A perovskite component annealing part, its annealing method, and a battery

Abstract

The present invention relates to the technical field of battery devices, and specifically provides a perovskite component annealing member, an annealing method thereof, and a battery. The annealing method of the perovskite component preform of the present invention includes: under the condition of the presence of a first electrode, passing an alternating current through the first electrode to perform annealing treatment on the perovskite component preform to obtain a perovskite component annealing member; the perovskite component preform includes a perovskite active layer, a hole transport layer, and an FTO glass; the distance between the first electrode and the perovskite active layer is ≥ 2 cm. Compared with the prior art, this method passes an alternating current through the first electrode to generate an alternating magnetic field, thereby inducing the formation of eddy currents inside the perovskite active layer, and using the Joule heat formed by the eddy currents to anneal the perovskite active layer, which has the characteristics of good temperature uniformity and high annealing temperature rise rate, and at the same time minimizes the heat loss during the annealing process.

Description

Technical Field

[0001] The present invention relates to the technical field of battery devices, and more specifically, to a perovskite component annealing member, an annealing method thereof, and a battery. Background Art

[0002] Perovskite solar cells are solar cells that use perovskite-type organometallic halide semiconductors as light-absorbing materials and belong to the third generation of solar cells. More and more attention has been paid to the research of perovskite component prefabricates, which are the key functional layers. The film layer structure of the perovskite component prefabricate from bottom to top is: glass, FTO, NiO x hole transport layer, perovskite active layer. After annealing the perovskite component prefabricate, a perovskite thin film material is obtained. Due to the large light absorption coefficient, high carrier lifetime, high charge mobility, and extremely low defect state density of the perovskite thin film material, it shows great application value in solar cells and other optoelectronic devices.

[0003] At present, the annealing process of perovskite thin films mainly includes two types: 1) Gas-phase medium annealing process, that is, the perovskite thin film after the coating process is placed in a specific environmental atmosphere, such as inert gases such as air and nitrogen, and annealed by applying an external heat source. Here, the uniformity of perovskite grain growth is guaranteed by the uniformity of the external heat source. In order to ensure the effect of the perovskite thin film annealing process, a heat source with strong uniformity is often used for the annealing process. Common heat sources mainly include contact-type metal hot stages, non-contact infrared radiation light sources, etc. 2) Liquid-phase medium annealing process, in which the coated perovskite thin film is placed in anisole solution, and the solution is heated to 160 °C and maintained at a constant temperature to achieve the annealing treatment of the perovskite thin film. The liquid working medium annealing process aims to create a uniform chemical environment and a constant heating field to regulate the crystal growth process of the perovskite thin film. With the continuous deepening of the perovskite industrialization process, perovskite thin films are continuously tending to be large-area, which puts forward new requirements for the preparation process of perovskite thin films, especially the annealing process. As the coating area of the perovskite precursor solution continues to increase, the annealing process suitable for small-area perovskite thin films cannot ensure the crystal growth effect of large-area perovskite thin films. The traditional annealing process for large-area perovskite annealing has the following problems: 1) Poor temperature uniformity during annealing; 2) Slow temperature rise rate during annealing, which is not conducive to the volatilization of organic components and solvents; 3) High energy consumption and serious heat loss during annealing. Therefore, it is of great significance to study an annealing process suitable for large-area perovskite thin films. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a perovskite component annealing device, an annealing method thereof, and a battery, which have advantages such as good temperature uniformity and small energy consumption loss, and are applicable to the rapid annealing process of a large-area perovskite active layer.

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

[0006] An annealing method for a perovskite component preform, comprising: in the presence of a first electrode, passing an alternating current through the first electrode to perform annealing treatment on the perovskite component preform to obtain a perovskite component annealing device;

[0007] The perovskite component preform includes a perovskite active layer, a hole transport layer, and an FTO glass;

[0008] The distance between the first electrode and the perovskite active layer > 2 cm.

[0009] The alternating current mode of the present invention is a sinusoidal alternating current or a cosine-type alternating current.

[0010] The inventors found in the research that after passing an alternating current through the first electrode, an alternating magnetic field is generated. When the perovskite is placed as a conductor in the alternating magnetic field, an induced current is generated in the conductor and the current forms a closed-loop eddy current in the conductor. The Joule heat generated by the eddy current can anneal the perovskite active layer. The faster the magnetic field changes, the greater the induced electromotive force, the stronger the eddy current, and the more significant the Joule heat effect of the conductor.

[0011] The present invention has no special limitation on the material of the electrode, and conventional metal electrodes or graphite electrodes can be used. The material of the metal electrode can be one or more of brass, cast iron, or tungsten alloy.

[0012] The first electrode is preferably a brass electrode; the shape of the first electrode is preferably cylindrical, and the diameter of the bottom circle is 1 - 20 mm, preferably 2 mm.

[0013] In the present invention, the first electrode is located on the side of the perovskite component preform close to the perovskite active layer.

