Flexible lead-free piezoelectric composite film and preparation method thereof, and electronic device

1 . A method of preparing a flexible lead-free piezoelectric composite film, comprising:

(A) preparing a SrSb x Sc 2-x TaCl 2 O 8 precursor powder doped with a rare-earth element, wherein 0.8<x<1.2;

(B) coating the SrSb x Sc 2-x TaCl 2 O 8 precursor powder with a shell to form a core-shell nanoparticle, wherein the shell is made from BaTiO 3 ; and

(C) dispersing the core-shell nanoparticle in a polyvinylidene fluoride (PVDF) matrix to obtain the flexible lead-free piezoelectric composite film.

2 . The method according to claim 1 , wherein in step (A), the rare-earth element is a lanthanide element.

3 . The method according to claim 1 , wherein step (A) comprises:

(A1) weighing Sr(NO 3 ) 2 , SbCl 3 , Sc(NO 3 ) 3 ·6H 2 O, TaCl 5 and a rare earth nitrate based on a stoichiometric ratio, and dissolving Sr(NO 3 ) 2 , SbCl 3 , Sc(NO 3 ) 3 ·6H 2 O, TaCl 5 and the rare earth nitrate in a polar solvent to obtain a mixture solution;

(A2) subjecting the mixture solution to hydrothermal synthesis in a sealed container, and cooling to obtain an intermediate product; and

(A3) subjecting the intermediate product to centrifugation, washing and drying to obtain the SrSb x Sc 2-x TaCl 2 O 8 precursor powder doped with the rare-earth element.

4 . The method according to claim 3 , wherein in step (A1), the rare earth nitrate is selected from the group consisting of Eu(NO 3 ) 3 ·6H 2 O, Er(NO 3 ) 3 ·5H 2 O, Yb(NO 3 ) 3 ·4H 2 O, Tm(NO 3 ) 3 ·4H 2 O and a combination thereof, and a total molar amount of the rare-earth element is 0.5-5.0% of a molar amount of Sr in the SrSb x Sc 2-x TaCl 2 O 8 precursor powder.

5 . The method according to claim 3 , wherein in step (A1), the polar solvent is a mixture of ethylene glycol and water in a volume ratio of 2-4:1, and a solid-to-liquid ratio for dissolution is 0.10±0.05 g/mL.

6 . The method according to claim 3 , wherein the step (A2) is performed through steps of:

heating the mixture solution to 170-190° C. at a rate of 5° C./min followed by holding at 170-190° C. for 7-9 h;

heating the mixture solution to 210-230° C. at a rate of 1° C./min followed by holding at 210-230° C. for 10-15 h; and

naturally cooling the mixture solution to 60° C.

7 . The method according to claim 1 , wherein step (B) comprises:

(B1) ultrasonically dispersing the SrSb x Sc 2-x TaCl 2 O 8 precursor powder in an anhydrous ethanol to form a suspension of the SrSb x Sc 2-x TaCl 2 O 8 precursor powder;

(B2) simultaneously dropwise adding a barium ion source solution and titanium ion source solution at an equal rate to the suspension under mechanical stirring, followed by directed heterogeneous nucleation to achieve a shell-coating treatment, so as to obtain an intermediate product; and

(B3) subjecting the intermediate product to centrifugation to collect a precipitate, and calcining the precipitate to form the core-shell nanoparticle.

8 . The method according to claim 7 , wherein the barium ion source solution is a solution of barium acetate in ethanol; and the titanium ion source solution is a complex of tetrabutyl titanate and acetylacetone.

9 . The method according to claim 1 , wherein step (C) comprises:

(C1) mixing the core-shell nanoparticle with a solution of the PVDF matrix to obtain a solid-liquid mixture;

(C2) subjecting the solid-liquid mixture to roll milling to obtain a slurry; and

(C3) subjecting the slurry to tape casting to form the flexible lead-free piezoelectric composite film.

10 . The method according to claim 9 , wherein the step (C) further comprises:

(C4) after step (C3), subjecting the flexible lead-free piezoelectric composite film to an internal stress relief treatment.

11 . The method according to claim 9 , wherein the solution of the PVDF matrix is a solution of PVDF in N-methylpyrrolidone (NMP), and a weight ratio of PVDF to NMP is 1:8-12; and

the solution of the PVDF matrix further contains an initiator and a dispersant.

12 . The method according to claim 1 , wherein a diameter of a core part of the core-shell nanoparticle is 80-150 nm; and a thickness of a shell part of the core-shell nanoparticle is 5-50 nm.

13 . The method according to claim 1 , wherein a weight percentage of the core-shell nanoparticle in the flexible lead-free piezoelectric composite film is 30-70%; and

the PVDF matrix is a PVDF polymer with a β-crystalline phase content exceeding 80%.

14 . An electronic device, comprising:

the flexible lead-free piezoelectric composite film according to claim 13 .

15 . The electronic device according to claim 14 , wherein the electronic device is an atomizer comprising:

an atomizing component;

wherein the atomizing component comprises a flexible substrate, an electrode layer, a piezoelectric functional layer and a waterproof protection layer stacked in sequence; and the piezoelectric functional layer is the flexible lead-free piezoelectric composite film.

16 . The electronic device according to claim 15 , wherein the electrode layer has an interdigital electrode structure with an electrode width of 50-200 μm and an electrode spacing of 100-300 μm.

17 . The electronic device according to claim 15 , wherein the flexible substrate is made of a polyimide (PI) film or a polyethylene terephthalate (PET) film; a thickness of the flexible substrate is 50-200 μm; and a surface roughness Ra of the flexible substrate is not greater than 0.1 μm.

18 . A flexible lead-free piezoelectric composite film, wherein the flexible lead-free piezoelectric composite film is prepared by the method according to claim 1 .