CN104032374A - Preparation method of lead titanate/zinc oxide composite nanostructure on flexible substrate - Google Patents

Abstract

The preparation method of the lead titanate/zinc oxide composite nanostructure on the flexible substrate disclosed by the present invention comprises the steps of: preparing powdered one-dimensional columnar structure lead titanate single crystal nanofibers by hydrothermal method, adding absolute ethanol and ultrasonically oscillating into suspension The liquid is dropped onto the silicon wafer, dried and annealed to obtain tetragonal lead titanate single crystal nanofibers, which are scraped off from the silicon wafer, added with absolute ethanol, and dropped onto the flexible substrate to form titanic acid on the flexible substrate. lead single crystal nanofiber film; then zinc acetate is used as the zinc oxide seed solution, and the mixed solution of zinc nitrate aqueous solution, hexamethylenetetramine aqueous solution and sodium citrate aqueous solution is the zinc oxide growth solution. Zinc oxide is grown on the flexible substrate of the fiber membrane to obtain a lead titanate/zinc oxide composite nanostructure on the flexible substrate. The process of the invention is simple, easy to control, pollution-free and low in cost. The lead titanate/zinc oxide composite nanostructures prepared on the flexible substrate have high purity and good dispersion.

Description

Preparation method of lead titanate/zinc oxide composite nanostructure on a flexible substrate

technical field

The invention relates to a preparation method of a lead titanate/zinc oxide composite nanostructure, in particular to a preparation method of a lead titanate/zinc oxide composite nanostructure on a flexible substrate.

Background technique

Lead titanate is a typical perovskite-type ferroelectric oxide. Due to its simple structure and strong piezoelectricity and ferroelectricity, lead titanate has been the prototype of research in the field of ferroelectricity and piezoelectricity since its discovery in the 1950s. It is of great significance for people to understand the electronic origin of piezoelectricity and ferroelectricity of perovskite oxides. In addition, it also has great application potential as a pyroelectric material and is a promising ferroelectric, piezoelectric, and pyroelectric material. Zhejiang University used polymer-assisted hydrothermal method for the first time to prepare lead titanate single crystal nanofibers with one-dimensional columnar structure (Zhaohui Ren, Gang Xu, Yong Liu, Xiao Wei, Yihan Zhu, Xiaobin Zhang, Guanglie Lv, Youwen Wang, Yuewu Zeng , Piyi Du, Wenjian Weng, Ge Shen, JZ Jiang and Gaorong Han, PbTiO ₃ Nanofibers with Edge-Shared TiO ₆ Octahedra, 2010, 132(16), 5572-5573.). In lead titanate crystals with this structure, the titanyl octahedrons are connected by common edges to form a one-dimensional columnar structure. This one-dimensional columnar structure lead titanate can be transformed into tetragonal phase (P4mm) lead titanate after annealing under certain conditions, while maintaining the morphology of one-dimensional nanofibers. However, the research on composite materials of this material and other oxides, especially the preparation and performance exploration of composite materials on flexible substrates is still in the exploratory stage, and there are no relevant reports at home and abroad.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a lead titanate/zinc oxide composite nanostructure on a flexible substrate with simple process and easy control.

The preparation method of the lead titanate/zinc oxide composite nanostructure on the flexible substrate of the present invention comprises the following steps:

1) Measure according to the chemical formula PbTiO ₃ of the one-dimensional columnar structure lead titanate single crystal nanofiber to be synthesized, weigh lead nitrate and dissolve it in deionized water, and adjust the Pb ²⁺ ion concentration to 0.25-1mol/L;

Dissolve butyl titanate in ethylene glycol methyl ether, adjust the concentration of Ti ⁴⁺ ions in the solution to 0.25-1mol/L, add ammonia water with a mass concentration of 30% until Ti ⁴⁺ ions are completely precipitated, filter, wash, and obtain titanium Precipitation of oxyhydroxides;

2) Prepare potassium hydroxide aqueous solution of 0.5-5mol/L and polyvinyl alcohol aqueous solution with a concentration of 2g/L respectively, and precipitate potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution, titanium oxyhydroxide and lead nitrate in step 1) The aqueous solution is added to the inner tank of the reactor together, the volume ratio of potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution and lead nitrate aqueous solution is 1:2:1, and the molar ratio of Ti ⁴⁺ and Pb ²⁺ in the lead nitrate solution is 1:1 , put the liner of the reaction kettle in the reaction kettle, seal it tightly, put it in a furnace at 180-200 ^o C and keep it warm for 8-12 hours, then cool it down to room temperature naturally in the air, take out the reaction product, filter it, and use deionized Washing with water and drying to obtain powdery one-dimensional columnar structure lead titanate single crystal nanofibers;

