Glove box for perovskite cell fabrication

Abstract

The embodiment of the present application provides a glove box for perovskite battery preparation. The glove box for perovskite battery preparation comprises a circulation loop, the circulation loop comprises a box, a solvent adsorption system, a gas reaction system and a water and oxygen circulation system connected in sequence; the gas reaction system is used for reacting with ammonia gas and acidic gas generated in the perovskite battery preparation process. By introducing the gas reaction system into the glove box, the ammonia gas and the acidic gas generated in the perovskite battery preparation process are reacted, the acidic gas and the ammonia gas are blocked from entering the water and oxygen circulation system, so that the atmosphere in the glove box is kept stable, and the service life of the glove box is prolonged.

Description

Technical Field

[0001] This application relates to the field of glove box technology, and more particularly to a glove box for the fabrication of perovskite solar cells. Background Technology

[0002] With the improvement of my country's energy structure, more and more new energy sources are replacing traditional thermal power generation. Among them, solar energy is a renewable energy source. Solar power generation is simple to install, requires little site space, and is suitable for various occasions and needs. Therefore, it is widely used in various fields.

[0003] Organic-inorganic hybrid perovskite materials possess advantages such as high absorption coefficient, tunable bandgap, long carrier diffusion length, and high defect tolerance, as well as simple fabrication processes and low material and fabrication costs. They are considered among the newest materials closest to commercialization in the photovoltaic market in recent years. After only a decade or so of research, single-junction perovskite solar cells have achieved high photoelectric conversion efficiencies, surpassing commercially available cadmium telluride and copper indium gallium selenide (CIGS) cells, and are very close to the mainstream crystalline silicon (26.7%) solar cells. Perovskite tandem solar cells combine high efficiency and low cost, and are considered one of the technologies with the potential to achieve large-scale ground-mounted photovoltaic applications. With their outstanding advantages of high efficiency, low cost, and simple fabrication processes, perovskite tandem solar cells have gradually become a hot topic in the global photovoltaic research field in recent years.

[0004] Currently, most laboratory perovskite preparations utilize spin-coating in a glove box. The atmosphere within the glove box significantly impacts device performance and success rate. Using a conventional glove box, it was found that the copper catalyst in the water-oxygen circulation system frequently fails, affecting the glove box's lifespan.

[0005] In the past, when using glove boxes, only the water and oxygen atmosphere and solvent atmosphere of the glove box were considered, while the volatile gases generated during the perovskite preparation process that have a significant impact on device performance were not noticed.

[0006] In view of the problems existing in the current technology, it is very necessary to develop a glove box for use in the production process of perovskite solar cells.

[0007] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Utility Model Content

[0008] This application provides a glove box for fabricating perovskite solar cells to solve or alleviate one or more of the technical problems mentioned above.

[0009] The first aspect of this application provides a glove box for preparing perovskite solar cells. The glove box for preparing perovskite solar cells includes a circulation loop, which includes a box body, a solvent adsorption system, a gas reaction system, and a water-oxygen circulation system connected in sequence. The gas reaction system is used to react with ammonia and acidic gases generated during the preparation of perovskite solar cells.

[0010] Optionally, the gas reaction system includes a gas reaction vessel, which includes a first region, a second region, and a partition separating the first region and the second region.

[0011] Optionally, the first region is provided with a first packing material, and the second region is provided with a second packing material.

[0012] Optionally, the average particle size of the first filler is 0.03 μm-180 μm.

[0013] Optionally, the first filler is calcium oxide, barium oxide, or calcium hydroxide.

[0014] Optionally, the first filler is filled by solid powder or spherical particles, and the volume ratio of the first filler in the first region is (0.3-1):1.

[0015] Optionally, the second filler is a sulfonic acid-based aerogel, functional fiber, or porous ceramic ball.

[0016] Optionally, the average particle size of the porous ceramic spheres is 0.03-200 μm.

[0017] Optionally, the second filler has a filling volume ratio of (0.3-1):1 in the second region.

[0018] Optionally, the partition is a metal mesh structure or a porous plastic structure.

[0019] Optionally, the number of layers in the partition is 1-5.

[0020] Optionally, the gas reaction vessel is also provided with a gas inlet and a gas outlet.

