Perovskite battery monomer, perovskite battery pack and preparation method and application of perovskite battery monomer and perovskite battery pack

Abstract

The invention discloses a perovskite cell monomer, a perovskite battery pack and a preparation method and application of the perovskite cell monomer and the perovskite battery pack, and relates to the technical field of solar cell preparation. The carbon-based back electrode layer, the porous insulating layer, the electron transport layer and the transparent front electrode layer are sequentially arranged on the glass substrate; wherein at least the porous insulating layer is filled with a perovskite material. The invention provides a novel trans-perovskite cell structure, the lower carbon-based back electrode layer and the porous insulating layer are firstly prepared during preparation, then the electron transport layer is prepared, the material selection range of the electron transport layer is wide, and the electron transport layer is not limited by temperature; the conversion efficiency of the perovskite battery monomer and the perovskite battery pack can be improved by selecting an electron transport layer material which is relatively good in conductivity and is manufactured at a low temperature.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cell preparation, and in particular to a perovskite battery cell and a perovskite battery pack, and a preparation method and application thereof. Background Art

[0002] Commonly used carbon-based perovskite structures require high-temperature processes, usually at temperatures above 400°C. In particular, the sintering of porous TiO2 requires sintering temperatures above 500°C to form a porous structure, which severely limits the choice of battery structure and materials, and even affects battery efficiency. Summary of the invention

[0003] The main purpose of the present invention is to propose a perovskite battery cell and a perovskite battery pack and a preparation method and application thereof, aiming to provide a new perovskite battery structure.

[0004] To achieve the above objectives, the present invention provides a perovskite battery cell, comprising:

[0005] a glass substrate; and,

[0006] A carbon-based back electrode layer, a porous insulating layer, an electron transport layer and a transparent front electrode layer are sequentially arranged on the glass substrate;

[0007] Wherein, at least the porous insulating layer is filled with perovskite material.

[0008] In one embodiment, the thickness of the carbon-based back electrode layer is 1 μm-50 μm; and / or,

[0009] The thickness of the porous insulating layer is 100 nm-5 μm; and / or,

[0010] The thickness of the electron transport layer is 10nm-50nm; and / or,

[0011] The thickness of the transparent front electrode layer is 10 nm-1 μm; and / or,

[0012] The material of the carbon-based back electrode layer includes carbon, graphene-doped carbon or carbon nanotube-doped carbon; and / or,

[0013] The material of the porous insulating layer includes one or more of zirconium dioxide, silicon dioxide and aluminum oxide; and / or,

[0014] The material of the electron transport layer includes at least one of titanium dioxide, tin dioxide, fullerene and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and / or,

[0015] The material of the transparent front electrode layer includes indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide or fluorine-doped tin oxide.

[0016] In one embodiment, the perovskite battery cell further includes a back electrode auxiliary layer, wherein the back electrode auxiliary layer is disposed between the carbon-based back electrode layer and the glass substrate, and the back electrode auxiliary layer includes a metal oxide layer.

[0017] In one embodiment, the back electrode auxiliary layer further includes a metal layer, and the metal layer is disposed between the metal oxide layer and the glass substrate.

[0018] In one embodiment, the back electrode auxiliary layer also includes a first insulating layer, which is arranged between the metal oxide layer and the carbon-based back electrode layer. The first insulating layer includes a plurality of insulating layers arranged at intervals along the plane where the metal oxide layer is located, and carbon is arranged in the intervals between the plurality of insulating layers to connect the carbon-based back electrode layer and the metal oxide layer.

[0019] In one embodiment, the material of the metal oxide layer includes indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide or fluorine-doped tin oxide; and / or,

[0020] The material of the metal layer includes one or more of Cu, Ag, Al and Mn; and / or,

[0021] The material of the first insulating layer includes at least one of a photosensitive resin and a thermosetting resin; and / or,

[0022] The thickness of the metal oxide layer is 20nm-1000nm; and / or,

[0023] The thickness of the metal layer is 20nm-100nm; and / or,

[0024] The thickness of the first insulating layer is 1 μm-5 μm.

[0025] In one embodiment, the perovskite battery cell further includes a dense electrode layer, and the dense electrode layer is disposed between the carbon-based back electrode layer and the back electrode auxiliary layer.

[0026] In one embodiment, the perovskite battery cell further includes a hole transport layer, and the hole transport layer is disposed between the carbon-based back electrode layer and the porous insulating layer.

[0027] The present invention also provides a perovskite battery pack, comprising:

[0028] a glass substrate; and,

[0029] A plurality of stacked monomer structures are arranged on the glass substrate, each of the stacked monomer structures comprises a carbon-based back electrode layer, a porous insulating layer, an electron transport layer and a transparent front electrode layer sequentially stacked on the glass substrate, and at least the porous insulating layer is filled with a perovskite material;

[0030] Wherein, the carbon-based back electrode layer of the stacked monomer structure and the transparent front electrode layer of the adjacent stacked monomer structure are connected to each other.

[0031] In one embodiment, the multiple stacked monomer structures are arranged at intervals along the plane where the glass substrate is located, and a second insulating layer is arranged on the glass substrate and between two adjacent stacked monomer structures, the second insulating layer has a first side end and a second side end corresponding to the two adjacent stacked monomer structures, the first side end of the second insulating layer at least covers the carbon-based back electrode layer of at least one of the stacked monomer structures, the second side end of the second insulating layer at least covers the porous insulating layer and the carbon-based back electrode layer of another stacked monomer structure, and in the direction from the first side end to the second side end, the second insulating layer is arranged in a slope on a side away from the glass substrate, and a transparent front electrode layer is arranged thereon.

[0032] In one embodiment, the material of the second insulating layer includes dense zirconium dioxide, dense aluminum oxide or organic resin; and / or,

[0033] The slope is A, A<70°.

[0034] The present invention also provides a method for preparing a perovskite battery monomer, wherein the electron transport layer is a dense structure, and the method for preparing the perovskite battery monomer comprises the following steps:

[0035] S1, providing a glass substrate, sequentially preparing a carbon-based back electrode layer and a porous insulating layer on the glass substrate, and performing high-temperature sintering;

[0036] S2, applying a perovskite precursor droplet onto the porous insulating layer, so that the perovskite precursor liquid at least fills the porous insulating layer, and performing annealing and crystallization;

[0037] S3. Prepare an electron transport layer and a transparent front electrode layer on the porous insulating layer to obtain a perovskite battery cell.

[0038] In one embodiment, in step S1, the temperature of the high temperature annealing is 150-450° C.; and / or,

[0039] In step S1, the high temperature annealing time is 30 min-60 min; and / or,

[0040] In step S2, the crystallization temperature is 100-150° C.; and / or,

[0041] In step S2, the crystallization time is 10 min-30 min; and / or,

[0042] In step S3, the method for preparing the transparent front electrode layer includes magnetron sputtering or plasma deposition.

[0043] In one embodiment, step S1 includes the following steps:

[0044] Coating a carbon-based back electrode layer slurry containing an additive on the glass substrate, and drying to obtain a first coating structure;

[0045] Applying the auxiliary agent-containing insulating layer slurry on the first coating structure, and drying to obtain a second coating structure;

[0046] The second coating structure is subjected to high temperature annealing to volatilize the auxiliary agent and form pores in the second coating structure.