3) Add the powdery one-dimensional columnar structure lead titanate single crystal nanofibers prepared in step 2) to absolute ethanol whose volume is 0.25 to 1 times the volume of the lead nitrate aqueous solution in step 2), and ultrasonically oscillate to obtain a suspension. Drop it on the cleaned silicon wafer until it is covered, dry, drop the suspension on the silicon wafer again, dry, repeat 4~5 times, then keep the silicon wafer at 600~750℃ for at least 1.5h, cool After taking it out, the tetragonal phase lead titanate single crystal nanofibers are obtained on the silicon wafer;

4) Scrape off the tetragonal lead titanate single crystal nanofiber film obtained in step 3) from the silicon wafer, add it to absolute ethanol whose volume is 0.25 to 1 times the volume of the lead nitrate aqueous solution in step 2), and ultrasonically oscillate to obtain Suspension, drop it on the cleaned flexible substrate until it is covered, dry, drop the suspension on the flexible substrate again, dry, repeat 4 to 5 times, and form lead titanate single crystal nanometer on the flexible substrate Fiber membrane;

5) Configure 0.001~0.01mol/L zinc acetate aqueous solution, and drop it on the flexible substrate with lead titanate single crystal nanofiber membrane in step 4) until it is covered, dry, and drop the zinc acetate aqueous solution on the flexible substrate again on, dry, repeat 4~5 times, and then keep it warm at 100℃ for 0.5~2h;

6) Prepare 0.001mol/L~0.1mol/L zinc nitrate aqueous solution, 0.001mol/L-0.1mol/L hexamethylenetetramine aqueous solution and 2~80mM/L sodium citrate aqueous solution respectively, and mix nitric acid Zinc aqueous solution, hexamethylenetetramine aqueous solution and sodium citrate aqueous solution are mixed and added to the reaction vessel at a volume ratio of 20:20:1, and the flexible substrate treated in step 5) is immersed in the mixed solution, sealed, and placed at 85~100°C Keep it warm for 0.5-12 hours, take it out after cooling, wash and dry to obtain the lead titanate/zinc oxide composite nanostructure on the flexible substrate.

In the present invention, the flexible base can be polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN) or polyimide (PI) .

The purity of lead nitrate, butyl titanate, potassium hydroxide, polyvinyl alcohol, zinc acetate, zinc nitrate, hexamethylenetetramine, absolute ethanol and sodium citrate is not lower than chemical purity.

The reaction kettle is a reaction kettle with a polytetrafluoroethylene liner and sealed with a stainless steel sleeve.

The invention has the advantages of simple process, easy control, no pollution and low cost, and the prepared lead titanate/zinc oxide composite nanostructure on the flexible substrate has high purity and good dispersibility. It can provide a development basis for the preparation of composite materials of perovskite oxides and semiconductor oxides.

Description of drawings

FIG. 1 is an XRD spectrum of the lead titanate/zinc oxide composite nanostructure on PET prepared in Example 1.

2 is a scanning electron microscope picture of the lead titanate/zinc oxide composite nanostructure on PET prepared in Example 1.

Detailed ways

The present invention will be further described below in conjunction with embodiment.

Example 1

1) Prepare 20ml of lead nitrate aqueous solution with a Pb ²⁺ ion concentration of 0.25mol/L; dissolve butyl titanate in ethylene glycol methyl ether to make the Ti ⁴⁺ ion concentration in the solution 0.25mol/L, add mass concentration 30% ammonia water until Ti ⁴⁺ ions are completely precipitated, filtered, washed, and titanium oxyhydroxide precipitates are obtained;

2) Prepare 20ml of 1mol/L potassium hydroxide aqueous solution and 40ml of 2g/L polyvinyl alcohol aqueous solution respectively, and combine potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution, titanium oxyhydroxide precipitation and step 1) lead nitrate aqueous solution together Add it to the inner tank of the reaction kettle, the molar ratio of Ti ⁴⁺ and Pb ²⁺ in the lead nitrate solution is 1:1, put it in the reaction kettle, seal it, keep it warm in a furnace at 180 ^o C, and after reacting for 12 hours, put it in The temperature is naturally cooled to room temperature in the air, the reaction product is taken out, filtered, washed with deionized water, and dried to obtain a powdery one-dimensional columnar structure lead titanate single crystal nanofiber;

