A method for preparing a perovskite battery

Abstract

The present invention provides a method for preparing a perovskite cell, comprising the following steps: S1, preparing a slow-release agent that gradually releases a defect passivator; S2, preparing a precursor solution and adding the slow-release agent during the preparation process; S3, using the precursor solution to prepare a perovskite film on the surface of a substrate; S4, preparing a hole transport-electron blocking layer and an electron transport-hole blocking layer on the surface of the perovskite film; S5, preparing electrodes on the surfaces of the hole transport-electron blocking layer and the electron transport-hole blocking layer. The present invention loads the defect passivator into porous or hollow metal nanospheres, organic matter with a mesoporous structure, an organic-inorganic composite, or a polymer. During the operation of the perovskite solar cell, the defect passivator is gradually released, thereby increasing the action time of the defect passivator and achieving the effect of extending the operation time of the perovskite solar cell device.

Description

Technical Field

[0001] The present invention relates to the field of batteries, and in particular to a method for preparing a perovskite battery. Background Art

[0002] The general structural formula of perovskite is ABX3, where A is a metal or organic cation, B is a metal cation, and X is a halogen element. The field of perovskite solar cells is currently booming, with photoelectric conversion efficiencies comparable to those of silicon-based solar cells. Due to their solution-based preparation process and high defect tolerance, they have garnered increasing attention and possess broad application prospects. Currently, perovskite solar cells can be categorized into planar and mesoporous structures. Planar structures are categorized into upright and inverted structures. The upright structure primarily utilizes tin oxide and titanium dioxide as charge transport layers, while the inverted structure primarily utilizes PEDOT:PSS, PTAA, nickel oxide, and other materials. The mesoporous structure primarily utilizes mesoporous titanium dioxide as the charge transport layer.

[0003] Dopants are often introduced into perovskites to passivate defects, thereby improving the efficiency and stability of perovskite solar cells. While these defect passivators can reduce defects in perovskite solar cell films, they are typically sacrificial materials that degrade during perovskite solar cell operation, losing their original defect passivation properties. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a method for preparing a perovskite battery.

[0005] To achieve the above objectives, the present invention adopts the following specific technical solutions:

[0006] A method for preparing a perovskite battery comprises the following steps:

[0007] S1. preparing a sustained-release agent for gradually releasing a defect passivating agent;

[0008] S2. preparing a precursor solution and adding a sustained-release agent during the preparation process;

[0009] S3, preparing a perovskite film on the surface of the substrate using a precursor solution;

[0010] S4, preparing a hole transport-electron blocking layer and an electron transport-hole blocking layer on the surface of the perovskite film;

[0011] S5. Prepare electrodes on the surfaces of the hole transport-electron blocking layer and the electron transport-hole blocking layer.

[0012] Preferably, the following steps are further included before step S1:

[0013] S0. Ultrasonic cleaning, drying, and baking the substrate are performed, and the substrate is placed in air for cooling.

[0014] Preferably, the following steps are further included between step S2 and step S3:

[0015] The substrate is subjected to a hydrophilic treatment, wherein the hydrophilic treatment method includes ultraviolet-ozone treatment, plasma treatment or spin coating a hydrophilic material on the substrate.

[0016] Preferably, step S1 includes:

[0017] S101, dissolving a defect passivating agent and a loading agent in a solvent to form a sustained-release agent solution;

[0018] S102, heating and stirring the sustained-release agent solution;

[0019] S103, drying the stirred sustained-release agent solution to obtain a sustained-release agent powder;

[0020] S104, washing the sustained-release agent powder with an organic solvent or water, and then drying the sustained-release agent to obtain the sustained-release agent.

[0021] Preferably, step S2 includes:

[0022] S201, adding materials for preparing a perovskite film and a sustained-release agent into a solvent;

[0023] S202, heating and stirring;

[0024] S203, filtering to obtain a precursor solution.

[0025] Preferably, step S3 includes:

[0026] S301, preparing a perovskite film on the surface of a substrate using a precursor solution, and using an anti-solvent during the preparation process;

[0027] S302, performing annealing treatment on the perovskite film.