[0047] In one embodiment, the auxiliary agent includes an inorganic auxiliary agent and / or an organic auxiliary agent, the inorganic auxiliary agent includes at least one of sodium bicarbonate, sodium carbonate and ammonium bicarbonate, and the organic auxiliary agent includes at least one of ethyl cellulose and propyl hydroxy cellulose; and / or,

[0048] The coating method includes screen printing.

[0049] The present invention also provides a method for preparing a perovskite battery monomer, wherein the electron transport layer is a porous structure, and the method for preparing the perovskite battery monomer comprises the following steps:

[0050] S10, providing a glass substrate, sequentially preparing a carbon-based back electrode layer, a porous insulating layer and an electron transport layer on the glass substrate, and performing high-temperature annealing;

[0051] S20, applying a perovskite precursor liquid droplet on the electron transport layer, so that the perovskite precursor liquid at least fills the electron transport layer and the porous insulating layer, and performing annealing and crystallization;

[0052] S30, preparing a transparent front electrode layer on the electron transport layer to obtain a perovskite battery cell.

[0053] The present invention also provides a method for preparing a perovskite battery pack, wherein the electron transport layer is a dense structure, and the method for preparing the perovskite battery pack comprises the following steps:

[0054] S100a, providing a glass substrate, sequentially preparing a carbon-based back electrode layer and a porous insulating layer on the glass substrate, and performing high-temperature annealing to obtain a first stacked body;

[0055] S200a, etching a plurality of etching grooves at intervals along the plane where the glass substrate is located, dividing the first stacked body into a plurality of first stacked structures, and preparing a second insulating layer in each of the etching grooves;

[0056] S300a, applying a perovskite precursor liquid droplet on the porous insulating layer of each of the first stacked structures, so that the perovskite precursor liquid at least fills the porous insulating layer, and performing crystallization;

[0057] S400a, preparing an electron transport layer on the porous insulating layer of each of the first stacked structures, and then preparing a transparent front electrode layer on the electron transport layer and the first insulating layer to obtain a plurality of stacked monomer structures, so that the transparent front electrode layer of each stacked monomer structure is connected to the carbon-based back electrode layer of the adjacent stacked monomer structure to obtain a perovskite battery group;

[0058] The crystallization temperature is greater than the temperature for preparing the electron transport layer.

[0059] The present invention also provides a method for preparing a perovskite battery pack, wherein the electron transport layer is a porous structure, and the method for preparing the perovskite battery pack comprises the following steps:

[0060] S100b, providing a glass substrate, sequentially preparing a carbon-based back electrode layer, a porous insulating layer and an electron transport layer on the glass substrate, and performing high-temperature annealing;

[0061] S200b, applying a perovskite precursor liquid droplet on the electron transport layer, so that the perovskite precursor liquid at least fills the electron transport layer and the porous insulating layer, and performing crystallization to obtain a second stacked body;

[0062] S300b, etching a plurality of etching grooves at intervals along the plane where the glass substrate is located, dividing the second stacked body into a plurality of second stacked structures, and preparing a second insulating layer in each of the etching grooves;

[0063] S400b, preparing a transparent front electrode layer on the electron transport layer of each of the second stacking structures to obtain a plurality of stacking monomer structures, so that the transparent front electrode layer of each of the stacking monomer structures is connected to the carbon-based back electrode layer of its adjacent stacking monomer structure to obtain a perovskite battery group.

[0064] The present invention also provides an electrical device, comprising the aforementioned perovskite battery cell.

[0065] The present invention also provides a charging system, comprising the aforementioned perovskite battery pack.

[0066] In the technical solution of the present invention, a new perovskite battery structure is provided, so that during preparation, the lower carbon-based back electrode layer and the porous insulating layer are prepared first, and then the electron transport layer is prepared. The material selection range of the electron transport layer is wide and is not restricted by temperature. When the electron transport layer material with good conductive performance is selected, the conversion efficiency of the perovskite battery cell and the perovskite battery pack can be better improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0068] Figure 1 A structural diagram of a perovskite battery cell in an embodiment of the present invention;

[0069] Figure 2 A structural diagram of a perovskite battery cell in another embodiment provided by the present invention;

[0070] Figure 3 This is a structural diagram of a perovskite battery pack in one embodiment of the present invention.

[0071] Description of Figure Numbers:

[0072] 100. Perovskite battery cell; 1. Glass substrate; 2. Carbon-based back electrode layer; 3. Porous insulating layer; 4. Electron transport layer; 5. Transparent front electrode layer; 6. Back electrode auxiliary layer; 61. Metal oxide layer; 62. Metal layer; 63. First insulating layer; 7. Second insulating layer; 200. Perovskite battery pack.

[0073] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0074] To make the purpose, technical scheme and advantages of the embodiment of the present invention clearer, the technical scheme in the embodiment of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiment, it is carried out according to the normal conditions or the conditions recommended by the manufacturer. If the reagents or instruments used do not specify the manufacturer, they are all conventional products that can be purchased commercially. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes, taking "A and / or B" as an example, including scheme A, or scheme B, or schemes that A and B meet at the same time. In addition, the technical schemes between the various embodiments can be combined with each other, but must be based on the ability of ordinary technicians in the field to achieve. When the combination of technical solutions is contradictory or cannot be achieved, it should be considered that the combination of such technical solutions does not exist, and is not within the scope of protection required by the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present invention.

[0075] Commonly used carbon-based perovskite structures require high-temperature processes, usually at temperatures above 400°C. In particular, the sintering of porous titanium dioxide (TiO2) requires sintering temperatures of more than 500°C to form a porous structure, which severely limits the choice of battery structure and materials, and even affects battery efficiency.

[0076] Specifically, the basic structure of the current porous battery is a conductive substrate, a porous electron transport layer, a porous insulating layer, and a carbon-based back electrode layer from bottom to top. Since the porous structure of the porous battery needs to be formed at a temperature of more than 400°C, a high-temperature process is required. Since porous batteries are usually prepared layer by layer from bottom to top, materials such as the electron transport layer in the lower layer often need to withstand high temperatures to avoid melting due to high temperatures. However, the conductivity of electron transport layer materials that can withstand high-temperature processes, such as titanium dioxide, is often not optimal, which limits the conversion efficiency of porous batteries.

[0077] In view of this, if Figure 1 As shown, the present invention provides a perovskite battery cell 100, comprising: a glass substrate 1; and a carbon-based back electrode layer 2, a porous insulating layer 3, an electron transport layer 4 and a transparent front electrode layer 5 arranged in sequence on the glass substrate 1; wherein at least the porous insulating layer 3 is filled with a perovskite material.

[0078] In the technical solution of the present invention, a new inverted structure of a perovskite battery is provided, that is, from bottom to top, a glass substrate 1, a carbon-based back electrode layer 2, a porous insulating layer 3, an electron transport layer 4 and a transparent front electrode layer 5 are sequentially provided. After inversion, the carbon-based back electrode layer 2 and the porous insulating layer 3 are located below, so that the electron transport layer 4 is prepared later, so its material can be titanium dioxide, or a material with better conductivity, that is, the material selection range of the electron transport layer 4 is wide, and it is not constrained by temperature. When the electron transport layer 4 material with better conductivity is selected, the conversion efficiency of the perovskite battery cell 100 and the perovskite battery pack 200 can be improved. It should be noted that the carbon-based back electrode layer 2 in the present invention also plays the role of a hole transport layer, so a separate hole transport layer may not be provided. At the same time, the pores of the porous insulating layer 3 of the present invention may be pores of various pore sizes such as micropores and mesopores, which are not limited here. In the present invention, at least the porous insulating layer 3 is filled with a perovskite material, that is, the porous insulating layer 3 protects the perovskite, and the perovskite material prevents leakage.