[0021] Optionally, the gas inlet is located in the first region of the gas reaction vessel for introducing unreacted gas.

[0022] Optionally, the gas outlet is located in the second region of the gas reaction vessel for discharging the reacted gas.

[0023] Optionally, the gas reaction vessel is a detachable structure for replacing the first packing and / or the second packing in the gas reaction vessel.

[0024] Optionally, the gas reaction system further includes a backup gas reaction tank and an automatic switching valve group.

[0025] Optionally, the backup gas reactor is connected in parallel with the gas reactor.

[0026] Optionally, the automatic switching valve assembly is used to automatically switch to a standby gas reaction tank when the gas reaction tank is saturated with adsorption.

[0027] Optionally, the water-oxygen circulation system includes a molecular sieve dryer and a copper catalyst reactor arranged in series.

[0028] Optionally, the molecular sieve dryer is used to adsorb water vapor.

[0029] Optionally, the copper catalyst reactor is used to decompose residual oxygen.

[0030] Optionally, the solvent adsorption system includes activated carbon for adsorbing organic solvents generated during the preparation of perovskite solar cells.

[0031] The embodiments of this application employing the above-described technical solution may have the following advantages: By introducing a gas reaction system into the glove box, which reacts with ammonia and acidic gases generated during the perovskite battery fabrication process, the ammonia and acidic gases are prevented from entering the water-oxygen circulation system, thereby ensuring a stable atmosphere in the glove box and extending its service life. Attached Figure Description

[0032] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.

[0033] Figure 1 This is a schematic diagram of the structure of the glove box for fabricating perovskite solar cells provided in a specific embodiment of this application; Figure 2 The chemical formula for the reaction in the specific embodiments of this application to remove ammonia gas generated during the preparation of perovskite solar cells; Figure 3 This is a schematic diagram of the structure of the gas reaction vessel in a specific embodiment of this application; Explanation of reference numerals in the attached figures: 1. First zone; 2. Second zone; 3. Interlayer; 4. Gas inlet; 5. Gas outlet. Detailed Implementation

[0034] The embodiments of this application are described in detail below, examples of which are illustrated in the accompanying drawings. In the drawings, for clarity, the dimensions of layers, regions, and elements, as well as their relative dimensions, may be exaggerated. Throughout, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0035] It should be understood that when an element or layer is referred to as "on," "adjacent to," "connected to," or "coupled to" other elements or layers, it may be directly on, adjacent to, connected to, or coupled to other elements or layers, or there may be intervening elements or layers. Conversely, when an element is referred to as "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" other elements or layers, there are no intervening elements or layers. It should be understood that although the terms first, second, third, etc., may be used to describe various elements, components, areas, layers, and / or portions, these elements, components, areas, layers, and / or portions should not be limited by these terms. These terms are only used to distinguish one element, component, area, layer, or portion from another element, component, area, layer, or portion. Therefore, without departing from the teachings of this application, the first element, component, area, layer, or portion discussed below may be referred to as a second element, component, area, layer, or portion. And the discussion of a second element, component, area, layer, or portion does not imply that the first element, component, area, layer, or portion necessarily exists in this application.

[0036] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise expressly limited. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0037] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0038] In this application, when numerical intervals (i.e., numerical ranges) are involved, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.

[0039] Exemplary embodiments according to this application will now be described in more detail with reference to the accompanying drawings. It should be understood that these exemplary embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein.

[0040] This application provides a glove box for fabricating perovskite solar cells, such as... Figure 1 As shown, the glove box for preparing perovskite solar cells includes a circulation loop, which includes a box body, a solvent adsorption system, a gas reaction system, and a water-oxygen circulation system connected in sequence. The gas reaction system is used to react with ammonia and acidic gases generated during the preparation of perovskite solar cells.