3) Add the powdery one-dimensional columnar structure lead titanate single crystal nanofibers prepared in step 2) into 5mL of absolute ethanol, and ultrasonically oscillate to obtain a dispersed suspension, which is added dropwise to the cleaned 3× 3cm ² silicon wafer until it is covered, put it under the infrared lamp to dry, drop the suspension liquid on the silicon wafer again, dry, after repeating this 4 times, a lead titanate single crystal nanofiber film is formed on the silicon wafer, and then Put it in a muffle furnace at 750 ^o C for 1.5 hours, cool to room temperature and take it out, so that the product phase changes into tetragonal phase lead titanate single crystal nanofibers;

4) Scrape off the tetragonal phase lead titanate single crystal nanofiber film obtained in step 3) from the silicon wafer, add it to 5mL of absolute ethanol, and ultrasonically oscillate to obtain a well-dispersed suspension. Add the suspension dropwise to the The cleaned PET is covered until it is covered, dried under an infrared lamp, and the suspension is dropped on the PET again, dried, and so repeated 4 times to form a lead titanate single crystal nanofiber film on the PET;

5) Configure zinc acetate aqueous solution with a concentration of 0.01mol/L as the secondary zinc oxide seed solution, drop the seed solution onto the PET with lead titanate single crystal nanofiber membrane in step 4) until it is covered, and place Dry in a drying oven at 60 ^o C for 5 minutes, drop the aqueous solution of zinc acetate on the PET again, and dry, repeat this 4 times, place the processed sample in a muffle furnace at 100 ^o C for 30 minutes, cool to room temperature and take it out;

6) Prepare 40ml of 0.05mol/L zinc nitrate aqueous solution, 40ml of 0.05mol/L hexamethylenetetramine aqueous solution and 2ml of 20mM/L sodium citrate aqueous solution, and mix them as zinc oxide growth solution and put them in the reaction In the container, immerse the sample treated in step 5) into the container containing the growth solution, seal it with plastic wrap and place it in an incubator at 90 ^o C, keep it warm for 2 hours, then cool it down to room temperature naturally, take out the sample, and wash it with deionized water. After drying, a lead titanate/zinc oxide composite nanostructure is obtained on the PET.

The XRD spectrum of the lead titanate/zinc oxide composite nanostructure on PET prepared in this example is shown in Figure 1. It can be seen that the sample has a good degree of crystallization and has tetragonal phase (P4mm) lead titanate and wurtzite oxidation. The diffraction peak of zinc indicates that the product is a composite of two materials. The corresponding SEM photos are shown in Figure 2, and the lead titanate/zinc oxide composite nanostructures are uniformly distributed on the PET. The obtained lead titanate/zinc oxide composite nanostructure on PET can withstand large deformation and has good flexibility.

Example 2

1) Prepare 20ml of lead nitrate aqueous solution with a Pb ²⁺ ion concentration of 0.5mol/L; dissolve butyl titanate in ethylene glycol methyl ether to make the Ti ⁴⁺ concentration in the solution 0.5mol/L, add mass 30% ammonia water until Ti ⁴⁺ ions are completely precipitated, filtered and cleaned to obtain titanium oxyhydroxide precipitation;

2) Prepare 20ml of 0.5mol/L potassium hydroxide aqueous solution and 40ml of 2g/L polyvinyl alcohol aqueous solution respectively, and deposit potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution, titanium hydroxide solution and lead nitrate aqueous solution in step 1) Add them together into the inner tank of the reaction kettle, the molar ratio of Ti ⁴⁺ and Pb ²⁺ in the lead nitrate solution is 1:1, place in the reaction kettle, seal it, keep it warm in a furnace at 200 ^o C, and after reacting for 12 hours, put it in the Naturally cool down to room temperature in the air, take out the reaction product, filter, wash with deionized water, and dry to obtain powdery one-dimensional columnar structure lead titanate single crystal nanofibers;

3) Add 10mL of absolute ethanol to the powdery one-dimensional columnar structure lead titanate single crystal nanofibers prepared in step 2), and ultrasonically oscillate to obtain a dispersed suspension, which is added dropwise to the cleaned 3×3cm ² silicon wafer Up until it is covered, dry it under an infrared lamp for 5 minutes, drop the suspension on the silicon wafer again, and dry it. After repeating 4 times, a lead titanate single crystal nanofiber film is formed on the silicon wafer, and then placed in the muffle Keep it in the furnace at 650 ^o C for 2 hours, take it out after cooling to room temperature, and make the product phase change into tetragonal phase lead titanate single crystal nanofibers.

