Perovskite battery based on special-shaped porous nickel oxide and preparation method thereof

Abstract

The invention discloses a special-shaped porous nickel oxide-based perovskite cell and a preparation method thereof, and belongs to the technical field of solar cells. The cell comprises a substrate, a special-shaped porous NiO layer, an SAM layer, a perovskite layer, an electron transport layer and a back electrode layer which are stacked in sequence. The SAM layer is in contact with the special-shaped porous NiO layer, fills and covers the porous surface of the special-shaped porous NiO layer, and is combined with the special-shaped porous NiO layer through chemical bonds. The problems of insufficient anchoring points and poor bonding strength of a self-assembled monomolecular layer (SAM) and a nickel oxide (NiO) layer of a perovskite cell in the prior art can be solved. And the obtained perovskite cell has relatively high open-circuit voltage (Voc) and relatively low series resistance (Rs).

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and particularly to a perovskite solar cell based on heteromorphic porous nickel oxide and a preparation method thereof. Background Art

[0002] Perovskite solar cells have become a research hotspot in the photovoltaic field due to their high efficiency and low-cost potential. As a key component, the hole transport layer (HTL) directly affects the carrier transport ability and device efficiency through its interfacial quality with the perovskite layer. The specific surface area of the traditional nickel oxide (NiO) layer is limited, and the self-assembled monolayer (SAM) is difficult to fully infiltrate, resulting in insufficient anchoring sites for SAM, unable to fully passivate the NiO surface and reduce the defect density, leading to the easy occurrence of interfacial non-radiative recombination. In the prior art, although the bonding strength can be partially improved through surface modification or introducing an intermediate layer, there is a lack of a method to optimize the uniform coverage of SAM and improve the bonding strength with SAM by changing the NiO structure. Therefore, there is an urgent need for an innovative solution that combines the structural design of NiO with interfacial chemistry enhancement to break through the bottleneck of the prior art. Summary of the Invention

[0003] The present invention provides a perovskite solar cell based on heteromorphic porous nickel oxide and a preparation method thereof, which can solve the problems of insufficient anchoring sites and poor bonding strength between the self-assembled monolayer (SAM) and the nickel oxide (NiO) layer in the perovskite solar cell in the prior art.

[0004] In a first aspect, the present invention provides a perovskite solar cell based on heteromorphic porous nickel oxide, which includes a substrate, a heteromorphic porous NiO layer, a SAM layer, a perovskite layer, an electron transport layer, and a back electrode layer stacked in sequence;

[0005] The SAM layer is in contact with the heteromorphic porous NiO layer, filling and covering its porous surface.

[0006] The substrate is used to transport the holes generated inside the perovskite solar cell to the outside of the perovskite solar cell; the heteromorphic porous NiO layer is configured to cover the substrate; the SAM layer is chemically bonded to the heteromorphic porous NiO layer and, together with the heteromorphic porous NiO layer, transports the generated holes to the substrate; the perovskite layer is configured to cover the SAM layer and is used to absorb the electron-hole pairs generated by sunlight; the electron transport layer is configured to cover the passivation layer and is used to transport the electrons generated by the perovskite layer; and the back electrode layer is configured to be disposed on the electron transport layer and is used to transport the generated electrons to the outside of the perovskite solar cell.

[0007] Further, the heteromorphic porous NiO layer includes three-dimensional heteromorphic porous NiO.

[0008] Further, the structure of the three-dimensional shaped porous NiO includes any one of a columnar structure, a helical structure, an inclined columnar structure, a zigzag structure, a C-shaped structure, and a Y-shaped structure.

[0009] Further, the raw material of the back electrode layer includes any one of a metal electrode, a metal oxide electrode, and a metal oxide / metal / metal oxide sandwich electrode.

[0010] Further, a passivation layer 1 is provided between the perovskite layer and the electron transport layer, and a passivation layer 2 is provided between the electron transport layer and the back electrode layer;

[0011] The raw material of the passivation layer 1 includes any one of PEAI, PDADI, PDAI, MgF, CsF, and LiF;

[0012] The raw material of the passivation layer 2 includes SnO2 and BCP.