[0079] It should be noted that the perovskite material in the present invention generally has an ABX3 structure, wherein the A position is generally an organic cation (such as methylamine ion, formamidine ion), the B position is a metal cation (such as lead ion), and the X position is a halogen anion (such as iodine ion, bromide ion, chloride ion). Common perovskite materials include CH3NH3PbI3, (FA)PbI3, etc.

[0080] In some embodiments of the present invention, the thickness of the carbon-based back electrode layer 2 is 1 μm-50 μm; and / or the thickness of the porous insulating layer 3 is 100 nm-5 μm; and / or the thickness of the electron transport layer 4 is 10 nm-50 nm; and / or the thickness of the transparent front electrode layer 5 is 10 nm-1 μm. The carbon-based back electrode layer, the porous insulating layer 3, the electron transport layer 4 and the transparent front electrode layer 5 are arranged within the above range to ensure that the efficiency of the perovskite battery cell 100 is high.

[0081] In some embodiments of the present invention, the material of the carbon-based back electrode layer 2 includes carbon, graphene-doped carbon or carbon nanotube-doped carbon. The above-mentioned carbon-based back electrode layer 2 material is selected to ensure that it does not react with the subsequent dripped perovskite solution or affect the stability of the perovskite material. Preferably, the material of the carbon-based back electrode layer 2 is graphene-doped carbon or carbon nanotube-doped carbon. Graphene or carbon nanotube doping will reduce the resistance of carbon and increase the conductivity of carbon, thereby improving the conductivity efficiency of the carbon-based back electrode layer 2. It should be noted that the carbon-based back electrode layer 2 of the present invention can be a dense structure or a porous structure.

[0082] In some embodiments of the present invention, the material of the porous insulating layer 3 includes one or more of zirconium dioxide, silicon dioxide and aluminum oxide. The porous insulating layer 3 material has high chemical stability and good insulation performance. As a protective layer or insulating layer, it prevents the perovskite material from having unnecessary chemical reactions with the external environment or electrode materials. At the same time, the porous material has a high specific surface area and a uniform pore size distribution, which can provide a good gas diffusion channel, which is conducive to promoting the growth of the perovskite material (that is, it can provide a larger space to accommodate the perovskite crystallization) and improving the stability and performance of the device.

[0083] In some embodiments of the present invention, the material of the electron transport layer 4 includes at least one of titanium dioxide, tin dioxide, fullerene and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. The material of the electron transport layer 4 is preferably fullerene or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. The high-temperature process temperature of the two electron transport layer 4 materials is low, and the perovskite crystals will not melt (about 150°C) and affect the battery efficiency. The electron transport layer 4 can also be multilayer, each layer of different materials, preferably a fullerene electron transport layer 4 and a tin dioxide electron transport layer 4.

[0084] In some embodiments of the present invention, the material of the transparent front electrode layer 5 includes indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide or fluorine-doped tin oxide. Selecting indium tin oxide (ITO), (indium zinc oxide) (IZO), (aluminum-doped zinc oxide) (AZO) or fluorine-doped tin oxide (FTO) can ensure that the transparent front electrode layer 5 has a higher light transmittance in the visible light absorption range and improve the light absorption efficiency.

[0085] like Figure 2 As shown, in some embodiments of the present invention, the perovskite battery cell 100 further includes a back electrode auxiliary layer 6, the back electrode auxiliary layer 6 is disposed between the carbon-based back electrode layer 2 and the glass substrate 1, and the back electrode auxiliary layer 6 includes a metal oxide layer 61. After the metal oxide layer 61 is disposed between the carbon-based back electrode layer 2 and the glass substrate 1, the metal oxide layer 61 and the carbon-based back electrode layer 2 serve together as the back electrode. Since the metal oxide layer 61 has a low resistance, it can compensate for the low battery conversion efficiency caused by the excessive resistance of the carbon-based back electrode layer 2. In addition, when the perovskite battery cell 100 is connected in series, due to the provision of the metal oxide layer 61, the series resistance can be prevented from being too large, thereby improving the conversion efficiency of the series battery group.

[0086] like Figure 2As shown, in some embodiments of the present invention, the back electrode auxiliary layer 6 also includes a metal layer 62, and the metal layer 62 is arranged between the metal oxide layer 61 and the glass substrate 1. The conductivity of metal is better than that of metal oxide, and the resistivity is low. The metal layer 62 is arranged between the metal oxide layer 61 and the glass substrate 1, which can further reduce the resistance of the carbon-based back electrode layer 2 and improve the battery conversion efficiency. It should be noted that in the present invention, when the carbon-based back electrode layer 2 is a porous structure, the perovskite solution enters the carbon-based back electrode layer 2 from top to bottom after being dripped. Since the perovskite solution is easy to react with the metal, the metal layer 62 is corroded, and the perovskite solution does not corrode the metal oxide layer 61, so the metal layer 62 needs to be arranged below the metal oxide.

[0087] like Figure 2 As shown, in some embodiments of the present invention, the back electrode auxiliary layer 6 further includes a first insulating layer 63, the first insulating layer 63 is disposed between the metal oxide layer 61 and the carbon-based back electrode layer 2, and the first insulating layer 63 includes a plurality of insulating layers spaced along the plane where the metal oxide layer 61 is located, and carbon is disposed in the intervals between the plurality of insulating layers to connect the carbon-based back electrode layer 2 and the metal oxide layer 61. In the technical solution of the present invention, since the thickness of the metal oxide layer 61 is relatively thin, when the density of the coating of the metal oxide layer 61 is relatively poor, the perovskite solution easily passes through the metal oxide layer 61 and enters the metal layer 62 to corrode it, and the first insulating layer 63 is disposed in the back electrode auxiliary layer 6 to prevent the perovskite solution from contacting the metal layer 62 through the pores of the metal oxide. Specifically, the first insulating layer 63 can be disposed between the metal oxide layer 61 and the carbon-based back electrode layer 2. When the first insulating layer 63 is disposed between the metal oxide layer 61 and the carbon-based back electrode layer 2, the first insulating layer 63 can be a plurality of insulating layers spaced along the plane where the metal oxide layer 61 is located, and carbon is disposed between adjacent insulating layers to connect the upper carbon-based back electrode layer 2 and the metal oxide layer 61 for electrical conduction. The provision of the first insulating layer 63 can reduce the area of ​​the perovskite solution contacting the metal layer 62 through the porous pores in the carbon-based back electrode layer 2 and the gaps in the metal oxide layer 61, and has a protective effect on the metal layer 62.

[0088] In some embodiments of the present invention, the material of the metal oxide layer 61 includes indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide or fluorine-doped tin oxide; and / or, the material of the metal layer 62 includes one or more of Cu, Ag, Al and Mn; and / or, the material of the first insulating layer 63 includes at least one of a photosensitive resin and a thermosetting resin; and / or, the thickness of the metal oxide layer 61 is 20nm-1000nm; and / or, the thickness of the metal layer 62 is 20nm-100nm; and / or, the thickness of the first insulating layer 63 is 1μm-5μm. In the technical solution of the present invention, the above-mentioned metal oxide material is not easily corroded by the perovskite solution, which can better improve the conductivity of the porous carbon layer; the material and thickness of the above-mentioned metal layer 62 can ensure its good conductivity; the material and thickness of the above-mentioned first insulating layer 63 can ensure its good insulation and compactness, and reduce the probability of the perovskite solution entering the metal layer 62.

