CN117500294A - Perovskite crystalline silicon HJT laminated battery - Google Patents

Perovskite crystalline silicon HJT laminated battery Download PDF

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CN117500294A
CN117500294A CN202311839508.6A CN202311839508A CN117500294A CN 117500294 A CN117500294 A CN 117500294A CN 202311839508 A CN202311839508 A CN 202311839508A CN 117500294 A CN117500294 A CN 117500294A
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perovskite
hjt
transport layer
hole transport
crystalline silicon
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CN117500294B (en
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任现坤
丁亮
王建伟
王象河
范作永
吕岩
陈冲
曹振
朱红
丁相萍
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Shandong Linuo Sunshine Power Technology Co ltd
Linyi Licheng New Energy Co ltd
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Linyi Licheng New Energy Co ltd
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Abstract

The invention discloses a perovskite crystal silicon HJT laminated battery, and relates to the field of perovskite crystal silicon laminated batteries. The perovskite crystal silicon HJT laminated cell comprises a crystal silicon cell and a perovskite cell, wherein the perovskite cell is positioned above the crystal silicon cell and comprises an electrode, an electron transport layer, a perovskite absorption layer, a hole transport layer and a first conductive substrate which are arranged from top to bottom. According to the invention, the black phosphazene is doped and modified by adopting Cu element, sc element and polynaphthalamide to prepare the hole transport layer material, so that the hole mobility and stability of the hole transport layer are improved, and the photoelectric conversion efficiency of the perovskite/crystalline silicon HJT laminated battery is improved.

Description

Perovskite crystalline silicon HJT laminated battery
Technical Field
The invention relates to the technical field of perovskite solar laminated cells, in particular to a perovskite crystal silicon HJT laminated cell.
Background
In recent years, with the rapid development of perovskite solar cell industrialization, crystalline silicon and perovskite are the two most cost-effective materials for achieving high efficiency in single junction cells, and thus, perovskite/crystalline silicon cells are the most potential technical route for next-generation industrialized photovoltaic cells. The perovskite/crystalline silicon HJT laminated battery utilizes a wide band gap of the perovskite battery material to set the perovskite battery material above the silicon-based battery, and can absorb high-energy photons which are difficult to be absorbed by the silicon-based battery and are located in a short band, so that solar incident light is utilized to a greater extent, the efficiency of a photovoltaic battery is further improved, and the solar battery has a higher theoretical efficiency limit, and HJT is most suitable for the perovskite layer due to the good amorphous silicon passivation layer, a symmetrical structure and Transparent Conductive Oxide (TCO).
At present, the perovskite/crystalline silicon HJT laminated cell structure is generally a structure that a perovskite cell and a heterojunction film crystalline silicon bottom cell are directly communicated, and the anode and the cathode of the cell are respectively positioned at two ends of the cell, which is equivalent to that the crystalline silicon bottom cell and the perovskite cell are connected in series. The theoretical efficiency of the perovskite/crystalline silicon laminated battery mainly depends on the property of the perovskite battery, the structure of the battery and the like, and the perovskite battery comprises a hole transmission layer, an electron transmission layer, a transparent conductive layer and a top electrode from bottom to top, and the working principle of the perovskite battery is as follows: when light is irradiated on the perovskite, electrons are transported to the electrode through the hole transport layer and then absorbed.
At present, PTAA and Spiro-OMeTAD are mostly adopted as hole transport layer materials, but carrier mobility is too low in the use process of the PTAA and the Spiro-OMeTAD, an auxiliary agent (Li-TFS) is required to be doped to improve mobility, but solubility of the auxiliary agent in a solvent (chlorobenzene) corresponding to the PTAA and the Spiro-OMeTAD is low, and additionally a solvent (Tbp) and an oxidant are required to be added to improve solubility of the auxiliary agent, but the added auxiliary agent and solvent can absorb water vapor molecules, so that the perovskite battery is disabled.
