Zirconium phosphate nano quantum dot light conversion material preparation equipment and preparation method thereof

Abstract

The invention relates to the technical field of photovoltaic material production, in particular to zirconium phosphate nano quantum dot light conversion material preparation equipment and a preparation method thereof. The zirconium phosphate nano quantum dot light conversion material preparation equipment comprises a protective shell, a first electrode, a second electrode, a third electrode, a fourth electrode, a fifth electrode, a sixth electrode, a fifth electrode and a sixth electrode, the protective shell is internally provided with a working cavity, and the working cavity is sequentially divided into a drying cavity, a standing cavity and a reaction cavity from top to bottom; the vacuum drying module is arranged in the drying cavity and is used for carrying out vacuum drying on reactants; the standing cooling module is arranged in the standing cavity; the reaction module is arranged in the reaction cavity and comprises a reaction main body, a planetary stirring mechanism and a rotary heat exchange mechanism; the stirring assembly is in driving connection with a sun gear of the planetary stirring mechanism, and the rotary heat exchange mechanism is in driving connection with a planetary gear to guide and heat reaction liquid in the reaction main body. By eliminating the influence of water in the reaction process, the zirconium phosphate nano quantum dot light conversion material can be simply and conveniently obtained, and the method has good application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photovoltaic material production, and particularly relates to a preparation device and method of zirconium phosphate nano quantum dot light conversion material. BACKGROUND

[0002] With the continuous development of the photovoltaic industry, crystalline silicon solar cells have been widely used due to their advantages such as no pollution, modularity, short construction period, and good operation reliability. However, solar photovoltaic modules packaged with EVA adhesive film are easily affected by factors such as light and heat due to long-term exposure to the natural environment, which can cause sodium ions to migrate by causing acetic acid produced by EVA hydrolysis to react with sodium salts in the glass, thereby causing a potential-induced degradation effect (PID). This degradation is generally more than 20%, and in severe cases, the degradation can be about 50%.

[0003] Currently, the utilization rate of commercially produced photovoltaic modules for sunlight is mostly between 20% and 23%, and the light conversion efficiency is far from saturation. This situation is mainly because the solar spectrum is very wide, only photons with energy greater than or equal to the band gap can excite electrons to generate current, and photons with energy lower than the band gap will directly penetrate, and photons with too high energy will dissipate the excess energy in the form of heat.

[0004] Therefore, how to improve the band gap of photovoltaic materials has become a research hotspot. Currently, perovskite materials (configuration CsPbX3) have become the mainstream of research because they can adjust the band gap by adjusting the formula. However, perovskite materials have their own lattice defects, and in the long-term use process, perovskite materials will decompose under the action of factors such as temperature, humidity, light, and circuit load, resulting in a potential-induced degradation effect, which leads to insufficient overall stability.

[0005] To solve this problem, researchers use quantum dot technology to load perovskite quantum dots through composite materials, thereby simultaneously achieving the effects of adjustable band gap and lower PID effect. However, existing composite methods mainly use spin coating or vapor deposition methods, which are complex and have high equipment costs. Therefore, how to continue to improve them to obtain a new generation of photovoltaic materials that can be mass-produced has become a difficult point. SUMMARY

[0006] The technical problem to be solved by the present application is to provide a preparation device and method of zirconium phosphate nano quantum dot light conversion material, which solves the problems of complex preparation steps and high equipment costs of existing nano quantum dot light conversion materials.

[0007] To solve the above technical problems, the technical scheme adopted by the present application is as follows: a preparation device of zirconium phosphate nano quantum dot light conversion material, comprising: The protective shell has an internal working cavity, which is divided into a drying cavity, a standing cavity and a reaction cavity from top to bottom; The vacuum drying module is arranged in the drying cavity and used for vacuum drying of the reactants; The standing cooling module is arranged in the standing cavity and includes a central tank and a first heat exchange pipeline, the central tank is communicated with a drying discharge pipe of the vacuum drying module, the first heat exchange pipeline is arranged around the outside of the central tank, the top of the central tank is provided with a central air inlet pipe, and the bottom of the central tank is provided with a central air outlet pipe; a spray arc wall is arranged in the central tank and forms a spacing cavity with the inner wall of the central tank, the spray arc wall is arranged around the bottom of the central tank, and a plurality of spray holes are arranged in the spray arc wall in an array mode; and the central air inlet pipe is communicated with the spacing cavity. The reaction module is arranged in the reaction cavity and includes a reaction body, a planetary stirring mechanism and a rotary heat exchange mechanism, the planetary stirring mechanism is arranged at the top of the reaction body and includes a driving motor, a planetary gear set and a stirring assembly, the planetary gear set includes a sun gear, a planet gear, a planet carrier, a ring gear and a fixed shaft sleeve, the sun gear is drivingly connected with the output end of the driving motor, the planet gear is engaged with the sun gear, the planet carrier is connected with the reaction body and limits the planet gear to only rotate, the fixed shaft sleeve is connected with the reaction body, and the ring gear is rotatably connected with the fixed shaft sleeve; the stirring assembly is drivingly connected with the sun gear, and the rotary heat exchange mechanism is drivingly connected with the planet gear, the planet gear drives the rotary heat exchange mechanism to rotate around the axis line thereof, and the reaction liquid in the reaction body is guided and heated. After the dried reactants are placed in the central tank, the gas from the central air inlet pipe is sprayed through the spray arc wall to make the reactants flow and enter the reaction module together with the gas.

[0008] In an embodiment, the rotary heat exchange mechanism includes a rotary base, a heat exchange plate set and a heat exchange pipe set, the rotary base is connected with the planet carrier, the planet gear is drivingly connected with the heat exchange plate set through an output shaft penetrating the rotary base, and the heat exchange plate set is embedded in the rotary base and rotatably connected with the rotary base. The rotary base has an annular medium output cavity and a medium input cavity, the diameter of the medium input cavity is larger than that of the medium output cavity, the heat conduction medium enters the medium input cavity through the heat exchange pipe set, and the heat conduction medium after heat exchange is output from the medium output cavity; the heat exchange plate set is provided with a medium flow channel, and the medium outlet and the medium inlet of the medium flow channel are respectively communicated with the openings of the medium output cavity and the medium input cavity.