4) Scrape off the tetragonal phase lead titanate single crystal nanofiber film obtained in step 3) from the silicon wafer, add 5mL of absolute ethanol, and ultrasonically oscillate to obtain a well-dispersed suspension, and add the suspension dropwise to the cleaned Put it on the PC until it is covered, dry it under an infrared lamp, drop the suspension on the PC again, and dry it. Repeat this 4 times to form a lead titanate single crystal nanofiber film on the PC;

5) Configure an aqueous zinc acetate solution with a concentration of 0.005mol/L as the secondary zinc oxide seed solution, drop the seed solution onto the PC with the lead titanate single crystal nanofiber film in step 4) until it is covered, and place Dry in a drying oven at 60 ^o C for 5 minutes, drop the zinc acetate aqueous solution on the PC again, and dry, repeat this 4 times, place the processed sample in a muffle furnace at 100 ^o C for 2 hours, cool to room temperature and take it out;

6) Prepare 20ml of 0.001mol/L zinc nitrate aqueous solution, 20ml of 0.001mol/L hexamethylenetetramine aqueous solution and 1ml of 2mM/L sodium citrate aqueous solution, and mix them as zinc oxide growth solution and put them in the reaction In the container, immerse the sample treated in step 5) into the container containing the growth solution, seal it with plastic wrap and place it in an incubator at 85 ^o C, keep it warm for 12 hours, and then cool it down to room temperature naturally, take out the sample, and wash it with deionized water. After drying, a lead titanate/zinc oxide composite nanostructure is obtained on the PC.

Example 3

1) Prepare 20ml of lead nitrate aqueous solution with a Pb ²⁺ ion concentration of 1mol/L; dissolve butyl titanate in ethylene glycol methyl ether to make the Ti ⁴⁺ concentration in the solution 1mol/L, add ammonia water with a mass concentration of 30% Until Ti ⁴⁺ ions are completely precipitated, filter and wash to obtain titanium oxyhydroxide precipitation;

2) Prepare 20ml of 2mol/L potassium hydroxide aqueous solution and 40ml of 2g/L polyvinyl alcohol aqueous solution respectively, and combine potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution, titanium oxyhydroxide precipitation and step 1) lead nitrate aqueous solution together Add it into the inner tank of the reaction kettle, the molar ratio of Ti ⁴⁺ and Pb ²⁺ in the lead nitrate solution is 1:1, put it in the reaction kettle, seal it, keep it warm in a furnace at 200 ^o C, and after reacting for 10 hours, put it in Naturally cool down to room temperature in the air, take out the reaction product, filter, wash with deionized water, and dry to obtain powdery one-dimensional columnar structure lead titanate single crystal nanofibers;

3) Add 20mL of absolute ethanol to the powdery one-dimensional columnar structure lead titanate single crystal nanofibers prepared in step 2), and ultrasonically oscillate to obtain a suspension, and add the suspension dropwise to the cleaned 3×3cm ² silicon wafer Up until it is covered, dry under 60 ^o C infrared lamp for 5min, drop the suspension on the silicon wafer again, dry, repeat this 5 times, and form a lead titanate single crystal nanofiber film on the silicon wafer, then put Put it into a muffle furnace at 600 ^o C for 4 hours, cool to room temperature and take it out, so that the product phase changes into tetragonal phase lead titanate single crystal nanofibers;

4) Scrape off the tetragonal phase lead titanate single crystal nanofiber film obtained in step 3) from the silicon wafer, add 10mL of absolute ethanol, and ultrasonically oscillate to obtain a suspension, and drop the suspension onto the cleaned PEN to its Spread it all over, dry it under an infrared lamp, drop the suspension on the PEN again, dry it, and repeat this 5 times to form a lead titanate single crystal nanofiber film on the PEN;