In the prior art, CN115232291A provides a modified hole transport material and application thereof in a perovskite solar cell, PTAA with the molecular weight of 15000-25000 is adopted as the hole transport material, so that the transport capacity of a PTAA hole transport layer for carriers is improved, but in the use process of PTAA, doping auxiliary agents (Li-TSF) and solvents (Tbp) are still needed to improve the mobility of PTAA, and the addition of the auxiliary agents and the solvents can absorb water molecules to cause the perovskite solar cell to lose efficacy, so that the service life of a device is too short. CN106129256B discloses a perovskite solar cell using black phosphorus as a hole transport layer and a preparation method thereof, titanium disulfide is used for doping black phosphorus, and titanium disulfide can only reduce crystal defects of the hole transport layer of the black phosphorus, so that photoelectric conversion efficiency is improved, but the black phosphorus is easier to react with water and oxygen to degrade under illumination conditions, the stability is poor, and the stability of the black phosphorus is not improved. CN106129256B discloses a perovskite solar cell level preparation method using black phosphorus/graphene as a hole transport layer, which sequentially deposits a black phosphorus layer and a graphene layer on a perovskite light absorption layer, and dopes metal Ti or Mo in the black phosphorus and the graphene to improve the carrier transport efficiency, but does not solve the problems of easy degradation and instability of the black phosphorus.
Therefore, a doping-modified hole transport material is needed for perovskite crystalline silicon HJT stacked cells to improve the hole mobility and stability of the hole transport layer, thereby improving the photoelectric conversion efficiency of the perovskite/crystalline silicon HJT stacked cell.
Disclosure of Invention
In view of the above prior art, an object of the present invention is to provide a perovskite crystal silicon HJT stacked cell. The doped modification of the polynaphthalamide, the Cu element and the Sc element is adopted to carry out the doped modification of the black phosphane, so that the lone electron in the black phosphane can be coordinated to form an electron pair, the chemical modification of the black phosphane can be carried out, the water oxygen isolation capability of the black phosphane is improved, the stability of the black phosphane is improved, the electrical property of the black phosphane is fully utilized, and meanwhile, the hole transmission efficiency of the perovskite HJT laminated battery can be improved through the doped modification of the metal element and the polynaphthalamide on the black phosphane.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a perovskite crystal silicon HJT laminated cell, which comprises the following components:
the perovskite battery is positioned above the crystalline silicon battery; the perovskite battery comprises an electrode, an electron transport layer, a perovskite absorption layer, a hole transport layer and a first conductive substrate which are arranged from top to bottom, wherein the hole transport layer is made of a hole transport layer material;
the hole transport layer material is prepared by the following method:
(1) Black phosphorus powder, cuCl solution, sc (NO) 3 ) 3 After the solution is mixed, the dispersion liquid is dispersed after ultrasonic treatment; centrifuging the dispersion liquid, and collecting precipitate obtained by centrifugation to obtain modified black phosphazene;
(2) Mixing modified black phosphazene, polynaphthalimide and water, reacting, filtering after the reaction is finished, collecting filtered solid, and drying to obtain the hole transport layer material.
Preferably, in the step (1), the preparation method of the CuCl solution comprises the following steps: placing CuCl into N-methyl pyrrolidone, and uniformly mixing to obtain a CuCl solution; the concentration of the CuCl solution is 4 multiplied by 10 -3 -6×10 -3 mol/L。
Preferably, in step (1), sc (NO 3 ) 3 The preparation method of the solution comprises the following steps: sc (NO) 3 ) 3 Placing into N-methylpyrrolidone, and mixing to obtain Sc (NO) 3 ) 3 A solution; the Sc (NO) 3 ) 3 The concentration of the solution was 4X 10 -3 -6×10 -3 mol/L。
Preferably, in step (1), the black phosphorus powder, cuCl solution and Sc (NO) 3 ) 3 The amount of solution added was 1mg: (1.5-2.5) mL: (1.5-2.5) mL.