[0009] In an embodiment, the heat exchange plate group comprises a rotating base and a plurality of heat plates intersecting on the axis in the rotating base, the rotating base is embedded in the rotating base and is in sealed connection with the rotating base, and the medium flow channel is arranged corresponding to the heat plate, each group of medium flow channels is extended upward from the outer bottom of the rotating base, the medium flow channel is extended to the top of the medium flow channel, then extended laterally to the center of the heat plate, and then extended vertically downward from the intersection of the heat plate to the bottom of the rotating base.

[0010] In an embodiment, the heat exchange pipe group comprises a conveying pipe, a liquid inlet ring pipe and a liquid outlet ring pipe, the liquid inlet ring pipe and the liquid outlet ring pipe are arranged below the planet carrier, the conveying pipe is extended downward from the top of the reaction body through the gap between the planet wheels and is in communication with the liquid inlet ring pipe and the liquid outlet ring pipe, and the liquid inlet ring pipe and the liquid outlet ring pipe are in communication with the medium output cavity and the medium input cavity respectively.

[0011] In an embodiment, the gear ring extends downwardly with a scraper, and the scraper is in abutment with the inner wall of the reaction body.

[0012] In an embodiment, the vacuum drying module comprises a drying body, a vacuum pipe, a spiral stirring mechanism and a heating mechanism, the drying body is entirely conical, the vacuum pipe is arranged at the top of the drying body, the spiral stirring mechanism is extended from the top of the drying body to the bottom of the drying body, the heating mechanism is sleeved outside the drying body, and the bottom of the drying body is provided with a drying discharge pipe.

[0013] In an embodiment, the standing cooling module further comprises an annular tank body, the annular tank body is arranged around the central tank body, the annular tank body is filled with molecular sieves, the bottom of the outer side of the annular tank body is provided with a compressed gas inlet pipe, the top of the inner side of the annular tank body is in communication with the central inlet pipe, and the compressed gas is dehydrated by molecular sieve adsorption and then enters the interval cavity.

[0014] In an embodiment, the standing cooling module further comprises a second heat exchange pipe, and the second heat exchange pipe is arranged outside the annular tank body.

[0015] The application also provides a preparation method of the preparation equipment for the zirconium phosphate nano quantum dot light conversion material. S1: Dehydrating zirconium phosphate in a vacuum drying module to obtain anhydrous zirconium phosphate; S2: After cooling the anhydrous zirconium phosphate obtained in S1 in a standing cooling module, the anhydrous zirconium phosphate is introduced into a reaction module, an exchange solvent is added and stirred and dispersed, then a cesium source is added, and ion exchange cesium loading is carried out by heating and stirring; S3: X source is added to the sample prepared in S2, and the synthesis of luminescent quantum dots is carried out by heating and stirring, and the product after synthesis is filtered, dried and crushed to obtain the zirconium phosphate nano quantum dot light conversion material; The zirconium phosphate is a sheet-like zirconium phosphate; The cesium source includes any one or combination of cesium sulfate, cesium nitrate and cesium chloride; The exchange solvent includes any one or combination of tetrahydrofuran, 3-methylpentane and chlorobenzene; The X source in the CsPbX3 quantum dot is a combination of any two of lead chloride, lead fluoride, lead bromide and lead iodide, and 0<=x<=3. The molar ratio of the zirconium phosphate, the exchange solvent, the cesium source and the X source is 1:(1-100):(0.01-0.2):(0.03-0.6).

[0016] Preferably, the cesium source is cesium chloride. Preferably, the exchange solvent is a mixture of tetrahydrofuran and 3-methylpentane, the volume ratio of tetrahydrofuran to 3-methylpentane is (1-2:1), and the X source in the CsPbX3 quantum dot is lead bromide and lead chloride, and the molar ratio of lead bromide to lead chloride is 1:2.

[0017] Preferably, the molar ratio of the zirconium phosphate, the exchange solvent, the cesium ion, the lead bromide and the lead chloride is 1:8:0.05:0.05:0.1.

[0018] In an embodiment, in S1, the dehydration heating temperature is 120-800 DEG C, and the heating time is 2-4 h. In S2, the cooling temperature is 40 DEG C-20 DEG C, the cooling standing time is 1-4 h, the heating temperature is 20-80 DEG C, and the stirring time is 2-6 h. In S3, the heating temperature is 20-80 DEG C, the stirring time is 2-6 h, the drying temperature is 80-200 DEG C, and the drying time is 2-5 h.

[0019] Preferably, in S1, the heating temperature is 160-170 DEG C, and the heating time is 3 h. In S2, the cooling temperature is 35 DEG C-25 DEG C, the cooling standing time is 3 h, the heating temperature is 40-45 DEG C, and the stirring time is 2 h. In S3, the heating temperature is 40-45 DEG C, the stirring time is 2 h, the drying temperature is 100-105 DEG C, and the drying time is 3 h.

[0020] The present application has the following advantages: The existing composite method needs to use a spin coating method or a vapor deposition method to composite the perovskite quantum dot and the support material due to the characteristics of the support material, and the steps are complex, and if a conventional synthesis method is used, the support material and various components need to be dispersed in a solvent. However, the perovskite quantum dot is very sensitive to water, oxygen and ultraviolet light, and is easily degraded into a non-luminous substance, resulting in a synthesis failure.

[0021] The zirconium phosphate nano quantum dot light conversion material preparation equipment provided by the application adopts a three-section structure, and drying cavity, standing cavity and reaction cavity are arranged as a whole, zirconium phosphate is vacuum dried in the drying cavity, so that the zirconium phosphate is dehydrated to obtain anhydrous zirconium phosphate, then the anhydrous zirconium phosphate is cooled by the standing cooling module, so that the temperature of the anhydrous zirconium phosphate is close to the temperature of the subsequent ambient air, and condensate water caused by temperature difference is avoided, and the anhydrous environment of the overall reaction system is ensured.