5) Configure zinc acetate aqueous solution with a concentration of 0.001mol/L as the secondary zinc oxide seed solution, drop the seed solution onto the PEN with lead titanate single crystal nanofiber membrane in step 4) until it is covered, and place Dry in a drying oven at 60 ^o C for 5 minutes, drop the zinc acetate aqueous solution on the PEN again, and dry, repeat this 5 times, place the processed sample in a muffle furnace at 100 ^o C for 1 hour, cool to room temperature and take it out;

6) Prepare 40ml of 0.05mol/L zinc nitrate aqueous solution, 40ml of 0.05mol/L hexamethylenetetramine aqueous solution, and 2ml of 20mM/L sodium citrate aqueous solution, and mix them as zinc oxide growth solution in In the reaction container, immerse the sample treated in step 5) into the container containing the growth solution, seal it with plastic wrap and place it in an incubator at 90 ^o C, keep it warm for 4 hours, then cool it down to room temperature naturally, take out the sample, and wash it with deionized water , and dried to obtain a lead titanate/zinc oxide composite nanostructure on PEN.

Example 4

1) Prepare 20ml of lead nitrate aqueous solution with a Pb ²⁺ ion concentration of 0.75mol/L; dissolve butyl titanate in ethylene glycol methyl ether to make the Ti ⁴⁺ concentration in the solution 0.75mol/L, and add a mass concentration of 30% ammonia water until Ti ⁴⁺ ions are completely precipitated, filtered and cleaned to obtain titanium oxyhydroxide precipitation;

2) Prepare 20ml of 5mol/L potassium hydroxide aqueous solution and 40ml of 2g/L polyvinyl alcohol aqueous solution, add potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution, titanium hydroxide precipitate and step 1) lead nitrate aqueous solution together Into the reactor liner, the molar ratio of Ti ⁴⁺ and Pb ²⁺ in the lead nitrate solution is 1:1, put it in the reactor, seal it, keep it warm in a furnace at 200 ^o C, and after reacting for 8 hours, place it in the air naturally cool down to room temperature, take out the reaction product, filter, wash with deionized water, and dry to obtain powdery one-dimensional columnar structure lead titanate single crystal nanofibers;

3) Add 10mL of absolute ethanol to the powdery one-dimensional columnar structure lead titanate single crystal nanofibers prepared in step 2), ultrasonically oscillate to obtain a dispersed suspension, and add the suspension dropwise to the cleaned 3×3cm ² Place the silicon wafer until it is fully covered, dry it under an infrared lamp for 5 minutes, drop the suspension on the silicon wafer again, and dry it. After repeating this 5 times, a lead titanate single crystal nanofiber film is formed on the silicon wafer, and then Put it in a muffle furnace at 700 ^o C for 2 hours, cool to room temperature and take it out, so that the product phase changes into tetragonal phase lead titanate single crystal nanofibers;

4) Scrape off the tetragonal phase lead titanate single crystal nanofiber film obtained in step 3) from the silicon wafer, add 20mL of absolute ethanol, and ultrasonically oscillate to obtain a well-dispersed suspension, add the suspension dropwise to the cleaned The PI is covered until it is covered, dried under an infrared lamp, and the suspension is dropped on the PI again, dried, and so repeated 4 times to form a lead titanate single crystal nanofiber film on the PI;

5) Configure zinc acetate aqueous solution with a concentration of 0.005mol/L as the secondary zinc oxide seed solution, drop the seed solution onto the PI with lead titanate single crystal nanofiber membrane in step 4) until it is covered, and place Dry in a drying oven at 60 ^o C for 5 minutes, drop the zinc acetate aqueous solution on the PI again, and dry, repeat this 4 times, place the processed sample in a muffle furnace at 100 ^o C for 30 minutes, cool to room temperature and take it out;

6) Prepare 40ml of 0.1mol/L zinc nitrate aqueous solution, 40ml of 0.1mol/L hexamethylenetetramine aqueous solution, and 2ml of 80mM/L sodium citrate aqueous solution, and mix them as zinc oxide growth solution in In the reaction container, immerse the sample treated in step 5) into the container containing the growth solution, seal it with plastic wrap and place it in an incubator at 100 ^o C, keep it warm for 0.5h, and then cool it down to room temperature naturally, take out the sample, and wash it with deionized water. After cleaning and drying, lead titanate/zinc oxide composite nanostructures were obtained on PI.