[0041] It should be noted that, as Figure 2As shown, during the perovskite preparation process, methylamine chloride (MACl) releases ammonia gases (exemplary, including methylamine) and acidic gases (exemplary, including hydrogen chloride). The ammonia and acidic gases produced significantly affect the efficiency and repeatability of the device. Excess ammonia reacts with the perovskite precursor formamidinium hydroiodide (FAI) to form Cis-MFAI. This substance further reacts with lead iodide (PbI2) to form a methylamine iodide-based perovskite (MAFPbI3) structure. This structure cannot transform into the perovskite phase, resulting in poor photoelectric performance and thus affecting the stability of the device. Acidic gases, especially hydrogen chloride, even at extremely low concentrations, can disrupt the perovskite film formation and crystallization process, affecting the quality of the perovskite film.

[0042] In existing glove boxes, the ammonia and acidic gases generated during the preparation of perovskite materials can affect the survival rate and efficiency of devices and damage the copper catalyst in the glove box circulation system, thereby reducing the service life of the glove box. This application introduces a gas reaction system between the solvent adsorption system and the water-oxygen circulation system of the glove box, which can react away the ammonia and acidic gases, thereby ensuring the stability of the atmosphere in the glove box, thus guaranteeing the survival rate and efficiency of devices, and effectively maintaining the service life of the glove box.

[0043] In some embodiments, the gas reaction system includes a gas reaction vessel, the gas reaction vessel including a first region, a second region, and a partition separating the first region and the second region.

[0044] In some embodiments, the first region is provided with a first packing material, and the second region is provided with a second packing material.

[0045] In this application, the main function of the gas reaction system is to remove ammonia and acidic gases generated during the preparation of perovskite materials. The gas reaction system includes a first region, a second region, and a partition. The first region is provided with a first packing material to remove acidic gases, and the second region is provided with a second packing material to remove ammonia gases. The partition separates the first and second packing materials while ensuring that gas can pass through and providing some support.

[0046] In some embodiments, the average particle size of the first filler is 0.03 μm-180 μm (exemplary average particle sizes are 0.03 μm, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, etc.).

[0047] In some embodiments, the first filler is calcium oxide, barium oxide, or calcium hydroxide.

[0048] In some embodiments, the first filler is filled by solid powder filling, and the filling volume ratio of the first filler in the first region is (0.3-1):1 (exemplary filling volume ratios are 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, etc.).

[0049] In this application, the first packing material is an alkaline substance, the purpose of which is to remove acidic gases, especially hydrogen chloride gas. The preferred alkaline substance is calcium oxide, barium oxide, or calcium hydroxide. Such alkaline substances are usually in powder form with an average particle size of 0.03 μm-180 μm. The first region is filled with powder. In order to ensure the reaction effect, the filling volume of the first packing material in the first region is (0.3-1):1. Within this filling volume range, it has a good acid removal effect. If the filling volume is too small, it is not conducive to the filling of acidic gases. If the filling volume is too large, it is not conducive to the overall gas passage.

[0050] In some embodiments, the second filler is a sulfonic acid-based aerogel, functional fiber, or porous ceramic ball.

[0051] In some embodiments, the average particle size of the porous ceramic spheres is 0.03-200 μm (exemplary average particle sizes are 0.03 μm, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, etc.).

[0052] In some embodiments, the second filler has a filling volume ratio of (0.3-1):1 in the second region (exemplary filling volume ratios are 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, etc.).

[0053] In this application, the purpose of the second packing material is to remove acidic gases, especially methylamine gas. Sulfonic acid-based aerogels, functional fibers, or porous ceramic balls are selected to effectively remove ammonia gases. The sulfonic acid-based aerogel is a functionalized aerogel material containing sulfonic acid groups (-SO3H), which can be purchased or prepared by introducing sulfonic acid groups into the aerogel framework (exemplary examples include silica, carbon-based, or polymer-based aerogels). The functional fibers are chitosan fibers, modified cellulose grafted with carboxylic acids or sulfonic acid groups to enhance adsorption, which can be purchased or prepared. The average particle size of the porous ceramic balls is 0.03-200 μm (exemplary examples are purchased from Xindelong Special Ceramics Co., Ltd., Shanghai Yingchuang Ruixin Materials, etc.). The filling volume ratio of the second packing material in the second region is (0.3-1):1. Within this filling volume range, it has a good ammonia removal effect. If the filling volume is too small, it is not conducive to the filling of ammonia gases; if the filling volume is too large, it is not conducive to the overall gas passage.

[0054] In some embodiments, the partition is a metal mesh structure or a porous plastic structure.