[0022] After standing, the reaction material is stable as a whole, and residues are extremely easy to occur when the reaction material is transported by physical means, therefore, the application is provided with a spraying arc wall, so that the reaction material can be fluidized in the central tank body, and the reaction material can be transported into the reaction module together with the gas, so that the quality of the overall reaction material composition is controllable, and the continuity and stability of production are ensured.

[0023] Since the overall system is an anhydrous system, the reaction solvent needs to use an exchange solvent. The exchange solvent has a low overall boiling point and is easy to volatilize, so that the safety during large-scale production is ensured, and high-speed stirring cannot be used, so that local overheating caused by high-speed stirring is avoided, and safety hazards are avoided. However, ion exchange of the cesium source and attachment of the perovskite quantum dot in the subsequent process require that the components in the reaction solution have good dispersion.

[0024] Therefore, the reaction module used in the application is matched with a planetary stirring mechanism and a rotary heat exchange mechanism, The rotary heat exchange mechanism is arranged around the stirring assembly, and the rotary heat exchange mechanism rotates around its own central axis while exchanging heat with the reaction solution through the planetary wheel. Through the joint action of the rotary heat exchange mechanism and the stirring assembly, the reaction solution in the reaction body forms a flow cycle, so that the components in the reaction solution can be fully dispersed under the condition of stable stirring temperature, and the reaction can be carried out normally.

[0025] In addition, the rotary heat exchange mechanism can make the reaction solution flow fully in the reaction cavity to form a turbulent flow. However, when different rotary heat exchange mechanisms rotate synchronously, small vortexes may be generated in the center, and the reaction solution in the center cannot flow to the outside, forming a stirring dead angle. In order to avoid the formation of a stirring dead angle in the center of the reaction cavity and prevent the reaction efficiency and reaction effect from being reduced due to the settlement of the reaction material in the reaction solution, the application as a whole adopts a planetary stirring mechanism, and the stirring assembly in the center of the reaction cavity disperses and guides the reaction solution in the middle part to the rotary heat exchange mechanism, so that the reaction solution in the central region cannot form a vortex and flow, and the mass transfer and heat transfer processes are not hindered. At the same time, the stable formation of the flow circulation cycle is ensured, and the overall stirring effect is ensured.

[0026] The zirconium phosphate nano quantum dot light conversion material prepared by the method has good particle dispersity, is easy to disperse uniformly, is resistant to high temperature, acid and alkali, and stable in performance; the preparation process is simple, has few steps, is convenient to operate, has low equipment requirement, is strong in replicability, can be applied to photovoltaic EVA adhesive film and glass curtain wall components, and has wide application prospect. Moreover, the zirconium phosphate substrate has strong metal ion exchange capacity, can inhibit potential decay caused by ion migration of photovoltaic cells, and has strong PID resistance. Meanwhile, different wavelengths of light can be achieved by adjusting the ratio of X sources, so that more light can be utilized, and the light conversion rate and the power generation efficiency of the solar photovoltaic component are significantly improved. The nano quantum dot light composite technology can also realize adjustable light emitting wavelength, so that the demand of glass curtain wall with different colors can be realized in subsequent practical application, and the light transmittance problem of the Low-E glass curtain wall photovoltaic component is reduced, the current ink process section is omitted, so that the overall manufacturing cost is reduced, and good practical value is obtained.

[0027] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent to those skilled in the art from the description, or can be learned by practice of the application. The objects and other advantages of the present application can be realized and attained by the structure and / or components particularly pointed out in the description and claims of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is a perspective view of an embodiment of the present application; Figure 2 is a top view of Figure 1 ; is a sectional view of ; is an enlarged view of B in Figure 3 ; is an enlarged view of C in Figure 2 ; is an enlarged view of D in ; is a perspective view of an embodiment of the present application; Figure 4 ; is a perspective view of an embodiment of the present application; Figure 3 ; is a perspective view of an embodiment of the present application; ; is a perspective view of an embodiment of the present application; Figure 5 ; is a perspective view of an embodiment of the present application; Figure 3 ; is a perspective view of an embodiment of the present application; ; is a perspective view of an embodiment of the present application; Figure 6 ; is a perspective view of an embodiment of the present application; ; is a perspective view of an embodiment of the present application; Figure 7 ; is a perspective view of an embodiment of the present application; Figure 6 ; is a perspective view of an embodiment of the present application; ; is a perspective view of an embodiment of the present application; Figure 8 ; is a perspective view of an embodiment of the present application; Figure 7 ; is a perspective view of an embodiment of the present application; ; is a perspective view of an embodiment of the present application;

[0029] ; is a perspective view of an embodiment of the present application; 1, protective shell; 2, vacuum drying module; 21, drying main body; 22, vacuum pipe; 23, spiral stirring mechanism; 24, heating mechanism; 25, drying discharge pipe; 26, heat insulation layer; 27, drying feeding pipe; 3, standing cooling module; 31, center tank body; 311, center exhaust pipe; 312, center air inlet pipe; 313, jet arc wall; 314, jet hole; 315, interval cavity; 32, first heat exchange pipeline; 33, annular tank body; 331, compressed gas air inlet pipe; 34, second heat exchange pipeline; 4, reaction module; 41, reaction main body; 411, reaction feeding pipe; 412, reaction exhaust pipe; 413, reaction discharge pipe; 42, planetary stirring mechanism; 421, driving motor; 422, planetary gear set; 4221, sun gear; 4222, planetary gear; 4223, planet carrier; 4224, ring gear; 4225, fixed shaft sleeve; 4226, scraper; 423, stirring assembly; 43, rotary heat exchange mechanism; 431, rotary base; 4311, medium output cavity; 4312, medium input cavity; 4313, medium flow channel; 432, heat exchange plate group; 4321, rotary base; 4322, heat conduction plate; 433, heat exchange pipe group; 4331, conveying pipe; 4332, liquid inlet ring pipe; 4333, liquid outlet ring pipe. DETAILED DESCRIPTION

[0030] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the following will be clearly and completely described with the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. As long as there is no conflict, the technical features designed in the different embodiments of the present application can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0031] In the description of the present application, it should be noted that all the terms used in the present application have the same meanings as those generally understood by the person of ordinary skill in the art to which the present application belongs, and should not be understood as the limitation of the present application. It should be further understood that the terms used in the present application should be understood as having the same meanings as the terms in the context of the present application and the related field, and should not be understood in an idealized or overly formal sense, unless defined as such in the present application.