[0028] Preferably, step S4 includes the following steps:

[0029] S401, preparing a hole transport layer in a first region on the surface of the perovskite film;

[0030] S402, preparing an electron blocking layer in the first region to form a hole transport-electron blocking layer structure in the first region;

[0031] S403, preparing an electron transport layer in the second region on the surface of the perovskite film;

[0032] S404 , preparing a hole blocking layer in the second region to form an electron transport-hole blocking layer structure in the second region.

[0033] Preferably, step S5 includes the following steps:

[0034] S501, preparing a first electrode on the surface of the electron blocking layer;

[0035] S502, preparing a second electrode on the surface of the hole blocking layer;

[0036] The first electrode and the second electrode are both interdigital back electrodes, and each includes an interdigital electrode and a main electrode.

[0037] The present invention can achieve the following technical effects:

[0038] The defect passivator is loaded into porous or hollow metal nanospheres, organic matter with a mesoporous structure, organic-inorganic composites or polymers. During the operation of the perovskite solar cell, the defect passivator will be gradually released, thereby increasing the action time of the defect passivator and achieving the effect of extending the operation time of the perovskite solar cell device. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 is a schematic flow chart of a method for preparing a perovskite battery according to an embodiment of the present invention;

[0040] Figure 2 is a schematic structural diagram of a sustained-release agent according to an embodiment of the present invention;

[0041] Figure 3 3 is a schematic top view of an interdigitated back electrode perovskite cell according to a method for preparing a perovskite cell according to an embodiment of the present invention;

[0042] Figure 4 1 is a side view schematic diagram of an interdigitated back electrode perovskite cell according to a method for preparing a perovskite cell according to an embodiment of the present invention;

[0043] Figure 5 This is a performance test diagram of an interdigitated back electrode perovskite cell according to a method for preparing a perovskite cell in an embodiment of the present invention.

[0044] The reference numerals include: first electrode 1 , second electrode 2 , perovskite film 3 , substrate 4 , hole transport layer 5 , electron blocking layer 6 , electron transport layer 7 , hole blocking layer 8 . DETAILED DESCRIPTION

[0045] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not constitute a limitation of the present invention.

[0046] Figure 1The process of the perovskite battery preparation method provided by the embodiment of the present invention is shown, which includes the following steps:

[0047] S1. Prepare a sustained-release agent that gradually releases a defect passivating agent.

[0048] To ensure the performance of defect passivators, the concept of a sustained-release agent is introduced during the perovskite film preparation process. The defect passivator is loaded into porous or hollow metal nanospheres, organic materials with mesoporous structures, organic-inorganic composites, or polymers. During the operation of the perovskite solar cell, the defect passivator is gradually released as a sustained-release agent, thereby increasing the duration of the defect passivator's action and extending the operating time of the perovskite solar cell device.

[0049] S2. Prepare a precursor solution and add a sustained-release agent during the preparation process.

[0050] S3. Prepare a perovskite film on the surface of the substrate using a precursor solution.

[0051] S4. Prepare a hole transport-electron blocking layer and an electron transport-hole blocking layer on the surface of the perovskite film.

[0052] S5. Prepare electrodes on the surfaces of the hole transport-electron blocking layer and the electron transport-hole blocking layer.

[0053] Figure 2 、 3 The structure of an interdigitated back electrode perovskite cell prepared according to the perovskite cell preparation method of an embodiment of the present invention is shown, including a substrate, a perovskite film, a hole transport-electron blocking layer, an electron transport-hole blocking layer and an electrode.

[0054] In one embodiment of the present invention, the following steps are further included before step S1:

[0055] S0. Ultrasonic cleaning, drying, and baking the substrate are performed, and the substrate is placed in air for cooling.

[0056] The substrate 4 can be a rigid substrate 4 such as glass; or a flexible substrate 4 such as polyethylene terephthalate (PET), polyimide (PI), or parylene.