[0013] In a second aspect, the present invention provides a method for preparing a perovskite battery based on shaped porous nickel oxide, comprising the following steps:

[0014] S1. Substrate pretreatment:

[0015] The ultrasonically cleaned substrate is subjected to ultraviolet-ozone treatment for 5-20 min;

[0016] S2. Preparation of the shaped NiO layer:

[0017] Using the vacuum inclined deposition technique, the angle of the substrate is inclined at 0-90° and rotated at 0-360° in three-dimensional space; using Ni, NiO, and doped NiOx targets as sources, with an oxygen partial pressure of 0.005-0.5 Pa, a shaped NiO layer with a deposition thickness of 10-50 nm is deposited;

[0018] S3. Preparation of the shaped porous NiO layer:

[0019] The shaped NiO layer is immersed in a 5-10 vol% H2O2 solution for 5-20 min, and then heated in an oven at 40-80 °C for 10-30 min to obtain the shaped porous NiO layer;

[0020] S4. Preparation of the SAM layer:

[0021] One of Me-4PACz, Me-2PACz, and 4PDACB is added to solvent 1 to prepare a solution with a concentration of 0.1-1 mg / mL. The solution is coated on the surface of the shaped porous NiO layer; after coating, it is placed in an atmospheric environment for 5-30 min; then annealed at 100-150 °C for 10-50 min to form a uniform monolayer; then annealed in argon or a nitrogen / hydrogen mixture at 100-350 °C for 0.5-2 h to obtain the SAM layer;

[0022] S5. Prepare the perovskite layer:

[0023] Add any one of CsPbI x Br 3-x , FAPbI x Br 3-x and MAPbI x Br 3-x to solvent 2 to prepare a precursor solution with a concentration of 0.5 - 2 g / mL, and coat the precursor solution on the SAM layer; then anneal at 100 - 150 °C for 30 - 90 min to form a perovskite layer with a thickness of 400 - 800 nm;

[0024] S6. Prepare the passivation layer 1:

[0025] Add the raw materials of the passivation layer 1 to solvent 3 to prepare a solution with a concentration of 0.5 mg / mL, coat the solution on the perovskite layer, and then anneal at 100 - 150 °C for 30 - 90 min to form a passivation layer 1 with a thickness of 5 - 20 nm;

[0026] S7. Prepare the electron transport layer:

[0027] Add the raw materials of the electron transport layer to solvent 4 to prepare a solution with a concentration of 5 - 50 mg / mL, coat the solution on the passivation layer 1; then anneal at 80 - 120 °C for 5 - 30 min to form an electron transport layer with a thickness of 20 - 100 nm; the raw materials of the electron transport layer include any one of SnO2, ZnO, TiO2, C60, and PCBM;

[0028] S8. Prepare the passivation layer 2:

[0029] On the electron transport layer, form a passivation layer 2 with a thickness of 5 - 15 nm by ALD using the raw materials of the passivation layer 2;

[0030] S9. Prepare the back electrode layer:

[0031] Form a back electrode layer with a thickness of 20 - 200 nm on the passivation layer 2 by vacuum evaporation or magnetron sputtering.

[0032] Furthermore, the substrate in step S1 is conductive glass with any one of the transparent conductive layers such as FTO, ITO, ICO, AZO, ICO, SnO2 / Ag / SnO2, ITO / Ag / ITO, and ITO / Cu / ITO plated on its surface.

[0033] Furthermore, the vacuum inclined deposition technique in step S2 is selected from any one of magnetron sputtering, electron beam evaporation, and laser pulse deposition methods.

[0034] Further, the solvent 1 in step S4 is any one or a mixture of ethanol, isopropanol, DMSO, and DMF; the coating method is any one of spin coating, slot coating, and inkjet drop coating.

[0035] Further, the solvent 2 in step S5 is any one or a mixture of DMF, DMSO, NMP, and ACN; the coating method is any one of spin coating, slot coating, and inkjet drop coating.