[0055] In some embodiments, the number of layers is 1 to 5 (exemplary, the number of layers is 1, 2, 3, 4 or 5).

[0056] In this application, the function of the partition is to separate the ammonia gas adsorbent material from the acid gas adsorbent material, while ensuring that the gas can pass through the partition and providing a certain support. In order to effectively achieve this effect, the partition adopts a multi-layer structure and uses a metal mesh structure or a porous plastic structure material.

[0057] In some embodiments, the gas reaction vessel is further provided with a gas inlet and a gas outlet; The gas inlet is located in the first area of ​​the gas reaction vessel and is used to input unreacted gas; The gas outlet is located in the second area of ​​the gas reaction vessel and is used to output the gas after the reaction.

[0058] In this application, a gas inlet and a gas outlet are provided on the reaction gas tank, wherein the gas outlet is directly connected to the solvent adsorption system or connected through a pipeline, and the gas outlet is directly connected to the water-oxygen circulation system or connected through a pipeline; that is, unreacted gas enters through the gas inlet, reacts sequentially through the first zone, the partition and the second zone, and after the reaction is completed, it is discharged into the water-oxygen circulation system through the gas outlet.

[0059] As a preferred technical solution of this application, the gas reaction system includes a gas reaction vessel, such as... Figure 3As shown, the gas reaction vessel includes a first region 1, a second region 2, a partition 3, a gas inlet 4, and a gas outlet 5. The first region 1 is filled with a first packing material, which is calcium oxide with a particle size of 0.03 μm-180 μm, and the filling method is powder filling with a filling ratio of 0.6:1. The second region 2 is filled with porous ceramic balls with a particle size of 0.03 μm-200 μm, and the filling ratio is 0.6:1. The partition 3 is composed of 5 layers of dense metal mesh.

[0060] In this process, the gas output from the solvent adsorption system enters the first region through the gas inlet, reacts with the first packing material in the first region to remove acidic gases, then passes through the partition, and then enters the second region to react with the second packing material in the second region to remove ammonia gases, and is discharged through the gas outlet.

[0061] In some embodiments, the gas reaction vessel is a detachable structure for replacing the first packing and / or the second packing in the gas reaction vessel.

[0062] In this application, the gas reaction vessel can be a detachable structure or a non-detachable structure, preferably a detachable structure, which facilitates timely replacement of the packing material and cleaning.

[0063] In some embodiments, the gas reaction system further includes a backup gas reaction tank and an automatic switching valve group; The backup gas reactor is connected in parallel with the gas reactor. The automatic switching valve assembly is used to automatically switch to a standby gas reaction tank when the gas reaction tank becomes saturated with adsorption.

[0064] In this application, a backup gas reaction tank is set up. When the gas reaction tank is saturated with adsorption, it automatically switches to the backup gas reaction tank, which facilitates the timely removal of acidic gases and ammonia gases produced by the reaction. It also provides a backup gas reaction tank when it is replaced or repaired. The automatic switching valve group can be operated manually or controlled automatically by machinery.

[0065] As a preferred technical solution of this application, the glove box includes a circulation loop, which includes a connected box body, a solvent adsorption system, a gas reaction system, and a water-oxygen circulation system. The gas reaction system includes a gas reaction tank, a standby gas reaction tank connected in parallel with the gas reaction tank, and an automatic switching valve group. When the gas reaction tank is saturated with adsorption, it automatically switches to the standby gas reaction tank.

[0066] In some embodiments, the water-oxygen circulation system includes a molecular sieve dryer and a copper catalyst reactor arranged in series; the molecular sieve dryer is used to adsorb water vapor; and the copper catalyst reactor is used to decompose residual oxygen.

[0067] This application does not limit the specific structure of the water-oxygen circulation system. Its purpose is to remove water vapor and oxygen. Those skilled in the art can select and adjust it according to actual needs.

[0068] In some embodiments, the solvent adsorption system includes activated carbon for adsorbing organic solvents generated during the fabrication of perovskite solar cells.

[0069] This application does not limit the specific structure of the solvent adsorption system; its purpose is to adsorb organic solvents, and those skilled in the art can adjust it according to actual needs.