[0089] In some embodiments of the present invention, the perovskite battery cell 100 further includes a dense electrode layer, which is disposed between the carbon-based back electrode layer 2 and the back electrode auxiliary layer 6. Due to the insufficient adhesion between the carbon-based back electrode layer 2 and the glass substrate 1 or even the metal oxide layer 61, the carbon-based back electrode layer 2 may fall off to a certain extent when immersed in the perovskite solution. Providing a dense electrode layer between the carbon-based back electrode layer 2 and the back electrode auxiliary layer 6 can improve the adhesion between the carbon-based back electrode layer and the glass substrate 1 or even the metal oxide layer 61, forming a combination of a dense electrode layer and a carbon-based back electrode layer 2, and improving the structural stability of the battery cell. The dense electrode layer refers to a non-porous electrode layer.

[0090] In some embodiments of the present invention, the thickness of the dense electrode layer is 1 μm-50 μm; and / or, the material of the dense electrode layer includes carbon, carbon nanotube-doped carbon or graphene-doped carbon. The thickness of the dense electrode layer within the above range can ensure that the carbon-based back electrode layer 2 and the lower glass substrate 1 or the metal oxide layer 61 have good adhesion and are not easy to separate; the material of the dense electrode layer can withstand the high temperature conditions of the upper porous structure, and can better bond the carbon-based back electrode layer 2 and the glass substrate 1 and even the metal oxide layer 61.

[0091] In some embodiments of the present invention, the perovskite battery cell 100 further includes a hole transport layer, which is disposed between the carbon-based back electrode layer 2 and the porous insulating layer 3. After the hole transport layer is disposed between the carbon-based back electrode layer 2 and the porous insulating layer 3, the carbon-based back electrode layer 2 and the hole transport layer simultaneously play a role in hole transport, thereby improving the hole extraction capability of the battery cell.

[0092] In some embodiments of the present invention, the material of the hole transport layer includes nickel oxide, copper thiocyanate, copper iodide or copper oxide; the thickness of the hole transport layer is 1nm-20nm. The thickness of the hole transport layer within the above range can ensure good hole extraction and transport effects. It should be noted that the hole transport layer can be a porous structure or a dense structure.

[0093] like Figure 3 As shown, the present invention also provides a perovskite battery pack 200, comprising: a glass substrate 1; and a plurality of stacked monomer structures arranged on the glass substrate 1, each of the stacked monomer structures comprising a carbon-based back electrode layer 2, a porous insulating layer 3, an electron transport layer 4 and a transparent front electrode layer 5 stacked in sequence on the glass substrate 1, at least the porous insulating layer 3 is filled with perovskite material; wherein the carbon-based back electrode layer 2 of the stacked monomer structure is interconnected with the transparent front electrode layer 5 of the adjacent stacked monomer structure.

[0094] In the technical solution of the present invention, a new battery pack structure is provided, that is, a plurality of stacked monomer structures are arranged on the same glass substrate 1, each stacked monomer structure comprises a carbon-based back electrode layer 2, a porous insulating layer 3, an electron transport layer 4 and a transparent front electrode layer 5 stacked sequentially on the glass substrate 1, wherein at least the porous insulating layer 3 in each stacked monomer structure is filled with a perovskite material, and the transparent front electrode layer 5 of each stacked monomer structure is interconnected with the carbon-based back electrode layer 2 of the adjacent stacked monomer structure to form a series structure. The electron transport layer 4 of the battery pack with this structure can be selected from materials with good conductivity and high electron transport efficiency, such as fullerene or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, so as to improve the conversion efficiency of the battery pack.

[0095] In some embodiments of the present invention, the plurality of stacked monomer structures are arranged along their stacking direction, or the plurality of stacked monomer structures are arranged at intervals along the plane where the glass substrate 1 is located. That is, the stacked monomer structures in the perovskite battery pack 200 can be at least stacked longitudinally (connected end to end), or can be arranged at intervals in the horizontal direction. Multiple stacked monomer structures with different connections can be applied to a variety of applications, expanding the application scenarios.

[0096] In some embodiments of the present invention, the multiple stacked monomer structures are arranged at intervals along the plane where the glass substrate 1 is located, and a second insulating layer 7 is arranged on the glass substrate 1 and between two adjacent stacked monomer structures, the second insulating layer 7 has a first side end and a second side end corresponding to the two adjacent stacked monomer structures, the first side end of the second insulating layer 7 at least covers the carbon-based back electrode layer 2 of at least one of the stacked monomer structures, the second side end of the second insulating layer 7 at least covers the porous insulating layer 3 and the carbon-based back electrode layer 2 of another stacked monomer structure, and in the direction from the first side end to the second side end, the second insulating layer 7 is arranged in a slope on a side away from the glass substrate 1, and a transparent front electrode layer 5 is arranged thereon.

[0097] In the technical solution of the present invention, a plurality of stacked monomer structures are arranged at intervals along the plane where the glass substrate 1 is located, and a second insulating layer 7 is arranged on the glass substrate 1 and between two adjacent stacked monomer structures, and the first side end of the second insulating layer 7 at least covers the carbon-based back electrode layer 2 of an adjacent stacked monomer structure, and the second side end of the second insulating layer 7 at least covers the porous insulating layer 3 and the carbon-based back electrode layer 2 of another adjacent stacked monomer structure, so as to avoid the transparent front electrode layer 5 in the same stacked monomer structure from contacting with the porous carbon layer of the lower layer and causing a short circuit. In addition, the second insulating layer 7 is arranged in a slope in the direction of the first side end pointing to the second side end, that is, the side of the second insulating layer 7 away from the glass substrate 1, and is used to receive the transparent front electrode layer 5, so that the transparent front electrode layer 5 of the previous stacked monomer structure is connected to the carbon-based back electrode layer 2 of the adjacent stacked monomer structure, so as to connect the battery cells in series to obtain a battery pack, thereby increasing the output voltage of the battery, reducing the current, and reducing the amount of wires used. The battery pack is suitable for large solar power stations, electric vehicle charging stations and other scenarios. It should be noted that the above-mentioned slope is an angle formed based on the plane of the carbon-based back electrode layer 2 of the next stacked monomer structure overlapped by the second insulating layer 7, and the angle is preferably less than 90°.

[0098] In some embodiments of the present invention, the material of the second insulating layer 7 includes dense zirconium dioxide, dense aluminum oxide or organic resin. The material of the second insulating layer 7 has good compactness and good chemical stability, and can well isolate the transparent front electrode layer 5 and the carbon-based back electrode layer 2 of the adjacent battery cell. Preferably, the material of the second insulating layer 7 is an organic resin, which includes a photosensitive resin, a photocurable resin, and a thermoplastic resin. The organic resin is easy to process and cure, and has good adhesion.

[0099] In some embodiments of the present invention, the slope is A, A<70°. When the slope is less than 70°, the transparent front electrode layer 5 is not easily disconnected from the carbon-based back electrode layer 2 of the adjacent stacked monomer structure, thereby avoiding the transparent front electrode layer 5 from being broken due to its thin thickness and disconnected from the carbon-based back electrode layer 2 of the adjacent battery cell, thereby improving the stability and conversion rate of the battery pack in series.