[0032] A kind of phosphorus acid zirconium nano quantum dot light conversion material preparation equipment, comprising: Protective shell 1, inside having working cavity, working cavity is separated into drying cavity, standing cavity and reaction cavity from top to bottom in sequence; Vacuum drying module 2, it is arranged in drying cavity, for carrying out vacuum drying to reactant; The static cooling module 3 is arranged in the static cavity and comprises a central tank 31 and a first heat exchange pipeline 32. The central tank 31 is communicated with the drying discharge pipeline 25 of the vacuum drying module 2. The first heat exchange pipeline 32 is arranged around the outer side of the central tank 31. The top of the central tank 31 is provided with a central air inlet pipeline 312. The bottom of the central tank 31 is provided with a central air outlet pipeline 311. The central tank 31 is provided with a spray arc wall 313. The spray arc wall 313 is arranged around the bottom of the central tank 31 and forms a spacing cavity 315 with the inner wall of the central tank 31. The spray arc wall 313 is provided with spray holes 314 in an array. The central air inlet pipeline 312 is communicated with the spacing cavity 315. The reaction module 4 is arranged in the reaction cavity and comprises a reaction body 41, a planetary stirring mechanism 42 and a rotary heat exchange mechanism 43. The planetary stirring mechanism 42 is arranged at the top of the reaction body 41 and comprises a driving motor 421, a planetary gear set 422 and a stirring assembly 423. The planetary gear set 422 comprises a sun gear 4221, a planet gear 4222, a planet carrier 4223, a ring gear 4224 and a fixed shaft sleeve 4225. The sun gear 4221 is drivingly connected with the output end of the driving motor 421. The planet gear 4222 is engaged with the sun gear 4221. The planet carrier 4223 is connected with the reaction body 41 and limits the planet gear 4222 to only rotate. The fixed shaft sleeve 4225 is connected with the reaction body 41. The ring gear 4224 is rotatably connected with the fixed shaft sleeve 4225. The stirring assembly 423 is drivingly connected with the sun gear 4221. The rotary heat exchange mechanism 43 is drivingly connected with the planet gear 4222. The planet gear 4222 drives the rotary heat exchange mechanism 43 to rotate around the axis thereof to guide and heat the reaction liquid in the reaction body 41.

[0033] The dried reaction substance is statically placed in the central tank 31. After the static placement is completed, the gas from the central air inlet pipeline 312 is sprayed by the spray arc wall to make the reaction substance flow and then enter the reaction module 4 together with the gas.

[0034] Preferably, the central air outlet pipeline 311 is provided with a filter screen for preventing the reaction substance from leaving the central tank 31 with the gas.

[0035] Preferably, the spacing cavity 315 has an upper large and lower small three-dimensional structure. In this way, the spray holes 314 at different positions are balanced in pressure, so that the operator can more stably control the flow state of the reaction substance.

[0036] Preferably, a plurality of spray arc walls 313 are arranged. Each spray arc wall 313 is correspondingly provided with a central air inlet pipeline 312, so that the operator can control the flow state of the reaction substance in the central tank 31 by controlling the air inlet amount of different central air inlet pipelines 312.

[0037] More preferably, the injection hole 314 adopts a flared structure, and is inclined upward as a whole, so that the gas inlet flows in the upward direction along the edge, and drives the reactants to float, accelerating the formation of the flow state.

[0038] Specifically, the person skilled in the art can adjust the gear ratio of the sun gear 4221 and the planetary gear 4222 in the planetary stirring mechanism 42 according to the need, and ensure that the dispersion is sufficient, without specific limitation.

[0039] Specifically, the stirring assembly 423 can adopt ordinary stirring paddles or spiral stirring paddles, anchor stirring paddles, etc., without interference with the rotating heat exchange mechanism 43, and the person skilled in the art can select a suitable stirring assembly 423 according to the need, without specific limitation.

[0040] Specifically, the reaction main body 41 is provided with a reaction feeding pipe 411 and a reaction exhaust pipe 412 at the top, and a reaction discharging pipe 413 at the bottom, and the reaction feeding pipe 411 extends into the reaction main body 41 through the gap of the planetary gear 4222.

[0041] Since the rotating heat exchange mechanism 43 needs to exchange heat with the reaction liquid during its own rotation, it is necessary to ensure that the input and output of the heat exchange medium are not affected by the rotation. Therefore, in the embodiment, the rotating heat exchange mechanism 43 includes a rotating base 431, a heat exchange plate group 432, and a heat exchange pipe group 433, the rotating base 431 is connected with the planet carrier 4223, the planetary gear 4222 is drivingly connected with the heat exchange plate group 432 through an output shaft penetrating the rotating base 431, and the heat exchange plate group 432 is embedded in the rotating base 431 and is rotatably connected with the rotating base 431. The rotating base 431 has an annular medium output cavity 4311 and a medium input cavity 4312, the diameter of the medium input cavity 4312 is larger than that of the medium output cavity 4311, the heat conduction medium enters the medium input cavity 4312 through the heat exchange pipe group 433, and the heat conduction medium after heat exchange is output from the medium output cavity 4311; the heat exchange plate group 432 is provided with a medium flow channel 4313, and the medium outlet and the medium inlet of the medium flow channel 4313 are in communication with the openings of the medium output cavity 4311 and the medium input cavity 4312, respectively.