Claims (4)

1. a preparation method of lead titanate/zinc oxide composite nanostructure on a flexible substrate, is characterized in that comprising the steps: 1) Measure according to the chemical formula PbTiO ₃ of the one-dimensional columnar structure lead titanate single crystal nanofiber to be synthesized, weigh lead nitrate and dissolve it in deionized water, and adjust the Pb ²⁺ ion concentration to 0.25-1mol/L; Dissolve butyl titanate in ethylene glycol methyl ether, adjust the concentration of Ti ⁴⁺ ions in the solution to 0.25-1mol/L, add ammonia water with a mass concentration of 30% until Ti ⁴⁺ ions are completely precipitated, filter, wash, and obtain titanium Precipitation of oxyhydroxides; 2) Prepare potassium hydroxide aqueous solution of 0.5-5mol/L and polyvinyl alcohol aqueous solution with a concentration of 2g/L respectively, and precipitate potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution, titanium oxyhydroxide and lead nitrate in step 1) The aqueous solution is added to the inner tank of the reactor together, the volume ratio of potassium hydroxide aqueous solution, polyvinyl alcohol aqueous solution and lead nitrate aqueous solution is 1:2:1, and the molar ratio of Ti ⁴⁺ and Pb ²⁺ in the lead nitrate solution is 1:1 , put the liner of the reaction kettle in the reaction kettle, seal it tightly, put it in a furnace at 180-200 ^o C and keep it warm for 8-12 hours, then cool it down to room temperature naturally in the air, take out the reaction product, filter it, and use deionized Washing with water and drying to obtain powdery one-dimensional columnar structure lead titanate single crystal nanofibers; 3) Add the powdery one-dimensional columnar structure lead titanate single crystal nanofibers prepared in step 2) to absolute ethanol whose volume is 0.25 to 1 times the volume of the lead nitrate aqueous solution in step 2), and ultrasonically oscillate to obtain a suspension. Drop it on the cleaned silicon wafer until it is covered, dry, drop the suspension on the silicon wafer again, dry, repeat 4~5 times, then keep the silicon wafer at 600~750℃ for at least 1.5h, cool After taking it out, the tetragonal phase lead titanate single crystal nanofibers are obtained on the silicon wafer; 4) Scrape off the tetragonal lead titanate single crystal nanofiber film obtained in step 3) from the silicon wafer, add it to absolute ethanol whose volume is 0.25 to 1 times the volume of the lead nitrate aqueous solution in step 2), and ultrasonically oscillate to obtain Suspension, drop it on the cleaned flexible substrate until it is covered, dry, drop the suspension on the flexible substrate again, dry, repeat 4 to 5 times, and form lead titanate single crystal nanometer on the flexible substrate Fiber membrane; 5) Configure 0.001~0.01mol/L zinc acetate aqueous solution, and drop it on the flexible substrate with lead titanate single crystal nanofiber membrane in step 4) until it is covered, dry, and drop the zinc acetate aqueous solution on the flexible substrate again on, dry, repeat 4~5 times, and then keep it warm at 100℃ for 0.5~2h; 6) Prepare 0.001mol/L~0.1mol/L zinc nitrate aqueous solution, 0.001mol/L-0.1mol/L hexamethylenetetramine aqueous solution and 2~80mM/L sodium citrate aqueous solution respectively, and mix nitric acid Zinc aqueous solution, hexamethylenetetramine aqueous solution and sodium citrate aqueous solution are mixed and added to the reaction vessel at a volume ratio of 20:20:1, and the flexible substrate treated in step 5) is immersed in the mixed solution, sealed, and placed at 85~100°C Keep it warm for 0.5-12 hours, take it out after cooling, wash and dry to obtain the lead titanate/zinc oxide composite nanostructure on the flexible substrate. 2. according to the preparation method of lead titanate/zinc oxide composite nanostructure on the flexible base described in claim 1, it is characterized in that described flexible base is polyethylene terephthalate, polycarbonate, poly Ethylene naphthalate or polyimide. 3. according to the preparation method of lead titanate/zinc oxide composite nanostructure on flexible substrate described in claim 1, it is characterized in that described lead nitrate, butyl titanate, potassium hydroxide, polyvinyl alcohol, zinc acetate The purity of zinc nitrate, hexamethylenetetramine, absolute ethanol and sodium citrate is not less than chemically pure. 4. according to the preparation method of the lead titanate/zinc oxide composite nanostructure on the flexible substrate described in claim 1, it is characterized in that described reaction kettle is to have polytetrafluoroethylene liner and adopt the closed reaction kettle of stainless steel sleeve .