[0100] The traditional porous battery comprises a conductive substrate, a porous electron transport layer 4, a porous insulating layer 3 and a carbon-based back electrode layer 2 from bottom to top. The preparation process is to first prepare the porous electron transport layer 4, the porous insulating layer 3 and the carbon-based back electrode layer 2, and then perform a high-temperature process (the high-temperature process temperature of the porous electron transport layer 4 is usually around 500°C) to form a porous structure, and then drip a perovskite precursor liquid. The capillary force of the carbon-based back electrode layer 2 material such as carbon is used to diffuse the perovskite precursor liquid in all the porous layers to crystallize, so that the perovskite precursor liquid forms a crystal nucleus and gradually grows into a perovskite crystal. However, in the above preparation method, on the one hand, since the carbon-based back electrode layer 2 is first in contact with the air, the perovskite precursor liquid inside the carbon-based back electrode layer 2 crystallizes first, and the perovskite solution inside the porous structure (porous insulating layer 3 and porous electron transport layer 4) of the lower layer will crystallize relatively later, resulting in a lack of perovskite solution in the porous structure of the lower layer, which directly affects the performance of the battery cell; on the other hand, in the crystallization process of the perovskite precursor liquid, since the upper carbon-based back electrode layer 2 crystallizes first, that is, the crystal nucleus is formed first, the perovskite precursor liquid diffused in the lower porous structure is easily affected by the growth of the crystal nucleus and adsorbed in the carbon-based back electrode layer 2, which reduces the perovskite crystallization of the lower layer, and the perovskite crystallization in the porous structure is unevenly distributed. It will also make the crystals in the carbon-based back electrode layer 2 too large. Due to the limited size of the porous structure, the excessively large crystals will cause the porous structure to break or even collapse, thereby exposing the perovskite crystals and affecting the battery performance. The present invention also provides a method for preparing a perovskite battery cell 100, wherein the electron transport layer 4 is a dense structure, and the method for preparing the perovskite battery cell 100 comprises the following steps:

[0101] S1, providing a glass substrate 1, sequentially preparing a carbon-based back electrode layer 2 and a porous insulating layer 3 on the glass substrate 1, and performing high-temperature sintering;

[0102] S2, applying a drop of a perovskite precursor liquid onto the porous insulating layer 3, so that the perovskite precursor liquid at least fills the porous insulating layer 3, and performing annealing and crystallization;

[0103] S3, preparing an electron transport layer 4 and a transparent front electrode layer 5 on the porous insulating layer 3 to obtain a perovskite battery cell 100.

[0104] In the technical solution of the present invention, a carbon-based back electrode layer 2 and a porous insulating layer 3 are first prepared on a glass substrate 1 in sequence, and after high-temperature annealing to form a porous structure, a perovskite precursor liquid is dripped and crystallized, and finally an electron transport layer 4 and a transparent front electrode layer 5 are prepared on the porous insulating layer 3. On the one hand, when the carbon-based back electrode layer 2 is a porous structure, the carbon-based back electrode layer 2 is located in the lower layer, and its capillary effect can also be exerted to make the perovskite precursor liquid dripped on the surface of the porous insulating layer 3 enter the porous structure (porous insulating layer 3 and carbon-based back electrode layer 2) better and more evenly. At the same time, during the crystallization process, since the upper porous insulating layer 3 first contacts the air to form a crystal nucleus, the uneven distribution and growth of perovskite crystals in the porous structure are avoided, the uniformity of the size and distribution of perovskite crystals is improved, and the efficiency of the battery cell is improved; on the other hand, the electron transport layer 4 can be replaced by a material that has less influence on the crystallization of perovskite, and the conductivity of the electron transport layer 4 can also be better improved. It should be noted that in the present invention, the electron transport layer 4 can be a porous structure or a dense structure, and can be a titanium dioxide material or a fullerene or other material. When the electron transport layer 4 is a porous material, since the underlying porous insulating layer 3 and the carbon-based back electrode layer 2 have good heat resistance and stability, the high-temperature process will not have an adverse effect on the underlying structure.

[0105] In some embodiments of the present invention, the crystallization temperature is greater than the temperature for preparing the electron transport layer 4. When the crystallization temperature of the perovskite material is higher than the temperature for preparing the electron transport layer 4, the perovskite crystallization in the porous structure is more stable when preparing the electron transport layer 4.

[0106] In some embodiments of the present invention, the material of the electron transport layer 4 includes fullerene or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. The preparation temperature of the above electron transport material is low, the effect on perovskite crystallization is small, and the preparation process is simple.

[0107] In some embodiments of the present invention, in step S1, the temperature of the high temperature annealing is 150-450°C; and / or, in step S1, the time of the high temperature annealing is 30min-60min. The temperature of the high temperature annealing within the above range can ensure the formation of a better, more stable, and larger specific surface area porous structure; the time of the high temperature annealing within the above range can ensure sufficient time to form a better porous structure to accommodate perovskite crystallization.

[0108] In some embodiments of the present invention, in step S2, the crystallization temperature is 100-150°C; and / or, in step S2, the crystallization time is 10min-30min. The crystallization temperature within the above range can ensure that the perovskite solution can quickly form crystal nuclei and grow uniformly; the crystallization time within the above range can ensure that the perovskite solution has sufficient time to form more crystals, and the size of the crystals is moderate, and the porous structure is not affected.

[0109] In some embodiments of the present invention, in step S3, the method for preparing the transparent front electrode layer 5 includes magnetron sputtering or plasma deposition. The method for preparing the transparent front electrode layer 5 is preferably magnetron sputtering, which has the advantages of fast deposition rate, good film uniformity and good adhesion.

[0110] In some embodiments of the present invention, step S1 comprises the following steps:

[0111] Coating a carbon-based back electrode layer 2 slurry containing an additive on the glass substrate 1 and drying the slurry to obtain a first coating structure;

[0112] Applying the auxiliary agent-containing insulating layer slurry on the first coating structure, and drying to obtain a second coating structure;

[0113] The second coating structure is subjected to high temperature annealing to volatilize the auxiliary agent and form pores in the second coating structure.

[0114] In the technical solution of the present invention, the carbon-based back electrode layer 2 and the porous insulating layer 3 are prepared by a slurry containing an auxiliary agent (i.e., a pore-forming agent). The pore-forming agent refers to a material that is volatile at a certain temperature. Under dry conditions, the substance volatilizes to form certain pores inside the raw materials of the carbon-based back electrode layer 2 and the porous insulating layer 3, which can be pores of the size of mesopores or micropores. A more stable porous structure can be obtained quickly by this method. It should be noted that the present invention can also first coat the carbon-based back electrode layer 2 slurry on the glass substrate 1 and then anneal at high temperature to obtain the carbon-based back electrode layer 2, and then coat the porous insulating layer 3 slurry on the carbon-based back electrode layer 2 and then anneal at high temperature to obtain two porous layers.

[0115] In some embodiments of the present invention, the additive includes an inorganic additive and / or an organic additive, the inorganic additive includes at least one of sodium bicarbonate, sodium carbonate and ammonium bicarbonate, and the organic additive includes at least one of ethyl cellulose and propyl hydroxy cellulose. The above additives have good volatility and the pores formed are suitable for the growth of perovskite crystals.

[0116] In some embodiments of the present invention, the coating method includes screen printing, which can make the coating layer more uniform, more precise, and easier to operate.