[0057] In this embodiment, the substrate 4 is ultrasonically cleaned in ethanol, acetone, and deionized water for 15 minutes respectively to remove impurities or dust on the surface of the substrate 4 to prevent them from affecting the subsequent preparation process; the cleaned substrate 4 is then blown dry with a nitrogen gun to remove residual cleaning agent; the substrate 4 is then placed in a 100-degree Celsius oven for drying for 15 minutes and finally placed in air to cool.

[0058] In one embodiment of the present invention, the following steps are further included between step S2 and step S3:

[0059] The substrate is subjected to a hydrophilic treatment, wherein the hydrophilic treatment method includes ultraviolet-ozone treatment, plasma treatment, or spin coating a hydrophilic material on the substrate; the hydrophilicity of the substrate 4 is improved to prepare for the subsequent preparation of the perovskite film 3.

[0060] In one embodiment of the present invention, step S1 includes:

[0061] S101, dissolving a defect passivating agent and a loading agent in a solvent to form a sustained-release agent solution.

[0062] Defect passivators include defect passivating materials such as Lewis acids, Lewis bases, amine salts, metal oxides, and antioxidants, and loading agents include hollow, porous, or mesoporous organics, inorganics, and organic-inorganic composites.

[0063] S102, heating and stirring the sustained-release agent solution.

[0064] S103, drying the stirred sustained-release agent solution to obtain sustained-release agent powder.

[0065] S104, washing the sustained-release agent powder with an organic solvent or water, and then drying the sustained-release agent to obtain the sustained-release agent.

[0066] In this example, reduced glutathione was used as the defect inactivator, and β-cyclodextrin molecules were used as the loading agent. One mole of β-cyclodextrin molecules and two moles of glutathione were dissolved in water and heated at 50 degrees Celsius with stirring overnight. The mixture was then dried in a vacuum oven at 60 degrees Celsius to obtain a sustained-release agent powder. The sustained-release agent powder was then washed three times with anhydrous ethanol. The mixture was then heated in a vacuum oven at 60 degrees Celsius for two hours to obtain the assembled sustained-release agent.

[0067] Figure 4 The structure of the sustained-release agent of an embodiment of the present invention is shown. The β-cyclodextrin molecule has a typical truncated cone-shaped cavity that can encapsulate glutathione to form a sustained-release agent. As an antioxidant, the β-cyclodextrin molecule reacts with the free radicals generated during the operation of the perovskite solar cell, destroying the cyclic molecular structure. Then, the glutathione loaded in the β-cyclodextrin molecule will be slowly released, which has the effect of passivating defects and improving the lifespan and stability of the perovskite solar cell during operation.

[0068] In one embodiment of the present invention, step S2 includes:

[0069] S201. Add materials for preparing perovskite thin film and a sustained-release agent into a solvent.

[0070] In the materials for preparing the perovskite film 3, the A-position cations include methylamine, formamidine, cesium, rubidium and other cations that can form three-dimensional perovskites, and cations that can form two-dimensional perovskites represented by phenylethylammonium iodide (PEAI); the B-position metal cations include lead, tin, copper, indium, bismuth, silver and other metal cations that can form a perovskite structure; the X-position includes anions that can form a perovskite structure represented by the halogen elements chlorine, bromine and iodine.

[0071] S202 , heating and stirring are performed to fully dissolve the materials for preparing the perovskite film 3 .

[0072] S203, filtering to obtain a precursor solution.

[0073] This example uses the widely studied methylamine lead iodide (MAPbI3) as an example to prepare the perovskite film 3. The preparation process is as follows:

[0074] Take methylammonium iodide and lead iodide in a 1:1 molar ratio and dissolve them in 200 ml of dimethyl sulfoxide (DMSO) and 800 ml of dimethylformamide (DMF), and add a sustained-release agent with a mass of 1-100 mg. Then, heat and stir at 55 degrees Celsius for 2 hours, and then filter using a 0.22-micron polytetrafluoroethylene filter to obtain a precursor solution.