Preferably, in step (1), the operation of ultrasonic treatment is as follows: and under the atmosphere of nitrogen and ice water bath, carrying out ultrasonic treatment for 8-12h at the ultrasonic power of 200-400W.
Preferably, in step (1), the centrifugation is performed by: the dispersion was centrifuged at 1800-2200rpm for 20min and 10000-15000rpm for 30min.
Preferably, in the step (2), the addition amount of the modified black phosphazene, the polynaphthalimide and the water is 100mg: (0.5-1.5) mg: (120-150) mL.
Preferably, in the step (2), the reaction temperature is 60-80 ℃ and the reaction time is 1-2h.
Preferably, in the step (2), the preparation method of the polynaphthalimide comprises the following steps: mixing phenylenediamine, 1,8 naphthalene dianhydride and benzoic acid, reacting for 9 hours at 180 ℃, adding isoquinoline for reacting for 9 hours, adding ethanol solution into the reacted solution after the reaction is finished, soaking for 24 hours, filtering, and drying at 120 ℃ to obtain the polynaphthalimide.
It is further preferred that the mass ratio of the materials of phenylenediamine, 1,8 naphthalene dianhydride, benzoic acid and isoquinoline be 1:1:2:2.
Preferably, in the step (2), the drying temperature is 40-50 ℃ and the drying time is 20-40min.
Preferably, the crystalline silicon battery is provided with an N-type amorphous silicon film, a first i-type amorphous silicon film, a monocrystalline silicon light absorption layer, a second i-type amorphous silicon film, a P-type amorphous silicon film and a second conductive substrate from top to bottom in sequence.
Preferably, the hole transport layer is prepared by the following method: and (3) dissolving the hole transport layer material in ethanol to obtain a mixed solution, spin-coating the mixed solution on the first conductive substrate, and annealing to obtain the hole transport layer.
Further preferably, the ratio of the hole transport layer material to ethanol is 1mg: (8-12) mL; the spin coating rotating speed is 3000-4000rpm, and the spin coating time is 20-30s; the annealing time is 100-110 ℃ and 10min.
The invention has the beneficial effects that:
the invention adopts black phosphazene as a hole transport layer material, and adopts polynaphthalimide, cu element and Sc element to carry out doping modification. The electron pair can be formed by coordination of the solitary electron of the black phosphane through doping modification, meanwhile, the chemical modification can be carried out on the black phosphane, the stability of the black phosphane is enhanced, the electrical property of the black phosphane is fully utilized, and meanwhile, the hole transmission efficiency of the black phosphane can be improved through doping modification of metal and polynaphthalimide on the black phosphane, so that the efficiency of the perovskite HJT laminated battery is enhanced.
Drawings
Fig. 1: the perovskite crystal silicon HJT laminated cell prepared in the embodiment 4 is subjected to normalized photoelectric conversion efficiency test result diagram under continuous solar illumination;
fig. 2: example 4 a J-V diagram of a perovskite crystalline silicon HJT laminate cell was produced.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background art, in order to enhance the theoretical efficiency of the battery, a laminated battery composed of a crystalline silicon battery and a perovskite battery has been developed, and a perovskite/crystalline silicon HJT laminated battery structure is one of the representatives of the laminated battery. The efficiency of a perovskite stacked cell is directly dependent on the properties of the perovskite cell, which are affected by the properties of the hole transport layer, etc.
In the prior art, the black phosphazene and allotropes thereof (purple phosphazene, red phosphazene and the like) are usually directly used as the hole transport layer material, while the black phosphazene has higher hole mobility and adjustable direct band gap, the black phosphazene has unstable chemical property, is easy to degrade and oxidize in the presence of water and oxygen, can accelerate the degradation under the condition of illumination, has larger hole mobility influenced by the structure, and has the hole mobility of only 350cm in the prior art 2 /(V.S). Therefore, in order to ensure the stability of the black phosphazene and further improve the hole transport efficiency, the black phosphazene needs to be doped and modified.