[0117] The present invention also provides a method for preparing a perovskite battery cell 100, wherein the electron transport layer 4 is a porous structure, and the method for preparing the perovskite battery cell 100 comprises the following steps:

[0118] S10, providing a glass substrate, sequentially preparing a carbon-based back electrode layer 2, a porous insulating layer 3 and an electron transport layer 4 on the glass substrate 1, and performing high-temperature annealing;

[0119] S20, applying a perovskite precursor liquid droplet on the electron transport layer 4, so that the perovskite precursor liquid at least fills the electron transport layer 4 and the porous insulating layer 3, and performing annealing and crystallization;

[0120] S30, preparing a transparent front electrode layer 5 on the electron transport layer 4 to obtain a perovskite battery cell 100.

[0121] In the technical solution of the present invention, when the electron transport layer 4 is a porous structure, it can be prepared simultaneously with the carbon-based back electrode layer 2 and the porous insulating layer 3, and then the perovskite precursor solution is dripped on the electron transport layer 4, so that the perovskite material crystallizes in the electron transport layer 4 and the porous insulating layer 3, or crystallizes in the electron transport layer 4, the porous insulating layer 3 and the carbon-based back electrode layer 2, thereby avoiding the melting of the perovskite crystals during the high-temperature process of the electron transport layer 4, affecting the distribution and size uniformity of the perovskite crystals in the porous insulating layer 3, and ensuring a high conversion efficiency of the battery.

[0122] The present invention also provides a method for preparing a perovskite battery pack 200, wherein the electron transport layer 4 is a dense structure, and the method for preparing the perovskite battery pack 200 comprises the following steps:

[0123] S100a, providing a glass substrate 1, sequentially preparing a carbon-based back electrode layer 2 and a porous insulating layer 3 on the glass substrate 1, and performing high-temperature annealing to obtain a first stacked body;

[0124] S200a, etching a plurality of etching grooves at intervals along the plane where the glass substrate 1 is located, dividing the first stacked body into a plurality of first stacked structures, and preparing a second insulating layer 7 in each of the etching grooves;

[0125] S300a, applying a drop of a perovskite precursor liquid on the porous insulating layer 3 of each of the first stacked structures, so that the perovskite precursor liquid at least fills the porous insulating layer 3, and performs crystallization;

[0126] S400a, preparing an electron transport layer 4 on the porous insulating layer 3 of each of the first stacked structures, and then preparing a transparent front electrode layer 5 on the electron transport layer 4 and the first insulating layer 63 to obtain a plurality of stacked monomer structures, so that the transparent front electrode layer 5 of each stacked monomer structure is connected to the carbon-based back electrode layer 2 of the adjacent stacked monomer structure, to obtain a perovskite battery group 200;

[0127] The crystallization temperature is greater than the temperature for preparing the electron transport layer 4 .

[0128] In the technical solution of the present invention, the method for preparing a battery pack through the above-mentioned integration has a simple operation process, and a battery assembly connected in series can be directly obtained. Among them, a first stack is prepared first, and then a plurality of etching grooves are obtained by interval etching. The etching grooves divide the first stack into a plurality of first stack structures, and then a second insulating layer 7 is prepared in the etching grooves to avoid the subsequent transparent front electrode layer 5 from contacting the carbon-based back electrode layer 2 of the same first stack structure during the integrated preparation, causing a short circuit during use. That is, after the carbon-based back electrode layer 2 and the porous insulating layer 3 are prepared, the etching grooves are first etched to obtain the second insulating layer 7, and then the perovskite precursor liquid is dripped in for crystallization, and finally the electron transport layer 4 and the transparent front electrode layer 5 are prepared on the porous insulating layer 3. This preparation method can prevent the second insulating layer 7 from being melted during the preparation of the electron transport layer 4 when the second insulating layer 7 is an organic resin, resulting in failure of the second insulating layer 7, thereby affecting the subsequent connection setting of the transparent front electrode layer 5. Among them, the material of the electron transport layer 4 includes a material that does not affect the crystallization of the perovskite and does not melt it, and the material of the second insulating layer 7 includes an organic resin. Preferably, the material of the second insulating layer 7 is dense titanium dioxide, which has a higher density than organic resin and can better prevent the perovskite precursor liquid from seeping through the second insulating layer 7. It should be noted that after step S400a, an etching process is also included, that is, etching away the transparent front electrode layer 5 in contact with other electrode layers to prevent poor contact.

[0129] It should be noted that the second insulating layer 7 can be prepared as a slope structure, so that the transparent front electrode layer 5 is laid on a gentle slope to connect to the carbon-based back electrode layer 2 of the adjacent first stacking structure, to prevent the transparent front electrode layer 5 of the first stacking structure of the previous section from being disconnected from the carbon-based back electrode layer 2 connected in series with it. Preferably, the carbon-based back electrode layer 2 is partially protruded on one side connected in series with the first stacking structure of the previous section, that is, the etching can be divided into two times, one time to etch away all layers until the glass substrate 1, the second time to etch away all layers on the carbon-based back electrode layer 2, and retain the carbon-based back electrode layer 2, so that the carbon-based back electrode layer 2 has a protruding structure on one side thereof, which is used to bear the slope of the second insulating layer 7 and provide space to contact with the transparent front electrode layer 5.

[0130] The present invention also provides a method for preparing a perovskite battery pack 200, wherein the electron transport layer 4 is a porous structure, and the method for preparing the perovskite battery pack 200 comprises the following steps:

[0131] S100b, providing a glass substrate 1, sequentially preparing a carbon-based back electrode layer 2, a porous insulating layer 3 and an electron transport layer 4 on the glass substrate 1, and performing high-temperature annealing;

[0132] S200b, applying a drop of a perovskite precursor liquid on the electron transport layer 4, so that the perovskite precursor liquid at least fills the electron transport layer 4 and the porous insulating layer 3, and performing crystallization to obtain a second stacked body;

[0133] S300b, etching a plurality of etching grooves at intervals along the plane where the glass substrate 1 is located, dividing the second stacked body into a plurality of second stacked structures, and preparing a second insulating layer 7 in each of the etching grooves;

[0134] S400b, preparing a transparent front electrode layer 5 on the electron transport layer 4 of each of the second stacking structures to obtain a plurality of stacking monomer structures, so that the transparent front electrode layer 5 of each of the stacking monomer structures is connected to the carbon-based back electrode layer 2 of its adjacent stacking monomer structure to obtain a perovskite battery group 200.

[0135] In the technical solution of the present invention, a third integrated method for preparing a perovskite battery pack 200 is provided, and the material of the second insulating layer 7 can be dense titanium dioxide or an organic resin. In this step, during assembly, the second insulating layer 7 is prepared after the porous electron transport layer 4 is completed to prevent the organic resin from being melted and failing during the high-temperature process of the porous structure, thereby affecting the subsequent connection setting of the transparent front electrode layer 5.

[0136] The present invention also provides an electrical device, including the aforementioned perovskite battery cell 100. The electrical device may be a watch, a mobile phone, etc. Since the electrical device includes the aforementioned perovskite battery cell 100, it has all the beneficial effects of the aforementioned perovskite battery cell 100, which will not be described one by one here.

[0137] The present invention also provides a charging system, including the aforementioned perovskite battery pack 200. The charging system includes devices such as a solar power station and an electric vehicle charging station. Since the charging system includes the aforementioned perovskite battery pack 200, it has all the beneficial effects of the aforementioned perovskite battery pack 200, which will not be described one by one here.