[0075] In one embodiment of the present invention, step S3 includes:

[0076] S301, using a precursor solution to prepare a perovskite film on the surface of a substrate, and using an anti-solvent during the preparation process.

[0077] The preparation methods of the perovskite film 3 include one-step spin coating, multi-step spin coating, evaporation, a combination of evaporation and spin coating, blade coating, spray coating, roll-to-roll and other preparation methods.

[0078] An antisolvent is used during the preparation process to optimize the crystal morphology of the perovskite film 3 and improve the performance of the perovskite film 3; the antisolvent materials include chlorobenzene, toluene, ether, ethylene glycol, ethyl acetate, etc., and the methods of using the antisolvent include dynamic drop coating, antisolvent bath, antisolvent atmosphere, etc.

[0079] S302, annealing the perovskite film to further optimize the crystal morphology of the perovskite film.

[0080] Annealing processes include hot plate, microwave, hot air flow and other methods.

[0081] In this embodiment, the substrate 4 is moved into a glove box, and a perovskite film 3 is prepared by a one-step antisolvent spin coating method; the spin coating parameters are as follows: a rotation speed of 3000-6000 rpm, a spin coating time of 25-90 seconds, and an acceleration of 1500-3000 rpm; 100-600 μL of antisolvent is added during the spin coating process; after the spin coating process is completed, the obtained perovskite film 3 is placed on a hot plate at 80-150 degrees Celsius for annealing operation for 15-30 minutes.

[0082] In one embodiment of the present invention, step S4 includes the following steps:

[0083] S401, preparing a hole transport layer in a first region on the surface of the perovskite film.

[0084] The materials of the hole transport layer include inorganic hole transport materials represented by molybdenum oxide and organic hole transport materials represented by polyparaphenylene vinylene, polythiophene, polysilane, triphenylmethane, triarylamine, hydrazone, pyrazoline, oxazole, carbazole, butadiene, etc.

[0085] S402 , preparing an electron blocking layer in the first region to form a hole transport-electron blocking layer structure in the first region.

[0086] Materials for the electron blocking layer include inorganic electron blocking materials represented by nickel oxide and organic electron blocking materials represented by 4, N, N'-bis(3-methylphenyl)-N, N'-diphenylbenzidine (TPD), di(1-naphthyl)-N, N'-diphenyl (NPB), tris(4-carbazolyl-9-ylphenyl)amine (TCTA), and 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC).

[0087] S403, preparing an electron transport layer in the second region on the surface of the perovskite film.

[0088] The materials of the electron transport layer include inorganic electron transport materials represented by C60 and organic electron transport materials represented by tris(8-hydroxyquinolyl)aluminum (Alq3), 4,4-bis(2,2-diphenylvinyl)-1,1-diphenyl (DVPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazol-5-yl]benzene (OXD), etc.

[0089] S404 , preparing a hole blocking layer in the second region to form an electron transport-hole blocking layer structure in the second region.

[0090] Materials for the hole blocking layer include inorganic hole blocking materials represented by lithium fluoride and organic hole blocking materials represented by 4,4-bis(2,2-diphenylvinyl)-1,1-diphenylene (DPVBi).

[0091] The preparation methods of the charge transport / blocking layer include evaporation, spin coating, spray coating, blade coating and the like.

[0092] In one embodiment of the present invention, step S5 includes the following steps:

[0093] S501, preparing a first electrode on the surface of the electron blocking layer;

[0094] S502, preparing a second electrode on the surface of the hole blocking layer;

[0095] The electrode structures of the first electrode and the second electrode include a main-gate-free electrode, a four-main-gate electrode, a point-connected electrode, etc., and are all in the shape of an interdigitated back electrode, including an interdigitated electrode and a main electrode.

[0096] The materials of the electrodes include metal materials such as gold, silver, and copper, as well as carbon-based materials represented by graphene.

[0097] The preparation methods of electrodes include evaporation, spin coating, blade coating, spraying, sputtering, electroplating, masking and the like.