Based on the above, the invention provides a hole transport layer material, which is prepared by adopting black phosphazene as the hole transport layer material and adopting polynaphthalimide, cu element and Sc element to carry out doping modification. First, black phosphorus powder, cuCl solution and Sc (NO 3 ) 3 Mixing the solutions to obtain modified black phosphane, realizing the primary modification of the Cu element and the Sc element on the black phosphane, and combining the Cu element and the Sc element with the lone electron of the black phosphane so as to enhance the stability and the hole mobility of the black phosphane; the invention also adopts polynaphthalamide to carry out secondary modification on the black phosphazene and carries out chemical modification on the black phosphazene, thereby improving the stability and the hole mobility of the black phosphazene. The invention has synergistic effect in improving the stability and hole mobility of the black phosphazene through the primary modification of Cu element and Sc element and the secondary modification of polynaphthalimide.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and are commercially available. Wherein, black phosphorus is purchased from the scientific and technological experimental materials company of the department of China.
Example 1: preparation of hole transport layer materials
(1) Placing CuCl into N-methylpyrrolidone, mixing to obtain a mixture with a concentration of 5×10 -3 A mol/L CuCl solution; sc (NO) 3 ) 3 Placing into N-methylpyrrolidone, and mixing to obtain a solution with a concentration of 5×10 -3 Sc (NO) in mol/L 3 ) 3 A solution;
black phosphorus powder, cuCl solution and Sc (NO 3 ) 3 The solution was prepared at 1mg:2mL: after 2mL of the mixture is added, carrying out ultrasonic treatment for 10 hours under the atmosphere of nitrogen and ice water bath at 300W, and dispersing the mixture; centrifuging the dispersion liquid at 2000rpm for 20min to remove non-stripped block black phosphorus, centrifuging at 12000rpm for 30min to remove N-methylpyrrolidone, and collecting precipitate obtained by centrifugation to obtain modified black phosphazene;
(2) Mixing phenylenediamine, 1,8 naphthalene dianhydride and benzoic acid, reacting for 9 hours at 180 ℃, adding isoquinoline for reacting for 9 hours, adding ethanol solution into the reacted solution after the reaction is finished, soaking for 24 hours, filtering, and drying at 120 ℃ to obtain polynaphthalimide, wherein the mass ratio of the phenylenediamine, 1,8 naphthalene dianhydride, benzoic acid to isoquinoline is 1:1:2:2;
modified black phosphazene, polynaphthalimide and water are added according to the addition amount of 100mg:1mg: after 135mL are uniformly mixed, the mixture is reacted for 1.5 hours at 70 ℃, filtered, the solid obtained by filtration is collected and dried for 30 minutes at 45 ℃, and the hole transport layer material is obtained.
Example 2: preparation of hole transport layer materials
(1) Placing CuCl into N-methylpyrrolidone, mixing to obtain a solution with a concentration of 4×10 -3 A mol/L CuCl solution; sc (NO) 3 ) 3 Placing into N-methylpyrrolidone, and mixing to obtain a solution with a concentration of 4×10 -3 Sc (NO) in mol/L 3 ) 3 A solution;
black phosphorus powder, cuCl solution and Sc (NO 3 ) 3 The solution was prepared at 1mg:1.5mL: after 1.5mL of the mixture is added, 200W of ultrasonic treatment is carried out for 12 hours under nitrogen atmosphere and ice water bath, and dispersion liquid is dispersed; centrifuging at 1800rpm for 20min to remove non-stripped black phosphorus, andcentrifuging at 10000rpm for 30min to remove N-methylpyrrolidone, and collecting precipitate obtained by centrifuging to obtain modified black phosphazene;
(2) Modified black phosphazene, polynaphthalimide and water are added according to the addition amount of 100mg:0.5mg: after 120mL of the mixture is uniformly mixed, the preparation method of the polynaphthalimide is the same as that of the example 1, the reaction is carried out for 2 hours at 60 ℃, the filtration is carried out, the solid obtained by the filtration is collected, and the drying is carried out for 40 minutes at 40 ℃, thus obtaining the hole transport layer material.
