105253909A (en) * 2015-08-31 2016-01-20 武汉理工大学 Preparation method of copper zinc tin sulfide nanocrystal with custerite structure
CN105470112A (en) * 2015-11-18 2016-04-06 广东工业大学 Method and application for preparing copper zinc tin sulfur semiconductor film on FTO substrate
CN105668643A (en) * 2016-01-11 2016-06-15 华南师范大学 Method for preparing lithium ion batteries cathode material
CN106379931A (en) * 2016-09-30 2017-02-08 昆明理工大学 Method for rapidly preparing copper-zinc-tin-sulfur nanoparticles
CN106517314A (en) * 2016-12-06 2017-03-22 昆明理工大学 Preparing method of CZTS particulates
CN106848289A (en) * 2017-02-26 2017-06-13 桂林理工大学 One species lotus root sheet spinel-type ZnMn2O4Raw powder's production technology
CN106848289B (en) * 2017-02-26 2020-04-14 桂林理工大学 Lotus root-like flaky spinel type ZnMn2O4Method for preparing powder
CN109207150A (en) * 2017-07-07 2019-01-15 天津师范大学 The hydrothermal preparing process of water-soluble alloy quantum dot and its application
CN107827158A (en) * 2017-10-08 2018-03-23 南京邮电大学 A kind of controllable preparation small size Cu2WS4The method of nanocube
CN109037042A (en) * 2018-07-27 2018-12-18 金陵科技学院 A method of copper-zinc-tin-sulfur film is prepared based on water nano ink
CN112034027A (en) * 2020-08-29 2020-12-04 南京航空航天大学 Electrochemical sensing electrode for measuring ammonia nitrogen ions in wastewater and preparation method thereof
CN112034027B (en) * 2020-08-29 2021-12-14 南京航空航天大学 Electrochemical sensing electrode for measuring ammonia nitrogen ions in wastewater and preparation method thereof

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Application publication date: 20131204