Perovskite film and method for manufacturing the same, perovskite battery and power consumption device

Abstract

The present invention provides a perovskite film and a method for producing the same, a perovskite battery and a power consumption device, wherein the perovskite film includes a perovskite substrate layer and a plurality of nanoprotrusions provided on at least one surface of the perovskite substrate layer and distributed at intervals.

Claims

1. It is a perovskite film, Perovskite substrate layer, A perovskite film comprising a plurality of nanoprotrusions provided on at least one surface of the perovskite substrate layer and distributed at intervals.

2. The perovskite film according to claim 1, wherein the average particle size of the nano-protrusions is 1 nm to 10 nm, and selectively 1 nm to 5 nm.

3. The perovskite film according to claim 1 or 2, wherein the distance between the center points of two adjacent nanoprotrusions is 2 nm to 1 μm, and selectively 10 nm to 0.5 μm.

4. The aforementioned nanoprotrusions are (1) The nanoprotrusions have an irregular columnar shape, (2) The chemical composition of the nanoprotrusions is L ｍ A ｎ－１ B ｎ X ３ｎ＋１ It includes 1 ≤ m ≤ 2, n ≥ 1 and is an integer, where L ion is NH ４ ＋ The following conditions must be met: Ion A is a monovalent cation, Ion B is a divalent metallic cation, Ions C and D are monovalent and trivalent metallic cations, respectively, and Ion X is a monovalent anion. The A ion is an organic cation, Li ＋ , Na ＋ , K ＋ , Rb ＋ and Cs ＋ and includes one or more of them, Selectively, the organic cation comprises at least one of an organic amine ion, a formamidino group, and an imidazole group. More selectively, the organic amine ion comprises at least one of a methylamine group, an ethylamine group, a propylamine group, a butylamine group, a pentylamine group, and a hexylamine group. Selectively, the A ion is an organic amine ion and Cs ＋ This includes one or more of the following: ◆B ions are Pb ２＋ Sn ２＋ Be ２＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ , Zn ２＋ , Ge ２＋ Fe ２＋ Co ２＋ ,Cd ２＋ and Ni ２＋ This includes one or more of the following: Selectively, the B ion is Pb ２＋ and Sn ２＋ This includes one or two of the following: The aforementioned C ion is Cs ＋ Ag ＋ _K ＋ and Ru ＋ This includes one or more of the following: The aforementioned D ion is Bi ３＋ Ni ３＋ Fe ３＋ and Cu ３＋ This includes one or more of the following: The aforementioned X ion is F － , Cl － , Br － and I － This includes one or more of the following: Selectively, the X ion is Cl － , Br － and I － A perovskite film according to any one of claims 1 to 3, comprising one or more of the above.

5. The aforementioned perovskite substrate layer is (1) The thickness of the perovskite substrate layer is 100 nm to 1000 nm, and selectively 500 nm to 800 nm, (2) The chemical composition of the perovskite substrate layer is compound ABX ３ Or A ２ CDX ６ It contains, where ion A is a monovalent cation, ion B is a divalent metallic cation, ions C and D are monovalent and trivalent metallic cations, respectively, and ion X is a monovalent anion, satisfying at least one of these conditions. The aforementioned A ion is an organic cation, Li ＋ Na ＋ _K ＋ , Rb ＋ and Cs ＋ This includes one or more of the following: Selectively, the organic cation comprises at least one of an organic amine ion, a formamidino group, and an imidazole group. More selectively, the organic amine ion comprises at least one of a methylamine group, an ethylamine group, a propylamine group, a butylamine group, a pentylamine group, and a hexylamine group. Selectively, the A ion is an organic amine ion and Cs ＋ This includes one or more of the following: ◆B ions are Pb ２＋ Sn ２＋ Be ２＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ , Zn ２＋ , Ge ２＋ Fe ２＋ Co ２＋ ,Cd ２＋ and Ni ２＋ This includes one or more of the following: Selectively, the B ion is Pb ２＋ and Sn ２＋ This includes one or two of the following: The aforementioned C ion is Cs ＋ Ag ＋ _K ＋ and Ru ＋ This includes one or more of the following: The aforementioned D ion is Bi ３＋ Ni ３＋ Fe ３＋ and Cu ３＋ This includes one or more of the following: The aforementioned X ion is F － , Cl － , Br － and I － This includes one or more of the following: Selectively, the X ion is Cl － , Br － and I － This includes one or more of the following: Selectively, the chemical composition of the perovskite substrate layer is organic halide Cs ｘ FA ｙ MA ｚ PbI ３ A perovskite film according to any one of claims 1 to 4, comprising x + y + z = 1, 0 ≤ x ≤ 0.05, 0.8 ≤ y ≤ 0.95, and 0 ≤ z ≤ 0.

1.

6. A method for producing a perovskite film, A step of manufacturing a perovskite substrate layer on a support layer, A method comprising the steps of contacting a solution of ammonium salt with the surface of the perovskite substrate layer and performing a first annealing treatment to form a plurality of nanoprotrusions distributed at intervals on the surface of the perovskite substrate layer, thereby forming a perovskite composite and obtaining the perovskite film.