Example 3: preparation of hole transport layer materials
(1) Placing CuCl into N-methylpyrrolidone, and mixing to obtain a mixture with a concentration of 6×10 -3 A mol/L CuCl solution; sc (NO) 3 ) 3 Placing into N-methylpyrrolidone, and mixing to obtain a solution with a concentration of 6×10 -3 Sc (NO) in mol/L 3 ) 3 A solution;
black phosphorus powder, cuCl solution and Sc (NO 3 ) 3 The solution was prepared at 1mg:2.5mL:2.5mL of the solution is mixed, and then treated by 400W ultrasonic waves for 8 hours in a nitrogen atmosphere and an ice water bath, so as to obtain dispersion; centrifuging the dispersion liquid at 2200rpm for 20min to remove non-stripped block black phosphorus, centrifuging at 15000rpm for 30min to remove N-methylpyrrolidone, and collecting precipitate obtained by centrifugation to obtain modified black phosphazene;
(2) Modified black phosphazene, polynaphthalimide and water are added according to the addition amount of 100mg:1.5mg: after 150mL of the mixture is uniformly mixed, the preparation method of the polynaphthalimide is the same as that of the example 1, the reaction is carried out for 1h at 80 ℃, the filtration is carried out, the solid obtained by the filtration is collected, and the drying is carried out for 20min at 50 ℃, thus obtaining the hole transport layer material.
Example 4: preparation of perovskite crystal silicon HJT laminated cell
(1) Sequentially depositing a first i-type amorphous silicon film and an N-type amorphous silicon film on the front side of monocrystalline silicon by adopting a chemical vapor deposition method, sequentially depositing a second i-type amorphous silicon film and an N-type amorphous silicon film on the back side of monocrystalline silicon, and depositing a TCO conductive film serving as a second conductive substrate on the back side of a P-type amorphous silicon film to obtain a crystalline silicon battery;
the thickness of the monocrystalline silicon is 250 mu m, the thicknesses of the first i-type amorphous silicon film and the second i-type amorphous silicon film are 5nm, the thickness of the N-type amorphous silicon film is 10nm, the thickness of the P-type amorphous silicon film is 20nm, and the thickness of the TCO conductive film is 80nm;
(2) An N-type amorphous silicon film at the uppermost layer of the crystalline silicon battery is used as a first conductive substrate by vapor deposition TCO conductive film, and then a hole transport layer is prepared by spin coating; the parameters of the hole transport layer prepared by the spin coating method are as follows: preparing the hole transport material prepared in the embodiment 1, dissolving the hole transport material in ethanol to obtain a mixed solution, spin-coating the mixed solution on the TCO conductive film, and annealing for 10min at 105 ℃ to obtain the hole transport layer, wherein the spin-coating speed is 3500rpm, the spin-coating time is 25s, and the feed liquid ratio of the hole transport layer material to the ethanol is 1mg:10mL;
then a perovskite structure light absorption layer and an electron transport layer are sequentially deposited on the front surface of the hole transport layer by adopting a spin coating method, and then gold is evaporated to serve as an electrode, so that the perovskite crystal silicon HJT laminated battery is obtained;
wherein the thickness of the hole transport layer is 10nm; the electron transport layer material is TiO 2 The thickness of the electron transport layer is 30nm; the first conductive substrate is a TCO conductive film, and the thickness of the first conductive substrate is 100nm; the thickness of the perovskite structure light absorption layer is 600nm.
Example 5: preparation of perovskite crystal silicon HJT laminated cell
This embodiment differs from embodiment 4 in that: the hole transport layer is obtained by spin coating the hole transport layer material prepared in the embodiment 2; in the spin coating process, the spin coating rotating speed is 3000rpm, the spin coating time is 20s, the annealing temperature is 100 ℃, the annealing time is 10min, and the feed liquid ratio of the hole transport layer material to ethanol is 1mg:8mL.