[0042] In the embodiment, the heat exchange plate group 432 comprises a rotating base 4321 and a plurality of heat plates 4322 intersecting on the axis of the rotating base 4321, the rotating base 4321 is embedded in the rotating base 431 and is in sealed connection with the rotating base 431, and the medium flow channel 4313 is arranged corresponding to the heat plate 4322, each group of medium flow channels 4313 is extended upward from the outer bottom of the rotating base 4321, the medium flow channel 4313 is extended to the top of the medium flow channel 4313, then extended laterally to the center of the heat plate 4322, and then extended vertically downward from the intersection of the heat plate 4322 to the bottom of the rotating base 4321. Specifically, since the heat exchange plate group 432 is a vertical plate structure, when the heat exchange plate group 432 rotates, compared with the stirring paddle, the reaction liquid can be disturbed in a large range, and at the same time, the plate structure can push the reaction liquid as a whole, so as to reduce the generation of cavitation phenomenon and the gasification of exchange solvent, and further improve the safety.

[0043] Specifically, the openings of the medium output cavity 4311 and the medium input cavity 4312 are annular, and after the rotating base 4321 is embedded, the two ends of the medium flow channel 4313 are in communication with the medium output cavity 4311 and the medium input cavity 4312 respectively, so that the heat exchange medium can circulate along the medium flow channel 4313 under the condition of overall rotation, thereby ensuring the heat exchange effect.

[0044] At the same time, since the top of the reaction body 41 is the planetary stirring mechanism 42, in order to avoid the interference of the heat exchange pipe group 433 with the operation of the heat exchange pipe group 433, in the embodiment, the heat exchange pipe group 433 comprises a conveying pipe 4331, a liquid inlet ring pipe 4332 and a liquid outlet ring pipe 4333, the liquid inlet ring pipe 4332 and the liquid outlet ring pipe 4333 are arranged below the planet carrier 4223, the conveying pipe 4331 is extended downward from the top of the reaction body 41 through the gap between the planet wheels 4222 and is in communication with the liquid inlet ring pipe 4332 and the liquid outlet ring pipe 4333, and the liquid inlet ring pipe 4332 and the liquid outlet ring pipe 4333 are in communication with the medium output cavity 4311 and the medium input cavity 4312 respectively.

[0045] Since the reaction liquid is a whole suspension liquid and the solvent is an exchange solvent, during the reaction, the reaction slurry with high concentration and certain viscosity may be adhered to the inner wall of the reaction body 41. In the embodiment, the gear ring 4224 extends downwardly with a scraper 4226, and the scraper 4226 abuts against the inner wall of the reaction body 41.

[0046] In the embodiment, the vacuum drying module 2 comprises a drying body 21, a vacuum pipe 22, a spiral stirring mechanism 23 and a heating mechanism 24. The drying body 21 is conical in whole. The vacuum pipe 22 is arranged at the top of the drying body 21. The spiral stirring mechanism 23 extends from the top of the drying body 21 to the bottom of the drying body 21. The heating mechanism 24 is sleeved outside the drying body 21. The bottom of the drying body 21 is provided with a drying discharge pipe 25. The top of the drying body 21 is provided with a drying feeding pipe 27. Specifically, the spiral stirring mechanism 23 can be a spiral belt stirrer driven by a motor. The heating mechanism 24 is a heating jacket. The vacuum pipe 22 is connected with a vacuumizing device to make the inside of the drying body 21 in a vacuum state. The skilled in the art can make adjustment according to actual needs without specific limitation.

[0047] Further, the drying body 21 is sleeved with a heat insulation layer 26. After the heat insulation layer 26 is arranged, the heating efficiency of the drying body 21 can be improved. Meanwhile, heat loss or conduction to other modules can be avoided to improve the drying efficiency and ensure the normal progress of the reaction.

[0048] After cooling, although the heat exchange between the anhydrous zirconium phosphate and the surrounding air can be avoided, the condensed water can be prevented from being generated after the air after heat exchange touches the wall of the equipment. After standing, the anhydrous zirconium phosphate needs to be driven to form a fluidized state by introducing external compressed gas. After the compressed gas is introduced, the water vapor in the compressed gas can also be condensed during the conveying process, which can destroy the anhydrous environment. Therefore, in the embodiment, the standing cooling module 3 further comprises an annular tank 33. The annular tank 33 is arranged around the central tank 31. The annular tank 33 is filled with molecular sieves. The bottom of the outside of the annular tank 33 is provided with a compressed gas inlet pipe 331. The top of the inside of the annular tank 33 is in communication with the central gas inlet pipe 312. The compressed gas is dehydrated by molecular sieves and then enters the interval cavity 315.

[0049] Further, before the zirconium phosphate enters the standing cooling module 3, the standing cooling module 3 pre-introduces compressed gas into the annular tank 33. The dry compressed gas enters the central tank 31. The original air in the central tank 31 is discharged through the central exhaust pipe 311. Therefore, the anhydrous environment in the standing cooling module 3 is ensured, and the progress of the whole reaction is ensured. Further, after the air replacement of the central tank 31 is completed, the compressed gas is continuously introduced to replace the air in the reaction module 4. Therefore, the anhydrous environment in the whole reaction process is ensured.

[0050] In order to further reduce the temperature difference between the compressed air entering the central tank 31 and the zirconium phosphate and avoid condensation, in the embodiment, the standing cooling module 3 further comprises a second heat exchange pipe 34. The second heat exchange pipe 34 is arranged outside the annular tank 33.