[0036] Further, the solvent 3 in step S6 is any one or a mixture of ethanol, isopropanol, DMSO, and DMF; the coating method is any one of spin coating, slot coating, and inkjet drop coating.

[0037] Further, the solvent 4 in step S7 is chlorobenzene; the coating method is any one of spin coating, slot coating, and inkjet drop coating.

[0038] Further, the preparation of the passivation layer 1 in step S6 includes the following process steps:

[0039] Evaporate the raw material of the passivation layer 1 on the perovskite layer at an evaporation rate of 0.1 - 0.2 A / s to form a passivation layer 1 with a thickness of 0.1 - 5 nm.

[0040] Further, the raw material of the passivation layer 1 includes any one of MgF, CsF, and LiF.

[0041] Further, the preparation of the electron transport layer in step S7 includes the following process steps:

[0042] Evaporate C60 and PCBM on the passivation layer 1 at an evaporation rate of 0.1 - 0.5 A / s to form an electron transport layer with a thickness of 10 - 50 nm.

[0043] Further, the preparation of the passivation layer 2 in step S8 includes the following process steps:

[0044] Evaporate the raw material of the passivation layer 2 on the electron transport layer at an evaporation rate of 0.1 - 0.3 A / s to form a passivation layer 2 with a thickness of 2 - 10 nm.

[0045] Further, the raw material of the passivation layer 2 includes BCP.

[0046] Advantages of the present invention:

[0047] (1) The unique three-dimensional porous NiO structure with irregular shapes enhances the interfacial bonding force of SAM: The three-dimensional porous NiO with irregular shapes prepared by the vacuum inclined deposition technique in the present invention has a unique multi-dimensional pore structure, including through-pores formed by irregular protrusions and micropores formed on the NiO surface by H2O2 treatment, which significantly increases the specific surface area and provides dense anchoring sites for SAM molecules. The through-pores of the irregular porous NiO allow SAM molecules to be uniformly distributed along the inner wall of the pores, and the micropores on the NiO surface further optimize the attachment state of SAM molecules, enabling SAM molecules to fully contact the NiO surface. Thanks to this composite structure, SAM and NiO are more likely to form a continuous passivation layer through Ni-O-P chemical bonds, thereby effectively reducing the defect density of NiO, greatly improving the charge extraction-transport ability, increasing the carrier concentration, and reducing the non-radiative recombination of carriers at the interface, thus significantly enhancing the open-circuit voltage and conversion efficiency of perovskite solar cells.

[0048] (2) Interface modification synergistically enhances the conductivity of the device: After the surface of the irregular porous NiO layer is hydroxylated (H2O2 treatment) in the present invention, the hydroxyl density on the NiO surface is significantly increased, which not only helps the bonding of NiO and SAM, but also reduces the series resistance (Rs) of the perovskite solar cell due to the high conductivity of the hydroxyl groups used for bonding, improves the carrier transport ability between the perovskite and the transport layer, and promotes the further improvement of the efficiency of perovskite solar cells.

[0049] (3) Process compatibility and industrialization potential: The vacuum inclined deposition technique used in the present invention is fully compatible with the existing production line in combination with the annealing step. By adjusting the substrate tilt angle and rotation speed, the structure of the through-pores of the irregular porous NiO can be precisely controlled, and NiO carriers matching various SAM materials can be prepared. This method does not require complex equipment modification and has strong process compatibility, providing a reliable technical path for the large-scale preparation of large-area perovskite solar cells. Brief Description of the Drawings

[0050] Figure 1 It is a schematic diagram of the vacuum inclined deposition technique of the present invention;

[0051] Figure 2 It is a schematic diagram of the NIO thin film structure prepared by the vacuum inclined deposition technique of the present invention;

[0052] Figure 3 It is a comparison diagram of the perovskite solar cell structures of the conventional (left) and those containing the irregular porous NiO layer (type Y) (right). Detailed Description of the Invention

[0053] The following is a detailed description of the specific implementation manners of the present invention, but it should be understood that the protection scope of the present invention is not limited by the specific implementation manners.