Example 6: preparation of perovskite crystal silicon HJT laminated cell
This embodiment differs from embodiment 4 in that: the hole transport layer is obtained by spin coating the hole transport layer material prepared in the embodiment 3; in the spin coating process, the spin coating rotating speed is 4000rpm, the spin coating time is 30s, the annealing temperature is 110 ℃, and the annealing time is 10min; the feed liquid ratio of the hole transport layer material to ethanol is 1mg:12mL.
Comparative example 1:
the present comparative example is different from example 4 in that the hole transport layer material is only unmodified black phosphorus powder.
Comparative example 2:
the present comparative example is different from example 4 in that the hole transport layer material is modified black phosphazene. The preparation method of the modified black phosphazene is the same as that of the example 1.
Comparative example 3:
the present comparative example differs from example 4 in that the hole transport layer material was prepared by the following method:
black phosphorus powder, polynaphthalimide and water were added in an amount of 100mg:1mg: after 135mL are uniformly mixed, reacting for 1.5h at 70 ℃, filtering, collecting the solid obtained by filtering, and drying for 30min at 45 ℃ to obtain the hole transport layer material.
Test example 1:
the hole transport materials in example 4 and comparative examples 1 to 3 were tested for hole mobility using a space charge limited current method. The method comprises the following specific steps:
(1) Sequentially placing the ITO glass substrate in acetone, ethanol and deionized water for ultrasonic treatment for 10min, and drying;
(2) Depositing the hole transport layer materials in the embodiment 4 and the comparative examples 1 to 3 on the dried ITO glass substrate by adopting a vapor deposition method to obtain an ITO glass substrate/hole transport layer, wherein the thickness of the hole transport layer is 120nm;
evaporating Al on the ITO glass substrate/hole transport layer to obtain a top electrode, wherein the thickness of the top electrode is 50nm, so that a single current carrying device is obtained, and the effective area of the device is 2cm multiplied by 2cm through the design of a mask;
(3) And analyzing J-U curves of the single current carrying device, taking data of a high bias space charge limited current region of each device, drawing a fitting straight line, and obtaining hole mobility of each hole transport material, wherein the results are shown in table 1.
Table 1 hole mobility of perovskite crystalline silicon HJT stack cell
As can be seen from Table 1, compared with comparative example 1, comparative examples 2 and 3 respectively doped with Cu and Sc metal elements on the black phosphorus alkene and doped with polynaphthalimide on the black phosphorus alkene, the hole mobility and the photoelectric conversion efficiency are slightly increased, and the hole mobility can be obviously enhanced by doping modification treatment of polynaphthalimide, cu and Sc metal elements on the black phosphorus alkene.
Test example 2:
the perovskite crystalline silicon HJT layered cell obtained in comparative example 1 and example 4 was placed in AM1.5 solar light with an intensity of 1000W/m 2 Stability testing was performed with continued illumination for 1000 hours and the results are shown in figure 2.
As can be seen from fig. 2, the photoelectric conversion efficiency of the perovskite crystal silicon HJT laminated cell prepared by the method is kept at 95% of the initial photoelectric conversion efficiency after the continuous operation for 750 hours, and can be kept at about 90% of the initial photoelectric conversion efficiency after the continuous operation for 1000 hours, while the laminated cell is prepared by only adopting the unmodified black phosphorus as the hole transport layer in comparative example 1, and the photoelectric conversion efficiency of the perovskite crystal silicon HJT laminated cell is kept at about 76% of the initial photoelectric conversion efficiency after the continuous operation for 1000 hours, so that the hole transport layer material prepared by the method has good stability, and the perovskite crystal silicon HJT laminated cell still has higher photoelectric conversion efficiency when the perovskite crystal silicon HJT laminated cell is used for the continuous operation for 1000 hours.