7. The solution of the ammonium salt is (1) The mass concentration of the ammonium salt solution is 0.05 mg / mL to 1 mg / mL, (2) The ammonium salt contains one or more of ethylenediamine, propylenediamine, butylenediamine, and p-phenylenediamine, (3) The method according to claim 6, wherein the solution of the ammonium salt contains a first organic solvent, and the first organic solvent contains one or more of isopropyl alcohol, ethanol, ethylene glycol, and glycerol, satisfying at least one of these conditions.

8. The first annealing process described above is (1) The temperature of the first annealing treatment is 90°C to 120°C, (2) The method according to claim 6 or 7, wherein at least one of the following conditions is met: the time of the first annealing treatment is 5 min to 10 min.

9. The method according to any one of claims 6 to 8, further comprising the step of performing an impurity removal treatment on the perovskite complex.

10. The above step of performing an impurity removal treatment on the perovskite complex is: The process includes the step of bringing a second organic solvent into contact with the surface of the perovskite composite and performing a second annealing treatment. Selectively, the second organic solvent comprises one or more of isopropyl alcohol, ethanol, ethylene glycol, and glycerol. Selectively, the temperature of the second annealing process is 90°C to 120°C. The method according to claim 9, wherein the duration of the second annealing treatment is selectively 5 min to 10 min.

11. The above step of manufacturing a perovskite substrate layer on a support layer is, The process involves bringing a perovskite precursor solution into contact with a poor solvent on the support layer to form a wet film of the perovskite substrate layer, The step includes performing a third annealing treatment on the wet film of the perovskite substrate layer to obtain the perovskite substrate layer, Selectively, the temperature of the third annealing process is 90°C to 150°C. The method according to any one of claims 6 to 10, wherein selectively, the duration of the third annealing process is 10 min to 40 min.

12. (1) The perovskite precursor solution contains compound ABX ３ Or A ２ CDX ６ This includes, where ion A is a monovalent cation, ion B is a divalent metallic cation, ions C and D are monovalent and trivalent metallic cations, respectively, and ion X is a monovalent anion. The A ion is an organic cation, Li ＋ , Na ＋ , K ＋ , Rb ＋ , and Cs ＋ and includes one or more of them, Selectively, the organic cation comprises at least one of an organic amine ion, a formamidino group, and an imidazole group. More selectively, the organic amine ion comprises at least one of a methylamine group, an ethylamine group, a propylamine group, a butylamine group, a pentylamine group, and a hexylamine group. Selectively, the A ion is an organic amine ion and Cs ＋ This includes one or more of the following: The B ion is Pb ２＋ , Sn ２＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Zn ２＋ , Ge ２＋ , Fe ２＋ , Co ２＋ , Cu ２＋ and Ni ２＋ and includes one or more of them, Selectively, the B ion is Pb ２＋ and Sn ２＋ This includes one or two of the following: The aforementioned C ion is Cs ＋ Ag ＋ _K ＋ and Ru ＋ This includes one or more of the following: The aforementioned D ion is Bi ３＋ Ni ３＋ Fe ３＋ and Cu ３＋ This includes one or more of the following: The aforementioned X ion is F － , Cl － , Br － and I － This includes one or more of the following: Selectively, the X ion is Cl － , Br － and I － This includes one or more of the following: Selectively, the perovskite precursor solution contains organic halides Cs ｘ FA ｙ MA ｚ PbI ３ The equation includes x + y + z = 1, 0 ≤ x ≤ 0.05, 0.8 ≤ y ≤ 0.95, and 0 ≤ z ≤ 0.

1. (2) The molar concentration of the perovskite precursor solution is 1 mol / L to 1.8 mol / L, (3) The method according to claim 11, wherein the poor solvent contains one or more of chlorobenzene, anisole, ethyl ether, and ethyl acetate, the method according to claim 11, wherein at least one of these conditions is met.

13. A perovskite battery comprising a perovskite film according to any one of claims 1 to 5 or a perovskite film manufactured by the method according to any one of claims 6 to 12.

14. The perovskite battery according to claim 13, comprising a first electrode, a perovskite layer, a first charge transport layer, and a second electrode, wherein the perovskite layer comprises a perovskite film, and the nanoprotrusions in the perovskite film face the first charge transport layer along the thickness direction of the perovskite layer.

15. The first charge transport layer comprises a first charge transport substrate layer and a filler provided on the surface of the first charge transport substrate layer, wherein the filler extends along the thickness direction of the first charge transport substrate layer and fills the voids formed by the nanoprotrusions. Selectively, the first charge transport layer includes an electron transport layer. The perovskite battery according to claim 14, wherein selectively, the chemical composition of the first charge transport substrate layer and the filler are the same.

16. The present invention further includes a second charge transport layer, the second charge transport layer being provided between the first electrode and the perovskite layer. The perovskite battery according to claim 14 or 15, wherein the second charge transport layer selectively includes a hole transport layer.

17. A power consumption device comprising a perovskite battery according to any one of claims 13 to 16.

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