[0014] The distance between the first electrode and the perovskite active layer is 2 - 5 cm, preferably 2 cm.

[0015] In the present invention, the annealing treatment includes:

[0016] Passing a first alternating current through the first electrode to achieve low-temperature pre-annealing treatment of the perovskite active layer;

[0017] Then passing a second alternating current through the first electrode to achieve high-temperature annealing treatment of the perovskite active layer;

[0018] In the low-temperature pre-annealing treatment, the frequency of the first alternating current is 20 to 50 kHz, preferably 20 kHz, the effective value is 10 to 30 A, preferably 10 A, and the treatment time is 30 to 50 s, preferably 30 s;

[0019] In the high temperature annealing treatment, the frequency of the second alternating current is 50-100 kHz, preferably 50 kHz, the effective value is 30-50 A, preferably 30 A, and the treatment time is 90-120 s, preferably 90 s.

[0020] In the present invention, a second electrode is provided between the first electrode and the perovskite active layer;

[0021] The material of the second electrode is one or more of graphite, brass, cast iron, and tungsten alloy;

[0022] In one embodiment of the present invention, the second electrode is a graphite electrode;

[0023] The distance between the second electrode and the perovskite active layer is ≥2 cm; the distance between the second electrode and the first electrode is preferably ≥1 cm;

[0024] A third electrode is provided on one side of the perovskite component preform close to the FTO glass; in one embodiment of the present invention, the third electrode is a graphite electrode; the third electrode is preferably in contact with the perovskite component preform; and further in contact with the FTO glass in the perovskite component preform.

[0025] After an alternating current is passed through the first electrode, an alternating magnetic field is generated. The second electrode and the third electrode induce eddy currents in the alternating magnetic field, thereby generating Joule heat. The second electrode is not in direct contact with the perovskite active layer, and the heat is transferred by radiation heat exchange. The Joule heat generated by the third electrode can be transferred to the perovskite active layer by heat conduction to perform heat treatment on it. That is, the dual-electrode Joule heat annealing process based on electromagnetic induction provided by the present invention is a dual-synergistic annealing process of heat conduction and radiation, and has the characteristics of good temperature uniformity, high annealing temperature rise rate and low energy loss.

[0026] The present invention also provides an annealed perovskite component obtained by the annealing method of the perovskite component preform.

[0027] The present invention also provides a battery, comprising the above-mentioned perovskite component annealing part.

[0028] The present invention has no special limitation on the battery, and any conventional battery in the art can be used to obtain the perovskite component annealing part obtained by the method of the present invention, preferably a solar cell.

[0029] The annealing process of the present invention applies an alternating current to the first electrode to generate an alternating magnetic field, thereby inducing eddy currents inside the perovskite active layer. The Joule heat formed by the eddy currents is used to anneal the perovskite active layer, which can minimize heat loss during the annealing process and also has characteristics such as good temperature uniformity and high annealing temperature rise rate.

[0030] After a second electrode is provided between the first electrode and the perovskite component preform, and a third electrode is provided on the side of the perovskite component preform close to the FTO glass, the second electrode and the third electrode heat the perovskite active layer by radiation, realizing a double-coordinated annealing process, which is suitable for the rapid annealing process of a large-area perovskite active layer, especially having great advantages in industrial production lines. Verified by the embodiments of the present invention, for the perovskite component annealed piece obtained by the annealing method of the present invention, during the low-temperature pre-annealing process, the surface steady-state average temperature of the perovskite active layer is 83.4 - 85.8 °C, the temperature extreme difference at multiple measurement points < 6.4 °C, and the temperature rise rate ≥ 125 °C / minute; during the high-temperature annealing process, the surface steady-state average temperature of the perovskite active layer is 163.2 - 168.7 °C, the temperature extreme difference at multiple measurement points < 7.4 °C, and the temperature rise rate ≥ 189.6 °C / minute. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic layout diagram of the electrodes and the perovskite component preform in Embodiment 1 of the present invention;

[0032] Figure 2 It is a schematic layout diagram of the alternating electrode, the top electrode, the perovskite component preform, and the back electrode in Embodiment 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] To further illustrate the present invention, the following detailed description is provided through the following embodiments. All raw materials used in the following embodiments of the present invention are commercially available products.

[0035] The preparation method of the component including the methylammonium lead iodide (MAPbI3) perovskite active layer in the embodiment of the present invention includes:

[0036] (1) Prepare NiO x hole transport layer on the FTO glass by magnetron sputtering, and the obtained hole transport layer has a thickness of 20 - 30 nm;

[0037] (2) Prepare the perovskite precursor solution. According to the stoichiometric ratio of MAPbI3, MAI:PbI2 = 1:1 (molar ratio), the perovskite concentration is 0.8 - 1.2 mol / L, and the solvent is N,N-dimethylformamide (DMF) and dimethylpropyleneurea (DMPU).