The perovskite crystalline silicon HJT layered cell obtained in example 4 was placed in AM1.5 sunlight with an intensity of 1000W/m 2 The J-V analysis was performed as shown in fig. 2, and the photoelectric conversion efficiency was calculated to be 30.72%, thus it was found that the hole transport material of the present invention is advantageous for improving the photoelectric conversion rate of the perovskite crystalline silicon HJT stacked cell.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims (9)

1. A perovskite crystalline silicon HJT stacked cell comprising:
the perovskite battery is positioned above the crystalline silicon battery; the perovskite battery comprises an electrode, an electron transport layer, a perovskite absorption layer, a hole transport layer and a first conductive substrate which are arranged from top to bottom, wherein the hole transport layer is made of a hole transport layer material;
the hole transport layer material is prepared by the following method:
(1) Black phosphorus powder, cuCl solution, sc (NO) 3 ) 3 After the solution is mixed, the dispersion liquid is dispersed after ultrasonic treatment; centrifuging the dispersion liquid, and collecting precipitate obtained by centrifugation to obtain modified black phosphazene;
(2) Mixing modified black phosphazene, polynaphthalimide and water for reaction, filtering after the reaction is finished, collecting filtered solid, and drying to obtain the hole transport layer material.
2. The perovskite crystalline silicon HJT stack cell of claim 1 wherein in step (1), the method of preparing the CuCl solution comprises: placing CuCl into N-methyl pyrrolidone, and uniformly mixing to obtain a CuCl solution; the concentration of the CuCl solution is 4 multiplied by 10 -3 -6×10 -3 mol/L；
Sc(NO 3 ) 3 The preparation method of the solution comprises the following steps: sc (NO) 3 ) 3 Placing into N-methylpyrrolidone, and mixing to obtain Sc (NO) 3 ) 3 A solution; the Sc (NO) 3 ) 3 The concentration of the solution was 4X 10 -3 -6×10 -3 mol/L。
3. The perovskite crystalline silicon HJT stack cell of claim 1, wherein in step (1), the black phosphorus powder, cuCl solution, and Sc (NO 3 ) 3 The amount of solution added was 1mg: (1.5-2.5) mL: (1.5-2.5) mL.
4. The perovskite crystalline silicon HJT stack cell of claim 1 wherein in step (1) the operation of ultrasonic treatment is: and under the atmosphere of nitrogen and ice water bath, carrying out ultrasonic treatment for 8-12h at the ultrasonic power of 200-400W.
5. The perovskite crystalline silicon HJT stack cell according to claim 1, wherein in step (2), the addition amount of modified black phosphazene, polynaphthalimide and water is 100mg: (0.5-1.5) mg: (120-150) mL.
6. The perovskite crystalline silicon HJT stack cell of claim 1 wherein in step (2) the reaction temperature is from 60 ℃ to 80 ℃ and the reaction time is from 1 hour to 2 hours.
7. The perovskite crystalline silicon HJT stack cell of claim 1, wherein the crystalline silicon cell comprises an N-type amorphous silicon film, a first i-type amorphous silicon film, a single crystalline silicon light absorbing layer, a second i-type amorphous silicon film, a P-type amorphous silicon film, and a second conductive substrate in this order from top to bottom.
8. The perovskite crystalline silicon HJT stack cell of claim 1 wherein the hole transporting layer is prepared by the method of: and (3) dissolving the hole transport layer material in ethanol to obtain a mixed solution, spin-coating the mixed solution on the first conductive substrate, and annealing to obtain the hole transport layer.
9. The perovskite crystalline silicon HJT stack cell of claim 8, wherein the hole transporting layer material to ethanol feed ratio is 1mg: (8-12) mL; the spin coating rotating speed is 3000-4000rpm, and the spin coating time is 20-30s; the annealing time is 100-110 ℃ and 10min.
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