[0051] The application further provides a preparation method of the preparation device adopting the zirconium phosphate nano quantum dot light conversion material. S1: dehydrate the zirconium phosphate in the vacuum drying module 2 to obtain anhydrous zirconium phosphate; S2: after the anhydrous zirconium phosphate obtained in S1 is cooled in the standing cooling module 3, the anhydrous zirconium phosphate is introduced into the reaction module 4, an exchange solvent is added and stirred and dispersed, then a cesium source is added, and ion exchange loading of cesium is carried out by heating and stirring; S3: in the sample prepared in S2, an X source is added, and synthesis of luminescent quantum dots is carried out by heating and stirring, and the product after synthesis is filtered, dried and crushed to obtain the zirconium phosphate nano quantum dot light conversion material; The zirconium phosphate is a sheet-like zirconium phosphate; The cesium source includes any one or combination of cesium sulfate, cesium nitrate and cesium chloride; The exchange solvent includes at least any one or combination of tetrahydrofuran, 3-methylpentane and chlorobenzene; The X source in the CsPbX3 quantum dot is a combination of any two of lead chloride, lead fluoride, lead bromide and lead iodide, and 0<=x<=3; The molar ratio of the zirconium phosphate, the exchange solvent, the cesium source and the X source is 1:(1-100):(0.01-0.2):(0.03-0.6).

[0052] Preferably, the cesium source is cesium chloride; the exchange solvent is a mixture of tetrahydrofuran and 3-methylpentane, the volume ratio of tetrahydrofuran to 3-methylpentane is (1-2):1; the X source in the CsPbX3 quantum dot is lead bromide and lead chloride, and the molar ratio of lead bromide to lead chloride is 1:2.

[0053] Preferably, the molar ratio of the zirconium phosphate, the exchange solvent, the cesium ion, lead bromide, lead chloride is 1:8:0.05:0.05:0.1, and the volume ratio of tetrahydrofuran to 3-methylpentane is 1.5:1.

[0054] In an embodiment, in S1, the dehydration heating temperature is 120-800℃, and the heating time is 2-4h; In S2, the cooling temperature is 40-20℃, the cooling standing time is 1-4h, the heating temperature is 20-80℃, and the stirring time is 2-6h; In S3, the heating temperature is 20-80℃, the stirring time is 2-6h, the drying temperature is 80-200℃, and the drying time is 2-5h.

[0055] Preferably, in S1, the heating temperature is 160-170℃, and the heating time is 3h; In S2, the cooling temperature is 35-25℃, the cooling standing time is 3h, the heating temperature is 40-45℃, and the stirring time is 2h; In S3, the heating temperature is 40-45℃, the stirring time is 2h, the drying temperature is 100-105℃, and the drying time is 3h.

[0056] According to the preparation device and the preparation method, the specific implementation is as follows: Example 1: S1: Take 285g of zirconium phosphate, dehydrate in the vacuum drying module 2 at 165℃ for 3h to obtain anhydrous zirconium phosphate.

[0057] S2: The anhydrous zirconium phosphate obtained in S1 is cooled to 20℃ in the static cooling module 3 for 3h, then introduced into the reaction module 4, and exchange solvent 610g and cesium chloride 8.4g are added and stirred at 42℃ for 2h.

[0058] S3: The sample prepared in S2 is added with lead bromide 18.6g and lead chloride 27.8g respectively, stirred at 42℃ for 2h, dried at 102℃ for 3h after filtration, and crushed to obtain zirconium phosphate nano quantum dot light conversion material.

[0059] The volume ratio of tetrahydrofuran to 3-methylpentane in the exchange solvent is 1.5:1.

[0060] Example 2: S1: Take 285g of zirconium phosphate, dehydrate in the vacuum drying module 2 at 125℃ for 3h to obtain anhydrous zirconium phosphate.

[0061] S2: The anhydrous zirconium phosphate obtained in S1 is cooled to 20℃ in the static cooling module 3 for 3h, then introduced into the reaction module 4, and exchange solvent 610g and cesium chloride 8.4g are added and stirred at 42℃ for 2h.

[0062] S3: The sample prepared in S2 is added with lead bromide 18.6g and lead chloride 27.8g respectively, stirred at 42℃ for 2h, dried at 102℃ for 3h after filtration, and crushed to obtain zirconium phosphate nano quantum dot light conversion material.

[0063] The volume ratio of tetrahydrofuran to 3-methylpentane in the exchange solvent is 1.5:1.

[0064] Example 3: S1: Take 285g of zirconium phosphate, dehydrate in the vacuum drying module 2 at 650℃ for 3h to obtain anhydrous zirconium phosphate.

[0065] S2: The anhydrous zirconium phosphate obtained in S1 is cooled to 20℃ in the static cooling module 3 for 3h, then introduced into the reaction module 4, and exchange solvent 610g and cesium chloride 8.4g are added and stirred at 42℃ for 2h.

[0066] S3: The sample prepared in S2 was added with lead bromide 18.6 g and lead chloride 27.8 g respectively, stirred at 42℃ for 2 h, dried at 102℃ for 3 h after filtration, and crushed to obtain the zirconium phosphate nano quantum dot light conversion material.

[0067] The volume ratio of tetrahydrofuran to 3-methylpentane in the exchange solvent was 1.5:1.

[0068] Example Four: S1: Take 285 g of zirconium phosphate, dehydrate in a vacuum drying module 2 at 165℃ for 3 h to obtain anhydrous zirconium phosphate.

[0069] S2: The anhydrous zirconium phosphate obtained in S1 was cooled to 20℃ in a static cooling module 3 for 3 h, then introduced into a reaction module 4, and added with exchange solvent 610 g and cesium chloride 8.4 g, stirred at 42℃ for 2 h.

[0070] S3: The sample prepared in S2 was added with lead bromide 37.2 g and lead chloride 55.6 g respectively, stirred at 42℃ for 2 h, dried at 102℃ for 3 h after filtration, and crushed to obtain the zirconium phosphate nano quantum dot light conversion material.

[0071] The volume ratio of tetrahydrofuran to 3-methylpentane in the exchange solvent was 1.5:1.

[0072] Example Five: S1: Take 285 g of zirconium phosphate, dehydrate in a vacuum drying module 2 at 650℃ for 3 h to obtain anhydrous zirconium phosphate.