[0098] In this embodiment, the interdigitated electrodes of the first electrode 1 and the second electrode 2 are alternately distributed, the width of the interdigitated electrodes ranges from 0.5 micrometers to 1 centimeter, the spacing between two adjacent interdigitated electrodes of the same electrode is from 0.5 micrometers to 1 centimeter, the spacing between the interdigitated electrodes of an electrode and the main electrode of another electrode is from 0.5 micrometers to 1 centimeter, and the spacing between two adjacent interdigitated electrodes of different electrodes is from 0.5 micrometers to 1 centimeter. The first electrode 1 and the second electrode 2 do not make direct contact.

[0099] Below through Figure 5 The advantages of the embodiments of the present invention are described as follows:

[0100] Figure 5 This is a performance test diagram of an interdigitated back electrode perovskite cell prepared according to the perovskite cell preparation method of an embodiment of the present invention. The parameters of the perovskite cell prepared according to the embodiment of the present invention are as follows: open circuit voltage is 1.103V, short circuit current is 23.34mA / cm 2 , through calculation, the filling factor is 67% and the conversion efficiency is 17.46%; the perovskite battery prepared in the embodiment of the present invention has good performance.

[0101] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0102] Although the embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art may make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

[0103] The above specific embodiments of the present invention do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a perovskite battery, characterized in that: The following steps are involved: S1. Preparing a sustained-release agent for gradually releasing a defect passivating agent; comprising: S101, dissolving the defect passivating agent and the loading agent in a solvent to form a sustained-release agent solution; S102, heating and stirring the sustained-release agent solution; S103, drying the stirred sustained-release agent solution to obtain a sustained-release agent powder; S104, washing the sustained-release agent powder with an organic solvent or water, and then drying the sustained-release agent to obtain the sustained-release agent; The defect passivating agent is reduced glutathione, and the loading agent is a β-cyclodextrin molecule; S2. preparing a precursor solution, and adding the sustained-release agent during the preparation process; S3, preparing a perovskite film on the surface of the substrate using the precursor solution; S4, preparing a hole transport-electron blocking layer and an electron transport-hole blocking layer on the surface of the perovskite film; specifically comprising the following steps: S401, preparing a hole transport layer in a first region on the surface of the perovskite film; S402, preparing an electron blocking layer in the first region to form a hole transport-electron blocking layer structure in the first region; S403, preparing an electron transport layer in the second region on the surface of the perovskite film; S404, preparing a hole blocking layer in the second region, so that the second region forms an electron transport-hole blocking layer structure; S5. Prepare electrodes on the surfaces of the hole transport-electron blocking layer and the electron transport-hole blocking layer.

2. The method for preparing a perovskite battery according to claim 1, wherein: Before step S1, the following steps are also included: S0. Ultrasonic cleaning, drying, and baking the substrate are performed, and the substrate is placed in air for cooling.

3. The method for preparing a perovskite battery according to claim 1, wherein: The following steps are also included between step S2 and step S3: The substrate is subjected to a hydrophilic treatment, wherein the hydrophilic treatment method includes ultraviolet-ozone treatment, plasma treatment or spin coating a hydrophilic material on the substrate.

4. The method for preparing a perovskite battery according to claim 1, wherein: The step S2 comprises: S201, adding the material for preparing the perovskite film and the sustained-release agent into a solvent; S202, heating and stirring; S203, filtering to obtain the precursor solution.

5. The method for preparing a perovskite battery according to claim 1, wherein: The step S3 comprises: S301, using the precursor solution to prepare the perovskite film on the surface of the substrate, and using an anti-solvent during the preparation process; S302 , performing annealing treatment on the perovskite film.

6. The method for preparing a perovskite battery according to claim 1, wherein: The step S5 comprises the following steps: S501, preparing a first electrode on the surface of the electron blocking layer; S502, preparing a second electrode on the surface of the hole blocking layer; The first electrode and the second electrode are both interdigitated back electrodes, and each includes an interdigitated electrode and a main electrode.

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