[0054] Example 1

[0055] This embodiment provides a perovskite battery based on heterogeneous porous nickel oxide. The battery includes a substrate, an inclined columnar heterogeneous porous NiO layer, a SAM layer, a perovskite layer, a passivation layer 1, an electron transport layer, a passivation layer 2, and a back electrode layer stacked in sequence, and is prepared by the following steps:

[0056] S1. Substrate pretreatment:

[0057] The FTO conductive glass is ultrasonically cleaned with detergent, deionized water, acetone, and isopropanol for 20 minutes each in sequence, and treated with ultraviolet-ozone for 15 minutes;

[0058] S2. Preparation of the inclined columnar heterogeneous NiO layer:

[0059] In a magnetron sputtering device, the substrate tilt angle is adjusted to 60°, the rotation speed is 100 r / min, using a Ni target as the source, the oxygen partial pressure is 0.3 Pa, and an inclined columnar heterogeneous NiO layer (porosity 40%, pore diameter 20 nm) with a deposition thickness of 50 nm is deposited;

[0060] S3. Preparation of the inclined columnar heterogeneous porous NiO layer:

[0061] The inclined columnar heterogeneous NiO layer is immersed in a 10 vol% H2O2 solution for 20 minutes, and then heated in an oven at 60 °C for 15 minutes to obtain the inclined columnar heterogeneous porous NiO layer;

[0062] S4. Preparation of the SAM layer:

[0063] Me-4PACz is added to ethanol to prepare a solution with a concentration of 0.5 mg / mL. The solution is spin-coated (3000 rpm, 30 s) on the surface of the inclined columnar heterogeneous porous NiO layer; after spin-coating, it is placed in the atmospheric environment for 30 minutes; then annealed at 100 °C for 10 minutes to form a uniform monolayer; then annealed at 350 °C for 1 hour in argon to promote the formation of Ni-O-P chemical bonds to obtain the SAM layer;

[0064] S5. Preparation of the perovskite layer:

[0065] CsPbI3 is added to DMF / DMSO to prepare a precursor solution with a concentration of 1 g / mL. The precursor solution is spin-coated on the SAM layer; then annealed at 150 °C for 60 minutes to form a perovskite layer with a thickness of 600 nm;

[0066] S6. Preparation of the passivation layer 1:

[0067] LiF is evaporated on the perovskite layer at an evaporation rate of 0.1 A / s to form a passivation layer 1 with a thickness of 2 nm;

[0068] S7. Preparation of the electron transport layer:

[0069] Deposit C60 on the passivation layer 1 at an evaporation rate of 0.1 A / s to form an electron transport layer with a thickness of 20 nm;

[0070] S8. Prepare the passivation layer 2:

[0071] Deposit BCP on the electron transport layer at an evaporation rate of 0.1 A / s to form a passivation layer 2 with a thickness of 8 nm;

[0072] S9. Prepare the back electrode layer:

[0073] Vacuum deposit an Au electrode on the passivation layer 2 to form a back electrode layer with a thickness of 100 nm.

[0074] Example 2

[0075] This example provides a perovskite solar cell based on Y-shaped porous nickel oxide. The cell includes a substrate, a Y-shaped porous NiO layer, a SAM layer, a perovskite layer, a passivation layer 1, an electron transport layer, a passivation layer 2, and a back electrode layer stacked in sequence, and is prepared by the following steps:

[0076] S1. Substrate pretreatment:

[0077] Ultrasonically clean the FTO conductive glass with detergent, deionized water, acetone, and isopropanol for 20 min each, and perform ultraviolet-ozone treatment for 15 min;

[0078] S2. Prepare the Y-shaped porous NiO layer:

[0079] In a magnetron sputtering device, stepwise adjust the substrate tilt angle (0° → 50° → 0°), use a NiO target as the source, and an oxygen partial pressure of 0.1 Pa to deposit a Y-shaped porous NiO layer with a thickness of 50 nm (porosity 45%, pore diameter 15 nm);

[0080] S3. Prepare the Y-shaped porous NiO layer:

[0081] Immerse the Y-shaped porous NiO layer in a 10 vol% H2O2 solution for 20 min, and then heat it in an oven at 60 °C for 15 min to obtain the Y-shaped porous NiO layer;

[0082] S4. Prepare the SAM layer:

[0083] Add Me-4PACz to ethanol to prepare a solution with a concentration of 0.5 mg / mL. Spin-coat the solution (3000 rpm, 30 s) on the surface of the Y-shaped porous NiO layer; after spin-coating, place it in the atmospheric environment for 30 min; then anneal it at 100 °C for 10 min to form a uniform monolayer; then anneal it at 350 °C for 1 h in argon to promote the formation of Ni-O-P chemical bonds to obtain the SAM layer;

[0084] S5. Prepare perovskite layer:

[0085] Add FAPbI3 to DMF / DMSO to prepare a precursor solution with a concentration of 1.2 g / mL, and spin-coat the precursor solution on the SAM layer; then anneal at 150 °C for 60 min to form a perovskite layer with a thickness of 700 nm;

[0086] S6. Prepare passivation layer 1:

[0087] Add PEAI to isopropanol to prepare a solution with a concentration of 0.5 mg / mL, spin-coat the solution (4000 rpm, 30 s) on the perovskite layer, and then anneal at 100 °C for 30 min to form a passivation layer 1 with a thickness of 10 nm;

[0088] S7. Prepare electron transport layer:

[0089] Add PCBM to chlorobenzene to prepare a solution with a concentration of 20 mg / mL, spin-coat the solution (3000 rpm) on the passivation layer 1; then anneal at 80 °C for 10 min to form an electron transport layer with a thickness of 40 nm;

[0090] S8. Prepare passivation layer 2:

[0091] On the electron transport layer, form a passivation layer 2 with a thickness of 10 nm by ALD of SnO2;

[0092] S9. Prepare back electrode layer:

[0093] Vacuum deposit an Ag electrode on the passivation layer 2 to form a back electrode layer with a thickness of 100 nm.

[0094] Example 3

[0095] Compared with Example 1, the difference in this example is that

[0096] "S6. Prepare passivation layer 1:

[0097] Evaporate LiF on the perovskite layer at an evaporation rate of 0.1 A / s to form a passivation layer 1 with a thickness of 2 nm;

[0098] S7. Prepare electron transport layer:

[0099] Evaporate C60 on the passivation layer 1 at an evaporation rate of 0.1 A / s to form an electron transport layer with a thickness of 20 nm;

[0100] S9. Prepare back electrode layer:

[0101] Vacuum deposit an Au electrode on the passivation layer 2 to form a back electrode layer with a thickness of 100 nm."

[0102] It is prepared by changing to the following steps:

[0103] "S6. Prepare the passivation layer 1:

[0104] Add PDADI to isopropanol to prepare a solution with a concentration of 0.5 mg / mL. Spin-coat the solution (4000 rpm, 30 s) on the perovskite layer, and then anneal it at 100 °C for 30 min to form a passivation layer 1 with a thickness of 10 nm;

[0105] S7. Prepare the electron transport layer:

[0106] Add C60 to chlorobenzene to prepare a solution with a concentration of 20 mg / mL. Spin-coat the solution (3000 rpm) on the passivation layer 1; then anneal it at 80 °C for 10 min to form an electron transport layer with a thickness of 40 nm;

[0107] S9. Prepare the back electrode layer:

[0108] Vacuum deposit a Cu electrode on the passivation layer 2 to form a back electrode layer with a thickness of 100 nm.";

[0109] The remaining raw materials and the preparation process are the same as those in Example 1.