[0073] S2: The anhydrous zirconium phosphate obtained in S1 was cooled to 20℃ in a static cooling module 3 for 3 h, then introduced into a reaction module 4, and added with exchange solvent 610 g and cesium chloride 8.4 g, stirred at 42℃ for 2 h.

[0074] S3: The sample prepared in S2 was added with lead bromide 9.3 g and lead chloride 13.9 g respectively, stirred at 42℃ for 2 h, dried at 102℃ for 3 h after filtration, and crushed to obtain the zirconium phosphate nano quantum dot light conversion material.

[0075] The volume ratio of tetrahydrofuran to 3-methylpentane in the exchange solvent was 1.5:1.

[0076] Example Six: S1: Take 285 g of zirconium phosphate, dehydrate in a vacuum drying module 2 at 650℃ for 3 h to obtain anhydrous zirconium phosphate.

[0077] S2: The anhydrous zirconium phosphate obtained in S1 is cooled to 20°C in the static cooling module 3 for 3h, and then introduced into the reaction module 4, while adding 610g of exchange solvent and 8.4g of cesium chloride, and stirring at 42°C for 2h.

[0078] S3: The sample obtained in S2 is added with 12.3g of lead fluoride and 46.1g of lead iodide respectively, and stirred at 42°C for 2h, and then dried at 102°C for 3h after filtration, and then crushed to obtain the zirconium phosphate nano quantum dot light conversion material.

[0079] The volume ratio of tetrahydrofuran to 3-methylpentane in the exchange solvent is 1.5:1.

[0080] The zirconium phosphate nano quantum dot light conversion materials obtained in Examples 1 to 6 are sampled and added to EVA adhesive films to obtain photovoltaic cells, and EVA adhesive films without addition and with only zirconium phosphate addition are used as comparative examples to test the PID resistance performance and the power generation efficiency of the cells, and the data are shown in Table 1: Table 1 Experimental results

[0081] As can be seen from the above data, although the addition of zirconium phosphate can greatly improve the PID resistance performance of the photovoltaic adhesive film, the utilization rate of sunlight is not obviously improved, while the addition of the zirconium phosphate nano quantum dot light conversion material provided by the present application can not only greatly improve the PID resistance performance, but also greatly improve the conversion efficiency of the cell, provide the utilization rate, and further reduce the cost of the photovoltaic cell.

[0082] It should be noted that the specific parameters or some commonly used reagents in the above examples are specific embodiments or preferred embodiments under the concept of the present application, but not a limitation; those skilled in the art can make adaptive adjustments within the concept and protection scope of the present application.

[0083] In addition, if not specially stated, the raw materials used can be conventional commercially available products in the art, or prepared by conventional methods in the art.

[0084] In addition, those skilled in the art should understand that although there are many problems in the prior art, each embodiment or technical solution of the present application can only be improved in one or several aspects, and it is not necessary to solve all the technical problems listed in the prior art or background art at the same time. Those skilled in the art should understand that what is not mentioned in a claim should not be considered as a limitation of the claim.

[0085] Although the terms such as protective shell, working cavity, etc. are used more frequently in this document, the possibility of using other terms is not excluded. The use of these terms is only for the convenience of describing and explaining the essence of the present application; it is against the spirit of the present application to interpret them as any kind of additional limitation; the terms "first", "second", etc. (if any) in the specification and claims of the embodiments of the present application are used to distinguish similar objects, and do not have to be used to describe a specific order or sequence.