[0138] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments and drawings. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0139] Example 1

[0140] A method for preparing a perovskite battery pack 200 comprises the following steps:

[0141] (1) Screen-printing carbon paste on a glass substrate 1 and heating it at 125°C to evaporate the solvent in the carbon paste. After the carbon paste is dried, screen-printing a layer of zirconium dioxide paste on the carbon paste layer and heating it at 125°C to evaporate the solvent in the zirconium dioxide paste. After the zirconium dioxide paste is dried, high-temperature annealing is performed at 400°C to evaporate the high molecular organic compound in the zirconium dioxide paste to form certain pores, thereby forming a dense carbon back electrode layer 2 and a porous insulating layer 3 with thicknesses of 30 μm and 3 μm, respectively.

[0142] The preparation method of the carbon slurry is as follows: after mixing carbon black, graphite, etc. in a ratio of 2:1, 50 mL of pine alcohol is added, and the mixture is fully stirred and ball-milled using a ball mill for 10 hours to obtain the carbon slurry.

[0143] The preparation method of zirconium dioxide slurry is as follows: weigh 15 μm ZrO2 particles, add 2 g of ethyl cellulose, mix evenly, add 50 mL of oleyl alcohol and a large amount of ethanol solvent, and ball mill to obtain zirconium dioxide slurry, and the ball milling time is 30 hours.

[0144] (2) Using a green picosecond laser, the components prepared in (1) are laser etched to remove the porous insulating layer 3 and the porous carbon back electrode layer 2. The etching width is 20 μm, and etching grooves are obtained between each single battery cell, as well as relatively independent single battery cells. During laser etching, part of the carbon back electrode layer 2 is exposed to facilitate connection with the front electrode of the adjacent battery cell to form a series circuit.

[0145] (3) An epoxy resin organic resin layer is prepared by coating in the etching groove, and after coating, it is heated and cured at 70°C to form an insulating layer at a certain angle, so that one side of it covers the carbon back electrode layer 2 and the porous insulating layer 3 of a stacked structure, and the other side overlaps the porous carbon back electrode layer 2 of the adjacent stacked structure, and the angle slope between the overlap and the horizontal direction is 60°.

[0146] (4) The FACsPbI3 perovskite precursor liquid was coated on the porous insulating layer 3 of each stacked structure using a slit coating method (20 mm / s speed), and then heated at 150° C. to crystallize the perovskite precursor liquid.

[0147] (5) An electron transport layer 4 of fullerene material with a thickness of 20 nm is prepared on the porous insulating layer 3 by thermal evaporation at an evaporation rate of 0.8 A / s, and then a 15 nm SnO2 electron transport layer 4 is further deposited using an atomic layer deposition (ALD) device, that is, the fullerene layer and the SnO2 layer together constitute the electron transport layer 4.

[0148] (6) An ITO transparent electrode layer with a thickness of 100 nm is prepared on the electron transport layer 4 by magnetic sputtering to form a transparent front electrode. In the entire battery structure, sunlight is incident from this side.

[0149] (7) Using laser etching, the transparent front electrode layer 5 in contact with other layers of each stacked structure is removed, so that the transparent front electrode layer 5 is only in contact with the carbon-based back electrode layer 2 of the stacked structure.

[0150] Example 2

[0151] Compared with Example 1, Example 2 is different in that:

[0152] In step (1), ethyl cellulose is added to the carbon slurry of the carbon back electrode layer 2, and sintered at high temperature together with the zirconium dioxide slurry to form a porous structure; wherein the preparation method of the carbon slurry is: carbon black, graphite, ethyl cellulose, etc. are mixed in a ratio of 2:1:0.1, 50 mL of pine alcohol is added, and the mixture is fully stirred and ball-milled using a ball mill for 10 hours to obtain a carbon slurry;

[0153] In step (5), the material of the electron transport layer 4 is porous titanium dioxide, wherein the preparation method of the porous titanium dioxide is similar to that of step (1).

[0154] Example 3

[0155] Compared with Example 1, Example 3 is different in that:

[0156] In step (1), an ITO metal oxide layer 61 with a thickness of 100 nm is first prepared on the glass substrate 1 by magnetron sputtering, and then a carbon-based back electrode layer 2 is prepared on the metal oxide layer 61 .

[0157] Example 4

[0158] Compared with Example 3, Example 4 is different in that:

[0159] In step (1), a copper metal layer 62 with a thickness of 100 nm is first prepared on the glass substrate 1 by magnetron sputtering, and then a 20 nm thick ITO metal oxide layer 61 is plated on the metal layer 62 by magnetron sputtering. Subsequently, a first insulating layer 63 of photoresist (photosensitive resin) with a thickness of 3 μm is prepared on the ITO by coating, and then the photosensitive resin is exposed, etched, and developed by an exposure machine to form through holes in the photosensitive resin insulating layer. Subsequently, steps such as screen printing of carbon slurry are performed, which are the same as in Example 1, wherein after carbon printing, these through holes are connected to the metal oxide at the bottom of the insulating layer to reduce the resistance of the carbon layer.

[0160] Performance Testing

[0161] The battery cells of Examples 1 to 4 were tested for short-circuit current density, open-circuit voltage, conversion efficiency, and fill factor. The test results are shown in Table 1.

[0162] Table 1 Conversion efficiency of battery cells of Examples 1 to 4

[0163] <![CDATA[Short-circuit current density (mA / cm 2 )]]> Open circuit voltage (v) Conversion efficiency (%) Fill factor (%) Example 1 23.8 0.98 18.1 77.2 Example 2 23.5 0.98 17.3 74.9 Example 3 22.5 1.05 19 79.6 Example 4 22.9 1.05 19.5 80.5

[0164] The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the patent protection scope of the present invention.

Claims

1. A perovskite battery cell, characterized in that: include: Glass substrate; as well as, A carbon-based back electrode layer, a porous insulating layer, an electron transport layer and a transparent front electrode layer are sequentially arranged on the glass substrate; Wherein, at least the porous insulating layer is filled with perovskite material.

2. The perovskite battery cell according to claim 1, characterized in that: The thickness of the carbon-based back electrode layer is 1 μm-50 μm; and / or, The thickness of the porous insulating layer is 100 nm-5 μm; and / or, The thickness of the electron transport layer is 10nm-50nm; and / or, The thickness of the transparent front electrode layer is 10 nm-1 μm; and / or, The material of the carbon-based back electrode layer includes carbon, graphene-doped carbon or carbon nanotube-doped carbon; and / or, The material of the porous insulating layer includes one or more of zirconium dioxide, silicon dioxide and aluminum oxide; and / or, The material of the electron transport layer includes at least one of titanium dioxide, tin dioxide, fullerene and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and / or, The material of the transparent front electrode layer includes indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide or fluorine-doped tin oxide.

3. The perovskite battery cell according to claim 1, characterized in that: The perovskite battery cell further includes a back electrode auxiliary layer, wherein the back electrode auxiliary layer is disposed between the carbon-based back electrode layer and the glass substrate, and the back electrode auxiliary layer includes a metal oxide layer.

4. The perovskite battery cell according to claim 3, characterized in that: The back electrode auxiliary layer further includes a metal layer, and the metal layer is disposed between the metal oxide layer and the glass substrate.

5. The perovskite battery cell according to claim 4, characterized in that: The back electrode auxiliary layer also includes a first insulating layer, which is arranged between the metal oxide layer and the carbon-based back electrode layer. The first insulating layer includes a plurality of insulating layers arranged at intervals along the plane where the metal oxide layer is located, and carbon is arranged in the intervals between the plurality of insulating layers to connect the carbon-based back electrode layer and the metal oxide layer.