[0110] Example 4

[0111] The difference between this example and Example 2 is that

[0112] "S6. Prepare the passivation layer 1:

[0113] Add PEAI to isopropanol to prepare a solution with a concentration of 0.5 mg / mL. Spin-coat the solution (4000 rpm, 30 s) on the perovskite layer, and then anneal it at 100 °C for 30 min to form a passivation layer 1 with a thickness of 10 nm;

[0114] S7. Prepare the electron transport layer:

[0115] Add PCBM to chlorobenzene to prepare a solution with a concentration of 20 mg / mL. Spin-coat the solution (3000 rpm) on the passivation layer 1; then anneal it at 80 °C for 10 min to form an electron transport layer with a thickness of 40 nm;

[0116] S9. Prepare the back electrode layer:

[0117] Vacuum deposit an Ag electrode on the passivation layer 2 to form a back electrode layer with a thickness of 100 nm."

[0118] It is prepared by changing to the following steps:

[0119] "S6. Prepare the passivation layer 1:

[0120] Deposit MgF on the perovskite layer at an evaporation rate of 0.1 A / s to form a passivation layer 1 with a thickness of 2 nm;

[0121] S7. Prepare the electron transport layer:

[0122] Deposit PCBM on the passivation layer 1 at an evaporation rate of 0.1 A / s to form an electron transport layer with a thickness of 20 nm;

[0123] S9. Prepare the back electrode layer:

[0124] Prepare a Cu electrode by magnetron sputtering on the passivation layer 2 to form a back electrode layer with a thickness of 50 nm.''

[0125] The remaining raw materials and the preparation process are the same as those in Example 2.

[0126] Example 5

[0127] Compared with Example 1, the difference is that

[0128] ``S9. Prepare the back electrode layer:

[0129] Deposit an Au electrode by vacuum evaporation on the passivation layer 2 to form a back electrode layer with a thickness of 100 nm.''

[0130] is changed to the following steps for preparation:

[0131] ``S9. Prepare the back electrode layer: Prepare a 30 nm ITO electrode and a 30 nm Cu electrode in sequence by magnetron sputtering on the passivation layer 2 to form a back electrode layer with a thickness of 60 nm.''

[0132] The remaining raw materials and the preparation process are the same as those in Example 1.

[0133] Comparative Example 1

[0134] Compared with Example 1, the difference is that

[0135] ``S2. Prepare the inclined columnar and irregular NiO layer:

[0136] In a magnetron sputtering device, adjust the substrate tilt angle to 60°, the rotation speed to 100 r / min, use a Ni target as the source, the oxygen partial pressure to 0.3 Pa, and deposit an inclined columnar and irregular NiO layer with a thickness of 50 nm (porosity 40%, pore diameter 20 nm);

[0137] S3. Prepare the inclined columnar and porous NiO layer:

[0138] The inclined columnar and abnormally shaped NiO layer was immersed in a 10 vol% H2O2 solution for 20 min, and then heated in an oven at 60 °C for 15 min to obtain an inclined columnar and abnormally shaped porous NiO layer;

[0139] It was prepared by changing to the following steps:

[0140] "S2. Preparation of the NiO layer:

[0141] In a magnetron sputtering device, using a Ni target as the source, with an oxygen partial pressure of 0.3 Pa, a NiO layer with a deposition thickness of 50 nm was deposited.";

[0142] The remaining raw materials and the preparation process were the same as those in Example 1.

[0143] Comparative Example 2

[0144] Compared with Example 1, the difference is that

[0145] "S2. Preparation of the inclined columnar and abnormally shaped NiO layer:

[0146] In a magnetron sputtering device, the substrate tilt angle was adjusted to 60°, the rotation speed was 100 r / min, using a Ni target as the source, with an oxygen partial pressure of 0.3 Pa, an inclined columnar and abnormally shaped NiO layer (porosity 40%, pore diameter 20 nm) with a deposition thickness of 50 nm was deposited;

[0147] S3. Preparation of the inclined columnar and abnormally shaped porous NiO layer:

[0148] The inclined columnar and abnormally shaped NiO layer was immersed in a 10 vol% H2O2 solution for 20 min, and then heated in an oven at 60 °C for 15 min to obtain an inclined columnar and abnormally shaped porous NiO layer;

[0149] It was prepared by changing to the following steps:

[0150] "S2. Preparation of the inclined columnar and abnormally shaped NiO layer:

[0151] In a magnetron sputtering device, the substrate tilt angle was adjusted to 60°, the rotation speed was 100 r / min, using a Ni target as the source, with an oxygen partial pressure of 0.3 Pa, an inclined columnar and abnormally shaped NiO layer (porosity 40%, pore diameter 20 nm) with a deposition thickness of 50 nm was deposited."