[0086] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A zirconium phosphate nanometer quantum dot light conversion material preparation device, characterized in that, The application relates to a vacuum drying and reaction device. The device comprises a protective shell (1) with an internal working cavity, which is divided into a drying cavity, a standing cavity and a reaction cavity from top to bottom; a vacuum drying module (2) arranged in the drying cavity and used for vacuum drying of reactants; a standing cooling module (3) arranged in the standing cavity and comprising a central tank (31) and a first heat exchange pipeline (32), the central tank (31) is communicated with a drying discharge pipeline (25) of the vacuum drying module (2), the first heat exchange pipeline (32) is arranged around the outer side of the central tank (31), a central air inlet pipeline (312) is arranged at the top of the central tank (31), a central air outlet pipeline (311) is arranged at the bottom of the central tank (31), a spraying arc wall (313) is arranged in the central tank (31) and surrounds the bottom of the central tank (31) to form a spacing cavity (315) with the inner wall of the central tank (31), a plurality of spraying holes (314) are arranged in the spraying arc wall (313) in an array mode, and the central air inlet pipeline (312) is communicated with the spacing cavity (315); and a reaction module (4) arranged in the reaction cavity and comprising a reaction main body (41), a planetary stirring mechanism (42) and a rotary heat exchange mechanism (43), the planetary stirring mechanism (42) is arranged at the top of the reaction main body (41) and comprises a driving motor (421), a planetary gear set (422) and a stirring assembly (423), the planetary gear set (422) comprises a sun gear (4221), a planet gear (4222), a planet carrier (4223), a ring gear (4224) and a fixed shaft sleeve (4225), the sun gear (4221) is drivingly connected with the output end of the driving motor (421), the planet gear (4222) is engaged with the sun gear (4221), the planet carrier (4223) is connected with the reaction main body (41) and limits the planet gear (4222) to only rotate around its own axis, the fixed shaft sleeve (4225) is connected with the reaction main body (41), and the ring gear (4224) is rotatably connected with the fixed shaft sleeve (4225), the stirring assembly (423) is drivingly connected with the sun gear (4221), and the rotary heat exchange mechanism (43) is drivingly connected with the planet gear (4222), the planet gear (4222) drives the rotary heat exchange mechanism (43) to rotate around its own axis to guide and heat the reaction liquid in the reaction main body (41). The dried reactants are placed in the central tank (31), and after standing, the air from the central air inlet pipeline (312) is sprayed through the spraying arc wall to make the reactants flow into the reaction module (4) together with the air. ​ ​ ​ 2.The device for preparing zirconium phosphate nanometer quantum dot light conversion material according to claim 1, characterized in that: The rotating heat exchange mechanism (43) comprises a rotating base (431), a heat exchange plate group (432) and a heat exchange pipe group (433), the rotating base (431) is connected with the planet carrier (4223), the planet wheel (4222) is drivingly connected with the heat exchange plate group (432) through an output shaft penetrating the rotating base (431), the heat exchange plate group (432) is embedded in the rotating base (431) and is rotatably connected with the rotating base (431); The rotating base (431) has an annular medium output cavity (4311) and a medium input cavity (4312), the diameter of the medium input cavity (4312) is greater than that of the medium output cavity (4311), the heat conducting medium enters the medium input cavity (4312) through the heat exchange pipe group (433), and the heat conducting medium after heat exchange is output from the medium output cavity (4311); the heat exchange plate group (432) is provided with a medium flow channel (4313), and the medium outlet and the medium inlet of the medium flow channel (4313) are respectively communicated with the openings of the medium output cavity (4311) and the medium input cavity (4312). 3.The device for preparing zirconium phosphate nanometer quantum dot light conversion material according to claim 2, characterized in that: The heat exchange plate group (432) comprises a rotating base (4321) and a plurality of heat spreading plates (4322) intersecting on the axis in the rotating base (4321), the rotating base (4321) is embedded in the rotating base (431) and is sealingly connected with the rotating base (431), the medium flow channel (4313) is provided correspondingly to the heat spreading plate (4322), each group of the medium flow channel (4313) is extended upward from the outer bottom of the rotating base (4321), the medium flow channel (4313) is extended to the top of the medium flow channel (4313), then is extended transversely to the center of the heat spreading plate (4322), and is vertically and downwardly extended from the intersection of the heat spreading plate (4322) to the bottom of the rotating base (4321). 4.The device for preparing zirconium phosphate nanometer quantum dot light conversion material according to claim 3, characterized in that: The heat exchange pipe group (433) comprises a conveying pipe (4331), a liquid inlet ring pipe (4332) and a liquid outlet ring pipe (4333), the liquid inlet ring pipe (4332) and the liquid outlet ring pipe (4333) are arranged below the planet carrier (4223), the conveying pipe (4331) is extended downward from the top of the reaction main body (41) through the gap between the planet wheels (4222) and is communicated with the liquid inlet ring pipe (4332) and the liquid outlet ring pipe (4333), and the liquid inlet ring pipe (4332) and the liquid outlet ring pipe (4333) are respectively communicated with the medium output cavity (4311) and the medium input cavity (4312). 5.The zirconium phosphate nanometer quantum dot light conversion material preparation device according to claim 1, characterized in that: The gear ring (4224) downwardly extends a scraper (4226), and the scraper (4226) abuts against the inner wall of the reaction main body (41). 6.The zirconium phosphate nanometer quantum dot light conversion material preparation device according to claim 1, characterized in that: The vacuum drying module (2) comprises a drying main body (21), a vacuum pipe (22), a spiral stirring mechanism (23) and a heating mechanism (24), the drying main body (21) is conical as a whole, the vacuum pipe (22) is arranged at the top of the drying main body (21), the spiral stirring mechanism (23) extends from the top of the drying main body (21) to the bottom of the drying main body (21), the heating mechanism (24) is sleeved outside the drying main body (21), and the bottom of the drying main body (21) is provided with the drying discharge pipe (25). 7.The zirconium phosphate nanometer quantum dot light conversion material preparation device according to claim 1, characterized in that: The standing cooling module (3) further comprises an annular tank body (33), the annular tank body (33) is arranged around the central tank body (31), the annular tank body (33) is filled with molecular sieves, the bottom of the outside of the annular tank body (33) is provided with a compressed gas inlet pipe (331), and the top of the inside of the annular tank body (33) is in communication with the central gas inlet pipe (312); after being dehydrated by adsorption of the molecular sieves, the compressed gas enters the interval cavity (315). 8.The device for preparing zirconium phosphate nanometer quantum dot light conversion material according to claim 7, characterized in that: The standing cooling module (3) further comprises a second heat exchange pipeline (34), and the second heat exchange pipeline (34) is arranged outside the annular tank body (33).

9. A production method using a production apparatus for a zirconium phosphate nano quantum dot light conversion material according to any one of claims 1 to 8, characterized by, The steps are as follows: S1: dehydrating zirconium phosphate in the vacuum drying module (2) to obtain anhydrous zirconium phosphate; S2: after cooling the anhydrous zirconium phosphate obtained in S1 in the standing cooling module (3), the anhydrous zirconium phosphate is introduced into the reaction module (4), an exchange solvent is added and stirred and dispersed, then a cesium source is added, and ion exchange is carried out to load cesium by heating and stirring; S3: X source is added to the sample prepared in S2, and luminescent quantum dots are synthesized by heating and stirring, and the synthesized product is filtered, dried and crushed to obtain zirconium phosphate nano quantum dot light conversion materials; The zirconium phosphate is sheet-like zirconium phosphate; The cesium source comprises any one or combination of cesium sulfate, cesium nitrate and cesium chloride; The exchange solvent comprises any one or combination of tetrahydrofuran, 3-methylpentane and chlorobenzene; In the CsPbX3 quantum dots, the X source is a combination of any two of lead chloride, lead fluoride, lead bromide and lead iodide, and 0<=x<=3; The molar ratio of the zirconium phosphate, the exchange solvent, the cesium source and the X source is 1:(1-100):(0.01-0.2):(0.03-0.6).

10. The method of claim 9, wherein: In S1, the dehydration heating temperature is 120-800 DEG C, and the heating time is 2-4 h; In S2, the cooling temperature is 40 DEG C-20 DEG C, the cooling standing time is 1-4 h, the heating temperature is 20-80 DEG C, and the stirring time is 2-6 h; In S3, the heating temperature is 20-80 DEG C, the stirring time is 2-6 h, the drying temperature is 80-200 DEG C, and the drying time is 2-5 h.

Images