[0070] In some embodiments, the glove box includes a box body. This application does not limit the specific structure of the box body, and those skilled in the art can adjust it according to actual needs.

[0071] As a preferred technical solution of this application, the glove box is applied to the perovskite battery production process. After repeated use, it was found that compared with conventional glove boxes, the copper catalyst in the water-oxygen circulation system of this application is not easily damaged, thus improving the service life of the glove box. This is mainly because a gas reaction system is added between the water-oxygen circulation system and the solvent adsorption system, which effectively removes the acidic gases and ammonia gases generated therein, thereby effectively avoiding damage to the glove box and increasing its service life.

[0072] It should be noted that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. The directional terms "inner" and "outer" refer to the inside or outside relative to the outline of the component itself. For example, if a device in the drawings is inverted, a device described as "above" or "on top of" other devices or structures will subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.

[0073] It should also be noted that the terms "one embodiment," "another embodiment," and "embodiment" used in this application refer to specific features, structures, or characteristics described in connection with that embodiment, which are included in at least one embodiment described in the general description of this application. The appearance of the same expression in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure, or characteristic is described in connection with any embodiment, the intention is to suggest that implementing such a feature, structure, or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0074] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0075] It should also be noted that the above are merely preferred embodiments of this application and do not limit the scope of patent protection of this application. Any equivalent structural or procedural changes made using the content of this application’s specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of this application.

Claims

1. A glove box for fabricating perovskite solar cells, characterized in that, The glove box for preparing perovskite solar cells includes a circulation loop, which includes a box body, a solvent adsorption system, a gas reaction system, and a water-oxygen circulation system connected in sequence. The gas reaction system is used to react with ammonia and acidic gases generated during the preparation of perovskite solar cells.

2. The glove box for perovskite battery fabrication according to claim 1, characterized in that, The gas reaction system includes a gas reaction tank, which includes a first region, a second region, and a partition separating the first region and the second region. The first region is provided with a first packing material, and the second region is provided with a second packing material.

3. The glove box for perovskite battery fabrication according to claim 2, characterized in that, The average particle size of the first filler is 0.03 μm-180 μm; The first filler is calcium oxide, barium oxide, or calcium hydroxide; The first filler is filled by solid powder or spherical particles, and the volume ratio of the first filler in the first region is (0.3-1):

1.

4. The glove box for perovskite battery fabrication according to claim 2, characterized in that, The second filler is a sulfonic acid-based aerogel, functional fiber, or porous ceramic ball; The average particle size of the porous ceramic spheres is 0.03-200 μm; The second filler has a volume ratio of (0.3-1):1 in the second region.

5. The glove box for fabricating perovskite solar cells according to claim 2, characterized in that, The partition is a metal mesh structure or a porous plastic structure; The number of layers in the partition is 1-5.

6. The glove box for perovskite battery fabrication according to claim 2, characterized in that, The gas reaction vessel is also equipped with a gas inlet and a gas outlet; The gas inlet is located in the first area of ​​the gas reaction vessel and is used to input unreacted gas; The gas outlet is located in the second area of ​​the gas reaction vessel and is used to output the gas after the reaction.

7. The glove box for perovskite battery fabrication according to claim 2, characterized in that, The gas reaction vessel is a detachable structure, used for replacing the first packing and / or the second packing in the gas reaction vessel.

8. The glove box for fabricating perovskite solar cells according to claim 1, characterized in that, The gas reaction system also includes a backup gas reaction tank and an automatic switching valve group; The backup gas reactor is connected in parallel with the gas reactor. The automatic switching valve assembly is used to automatically switch to a standby gas reaction tank when the gas reaction tank becomes saturated with adsorption.

9. The glove box for fabricating perovskite solar cells according to claim 1, characterized in that, The water-oxygen circulation system includes a molecular sieve dryer and a copper catalyst reactor arranged in series. The molecular sieve dryer is used to adsorb water vapor; The copper catalyst reactor is used to decompose residual oxygen.

10. The glove box for fabricating perovskite solar cells according to claim 1, characterized in that, The solvent adsorption system includes activated carbon, which is used to adsorb organic solvents generated during the preparation of perovskite solar cells.

Images