[0152] The perovskite cells of Examples 1 - 5 and Comparative Examples 1 - 2 were subjected to performance tests, and the test results are shown in Table 1.

[0153] Table 1

[0154] Item PCE / % Voc / V <![CDATA[Jsc / mA / cm 2 > Isc / A FF Rs / Ω Rsh / Ω Example 1 20.45 48.93 0.601 0.409 0.695 15.9 990.8 Example 2 20.14 48.85 0.578 0.392 0.713 12.4 982.6 Example 3 20.09 47.67 0.603 0.41 0.699 14.88 982.6 Example 4 19.94 49.69 0.541 0.367 0.741 15.9 978.3 Example 5 20.75 48.82 0.592 0.402 0.718 12.9 993.1 Comparative Example 1 9.22 38.65 0.531 0.359 0.462 45.9 529.3 Comparative Example 2 14.25 47.13 0.518 0.351 0.584 33.1 998.5

[0155] As can be seen from Table 1, the perovskite solar cells of Examples 1-5 have a high power conversion efficiency (PCE), a high open-circuit voltage (Voc), a high short-circuit current density (Jsc), a high short-circuit current (Isc), a high fill factor (FF), a low series resistance (Rs), and a high shunt resistance (Rsh). Compared with Example 1, in Comparative Example 1, the "oblique columnar heterogeneous porous NiO layer" was replaced with a "NiO layer", and the obtained perovskite solar cell had a lower PCE, Voc, Jsc, Isc, and FF, a higher Rs, and a lower Rsh. Compared with Example 1, in Comparative Example 2, the "oblique columnar heterogeneous NiO layer" was not treated with an H2O2 solution, and the "oblique columnar heterogeneous NiO layer" was used to replace the "oblique columnar heterogeneous porous NiO layer", and the obtained perovskite solar cell had a reduced PCE, Voc, Jsc, Isc, and FF, and the Rs increased to some extent.

[0156] The above discloses only several specific embodiments of the present invention. However, the embodiments of the present invention are not limited thereto, and any changes that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A perovskite battery based on heterogeneous porous nickel oxide, characterized in that, The battery includes a substrate, a shaped porous NiO layer, a SAM layer, a perovskite layer, an electron transport layer, and a back electrode layer that are stacked in sequence; The SAM layer contacts the shaped porous NiO layer, fills and covers its porous surface.

2. The perovskite battery based on the heteromorphic porous nickel oxide as described in claim 1, wherein The shaped porous NiO layer includes three-dimensional shaped porous NiO.

3. The perovskite battery based on the heteromorphic porous nickel oxide according to claim 2, wherein The structure of the three-dimensional shaped porous NiO includes any one of a columnar structure, a helical structure, an inclined columnar structure, a zigzag structure, a C-shaped structure, and a Y-shaped structure.

4. A perovskite battery based on a shaped porous nickel oxide as claimed in claim 1, wherein, The raw material of the back electrode layer includes any one of a metal electrode, a metal oxide electrode, and a metal oxide / metal / metal oxide sandwich electrode.

5. A perovskite battery based on a shaped porous nickel oxide as claimed in claim 1, wherein, A passivation layer 1 is provided between the perovskite layer and the electron transport layer, and a passivation layer 2 is provided between the electron transport layer and the back electrode layer; The raw material of the passivation layer 1 includes any one of PEAI, PDADI, PDAI, MgF, CsF, and LiF; The raw material of the passivation layer 2 includes SnO2 and BCP.