6. The perovskite battery cell according to claim 5, characterized in that: The material of the metal oxide layer includes indium tin oxide, indium zinc oxide, aluminum-doped zinc oxide or fluorine-doped tin oxide; and / or, The material of the metal layer includes one or more of Cu, Ag, Al and Mn; and / or, The material of the first insulating layer includes at least one of a photosensitive resin and a thermosetting resin; and / or, The thickness of the metal oxide layer is 20nm-1000nm; and / or, The thickness of the metal layer is 20nm-100nm; and / or, The thickness of the first insulating layer is 1 μm-5 μm.

7. The perovskite battery cell according to claim 3, characterized in that: The perovskite battery cell further includes a dense electrode layer, which is disposed between the carbon-based back electrode layer and the back electrode auxiliary layer.

8. The perovskite battery cell according to claim 1, characterized in that: The perovskite battery cell further includes a hole transport layer, which is disposed between the carbon-based back electrode layer and the porous insulating layer.

9. A perovskite battery pack, characterized in that: include: Glass substrate; as well as, A plurality of stacked monomer structures are arranged on the glass substrate, each of the stacked monomer structures comprises a carbon-based back electrode layer, a porous insulating layer, an electron transport layer and a transparent front electrode layer sequentially stacked on the glass substrate, and at least the porous insulating layer is filled with a perovskite material; Wherein, the carbon-based back electrode layer of the stacked monomer structure and the transparent front electrode layer of the adjacent stacked monomer structure are connected to each other.

10. The perovskite battery pack according to claim 9, characterized in that: The multiple stacked monomer structures are arranged at intervals along the plane where the glass substrate is located, and a second insulating layer is arranged on the glass substrate and between two adjacent stacked monomer structures. The second insulating layer has a first side end and a second side end corresponding to the two adjacent stacked monomer structures. The first side end of the second insulating layer covers at least one carbon-based back electrode layer of the stacked monomer structure, and the second side end of the second insulating layer covers at least the porous insulating layer and the carbon-based back electrode layer of another stacked monomer structure. In the direction from the first side end to the second side end, the second insulating layer is arranged in a slope on a side away from the glass substrate, and a transparent front electrode layer is arranged thereon.

11. The perovskite battery pack according to claim 10, characterized in that: The material of the second insulating layer includes dense zirconium dioxide, dense aluminum oxide or organic resin; and / or, The slope is A, A<70°.

12. A method for preparing a perovskite battery monomer as claimed in claim 1, characterized in that: The electron transport layer is a dense structure, and the preparation method of the perovskite battery monomer comprises the following steps: S1, providing a glass substrate, sequentially preparing a carbon-based back electrode layer and a porous insulating layer on the glass substrate, and performing high-temperature sintering; S2, applying a perovskite precursor droplet onto the porous insulating layer, so that the perovskite precursor liquid at least fills the porous insulating layer, and performing annealing and crystallization; S3. Prepare an electron transport layer and a transparent front electrode layer on the porous insulating layer to obtain a perovskite battery cell.

13. The method for preparing a perovskite battery monomer according to claim 12, characterized in that: In step S1, the high temperature annealing temperature is 150-450° C.; and / or, In step S1, the high temperature annealing time is 30 min-60 min; and / or, In step S2, the crystallization temperature is 100-150° C.; and / or, In step S2, the crystallization time is 10 min-30 min; and / or, In step S3, the method for preparing the transparent front electrode layer includes magnetron sputtering or plasma deposition.

14. The method for preparing a perovskite battery monomer according to claim 12, characterized in that: Step S1 includes the following steps: Coating a carbon-based back electrode layer slurry containing an additive on the glass substrate, and drying to obtain a first coating structure; Applying the auxiliary agent-containing insulating layer slurry on the first coating structure, and drying to obtain a second coating structure; The second coating structure is subjected to high temperature annealing to volatilize the auxiliary agent and form pores in the second coating structure.

15. The method for preparing a perovskite battery monomer according to claim 14, characterized in that: The auxiliary agent includes an inorganic auxiliary agent and / or an organic auxiliary agent, wherein the inorganic auxiliary agent includes at least one of sodium bicarbonate, sodium carbonate and ammonium bicarbonate, and the organic auxiliary agent includes at least one of ethyl cellulose and propyl hydroxy cellulose; and / or, The coating method includes screen printing.

16. A method for preparing a perovskite battery monomer as claimed in claim 1, characterized in that: The electron transport layer is a porous structure, and the preparation method of the perovskite battery monomer comprises the following steps: S10, providing a glass substrate, sequentially preparing a carbon-based back electrode layer, a porous insulating layer and an electron transport layer on the glass substrate, and performing high-temperature annealing; S20, applying a perovskite precursor liquid droplet on the electron transport layer, so that the perovskite precursor liquid at least fills the electron transport layer and the porous insulating layer, and performing annealing and crystallization; S30, preparing a transparent front electrode layer on the electron transport layer to obtain a perovskite battery cell.

17. A method for preparing a perovskite battery pack as claimed in claim 10, characterized in that: The electron transport layer is a dense structure, and the preparation method of the perovskite battery pack comprises the following steps: S100a, providing a glass substrate, sequentially preparing a carbon-based back electrode layer and a porous insulating layer on the glass substrate, and performing high-temperature annealing to obtain a first stacked body; S200a, etching a plurality of etching grooves at intervals along the plane where the glass substrate is located, dividing the first stacked body into a plurality of first stacked structures, and preparing a second insulating layer in each of the etching grooves; S300a, applying a perovskite precursor liquid droplet on the porous insulating layer of each of the first stacked structures, so that the perovskite precursor liquid at least fills the porous insulating layer, and performing crystallization; S400a, preparing an electron transport layer on the porous insulating layer of each of the first stacked structures, and then preparing a transparent front electrode layer on the electron transport layer and the first insulating layer to obtain a plurality of stacked monomer structures, so that the transparent front electrode layer of each stacked monomer structure is connected to the carbon-based back electrode layer of the adjacent stacked monomer structure to obtain a perovskite battery group; The crystallization temperature is greater than the temperature for preparing the electron transport layer.

18. A method for preparing a perovskite battery pack as claimed in claim 10, characterized in that: The electron transport layer is a porous structure, and the preparation method of the perovskite battery pack comprises the following steps: S100b, providing a glass substrate, sequentially preparing a carbon-based back electrode layer, a porous insulating layer and an electron transport layer on the glass substrate, and performing high-temperature annealing; S200b, applying a perovskite precursor liquid droplet on the electron transport layer, so that the perovskite precursor liquid at least fills the electron transport layer and the porous insulating layer, and performing crystallization to obtain a second stacked body; S300b, etching a plurality of etching grooves at intervals along the plane where the glass substrate is located, dividing the second stacked body into a plurality of second stacked structures, and preparing a second insulating layer in each of the etching grooves; S400b, preparing a transparent front electrode layer on the electron transport layer of each of the second stacking structures to obtain a plurality of stacking monomer structures, so that the transparent front electrode layer of each of the stacking monomer structures is connected to the carbon-based back electrode layer of its adjacent stacking monomer structure to obtain a perovskite battery group.

19. An electrical device, characterized in that: Comprising the perovskite battery cell according to any one of claims 1 to 8.

20. A charging system, characterized in that: A perovskite battery comprising the perovskite battery pack as claimed in any one of claims 9 to 11.

Images