6. The preparation method of a perovskite battery based on a special-shaped porous nickel oxide according to any one of claims 1-5, characterized in that, It includes the following steps: S1. Substrate pretreatment: The ultrasonically cleaned substrate is subjected to ultraviolet-ozone treatment for 5-20 min; S2. Preparation of the shaped NiO layer: Using the vacuum inclined deposition technique, the angle of the substrate is inclined at 0-90° and rotated at 0-360° in three-dimensional space; using Ni, NiO, and doped NiOx targets as sources, with an oxygen partial pressure of 0.005-0.5 Pa, a shaped NiO layer with a deposition thickness of 10-50 nm is deposited; S3. Preparation of the shaped porous NiO layer: The shaped NiO layer is immersed in a 5-10 vol% H2O2 solution for 5-20 min, and then heated in an oven at 40-80 °C for 10-30 min to obtain the shaped porous NiO layer; S4. Preparation of the SAM layer: One of Me-4PACz, Me-2PACz, and 4PDACB is added to solvent 1 to prepare a solution with a concentration of 0.1-1 mg / mL, and the solution is coated on the surface of the shaped porous NiO layer; after coating, it is placed in an atmospheric environment for 5-30 min; then annealed at 100-150 °C for 10-50 min to form a uniform monolayer; then annealed at 100-350 °C for 0.5-2 h in argon or a nitrogen / hydrogen mixture to obtain the SAM layer; S5. Preparation of the perovskite layer: Add any one of CsPbI x Br 3-x , FAPbI x Br 3-x and MAPbI x Br 3-x to Solvent 2 to prepare a precursor solution with a concentration of 0.5 - 2 g / mL, and coat the precursor solution on the SAM layer; then anneal at 100 - 150 °C for 30 - 90 min to form a perovskite layer with a thickness of 400 - 800 nm; S6. Preparation of the passivation layer 1: The raw material of the passivation layer 1 is added to solvent 3 to prepare a solution with a concentration of 0.5 mg / mL, and the solution is coated on the perovskite layer, and then annealed at 100-150 °C for 30-90 min to form a passivation layer 1 with a thickness of 5-20 nm; S7. Preparation of the electron transport layer: The raw material of the electron transport layer is added to solvent 4 to prepare a solution with a concentration of 5-50 mg / mL, and the solution is coated on the passivation layer 1; then annealed at 80-120 °C for 5-30 min to form an electron transport layer with a thickness of 20-100 nm; the raw material of the electron transport layer includes any one of SnO2, ZnO, TiO2, C60, and PCBM; S8. Preparation of the passivation layer 2: On the electron transport layer, the raw material of the passivation layer 2 is formed into a passivation layer 2 with a thickness of 5-15 nm by ALD; S9. Preparation of the back electrode layer: A back electrode layer with a thickness of 20 - 200 nm is formed on the passivation layer 2 by vacuum evaporation or magnetron sputtering.

7. The preparation method of a perovskite battery based on a special-shaped porous nickel oxide according to claim 6, characterized in that, The vacuum inclined deposition technique described in step S2 is selected from any one of magnetron sputtering, electron beam evaporation, and laser pulse deposition methods.

8. The preparation method of a perovskite battery based on heteromorphic porous nickel oxide according to claim 6, wherein, The preparation of the passivation layer 1 in step S6 includes the following process steps: The raw material of the passivation layer 1 is evaporated on the perovskite layer at an evaporation rate of 0.1 - 0.2 A / s to form a passivation layer 1 with a thickness of 0.1 - 5 nm.

9. The preparation method of a perovskite battery based on a shaped porous nickel oxide as claimed in claim 6, wherein, The preparation of the electron transport layer in step S7 includes the following process steps: C60 and PCBM are evaporated on the passivation layer 1 at an evaporation rate of 0.1 - 0.5 A / s to form an electron transport layer with a thickness of 10 - 50 nm.

10. The preparation method of a perovskite battery based on a shaped porous nickel oxide as claimed in claim 6, characterized in that, The preparation of the passivation layer 2 in step S8 includes the following process steps: The raw material of the passivation layer 2 is evaporated on the electron transport layer at an evaporation rate of 0.1 - 0.3 A / s to form a passivation layer 2 with a thickness of 2 - 10 nm.

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