[0038] (3) On the FTO glass, use the slot-die coating method to form a film of the perovskite solution obtained in step (1) and wait for subsequent annealing treatment.

[0039] Example 1

[0040] The annealing process of the perovskite active layer in this example includes the following steps:

[0041] (1) Use the slot-die coating process to prepare a component including a methylammonium lead iodide (MAPbI3) perovskite active layer. The component includes, from top to bottom: a perovskite active layer (perovskite thin film), NiO x hole transport layer, FTO, glass; the film area of the methylammonium lead iodide (MAPbI3) perovskite active layer is 10 cm × 10 cm, and the thickness is 460 nm.

[0042] (2) Place the component parallel between the top and back electrodes, with the back electrode in contact with the glass, and keep a 2 cm distance between the perovskite active layer and the top electrode to form a structure as shown in Figure 1 shown, and place the alternating electrode 2 cm above the top electrode to form a structure as shown in Figure 2 shown; the materials of the top and back electrodes are graphite, with a thickness of 0.5 cm, and the carrier electrode body (alternating electrode) of the alternating current is a cylinder with a diameter of 2 mm, and the electrode material is brass.

[0043] (3) Apply a low-frequency and low effective value alternating current to the alternating electrode to achieve low-temperature pre-annealing treatment of the perovskite active layer; the alternating current mode is a sinusoidal alternating current, the frequency range: 20 kHz, the effective value: 10 A, and the heat treatment time is 30 s.

[0044] (4) Apply a high-frequency and high effective value alternating current to the carrier electrode to achieve high-temperature annealing treatment of the perovskite active layer; the alternating current mode is a sinusoidal alternating current, the frequency range: 50 kHz, the effective value: 30 A, and the heat treatment time is 90 s.

[0045] (5) Cut off the alternating current acting on the carrier cell to end the annealing process and obtain the annealed perovskite component.

[0046] Measured by a high-temperature thermal imager, during the low-temperature pre-annealing process, the surface steady-state average temperature of the MAPbI3 perovskite active layer is 85.8 °C, the temperature extreme difference at multiple measurement points is <5.6 °C, and the temperature rise rate is ≥130 °C / min; during the high-temperature annealing process, the surface steady-state average temperature of the MAPbI3 perovskite active layer is 167.4 °C, the temperature extreme difference at multiple measurement points is <7.4 °C, and the temperature rise rate is ≥195.8 °C / min.

[0047] Example 2

[0048] The annealing process steps of the perovskite active layer in this example include:

[0049] (1) Prepare a component including a methylammonium lead iodide (MAPbI3) perovskite active layer by a slot-die coating process. The component includes, from top to bottom: a perovskite active layer (perovskite thin film), NiO x hole transport layer, FTO, glass; the film area of the methylammonium lead iodide (MAPbI3) perovskite active layer is 65 cm × 65 cm, and the thickness is 530 nm.

[0050] (2) Place the component parallel between the top and bottom electrodes, with the bottom electrode in contact with the glass. Keep a 2-cm spacing between the perovskite active layer and the top electrode, and place the alternating electrode 2 cm above the top electrode; the materials of the top and bottom electrodes are graphite, with a thickness of 0.5 cm. The carrier electrode body (alternating electrode) of the alternating current is a cylinder with a diameter of 2 mm, and the electrode material is brass.

[0051] (3) Apply a low-frequency and low-effective-value alternating current to the alternating electrode to achieve low-temperature pre-annealing of the perovskite active layer; the alternating current mode is a sinusoidal alternating current, the frequency range is 20 kHz, the effective value is 10 A, and the heat treatment time is 30 s.

[0052] (4) Apply a high-frequency and high-effective-value alternating current to the carrier electrode to achieve high-temperature annealing of the perovskite active layer; the alternating current mode is a sinusoidal alternating current, the frequency range is 50 kHz, the effective value is 30 A, and the heat treatment time is 90 s.

[0053] (5) Cut off the alternating current acting on the carrier cell to end the annealing process and obtain an annealed perovskite component.

[0054] Measured by a high-temperature thermal imager, during the low-temperature pre-annealing process, the surface steady-state average temperature of the MAPbI3 perovskite active layer is 83.4 °C, the temperature extreme difference at multiple measurement points is <6.4 °C, and the temperature rise rate is ≥125 °C / min; during the high-temperature annealing process, the surface steady-state average temperature of the MAPbI3 perovskite active layer is 163.2 °C, the temperature extreme difference at multiple measurement points is <5.8 °C, and the temperature rise rate is ≥189.6 °C / min.

[0055] Example 3

[0056] The annealing process of the perovskite active layer in this example includes the following steps:

[0057] (1) Prepare a component including a methylammonium lead iodide (MAPbI3) perovskite active layer by using a slot-die coating process. The component includes, from top to bottom: a perovskite active layer (perovskite thin film), NiO x hole transport layer, FTO, and glass; the film area of the methylammonium lead iodide (MAPbI3) perovskite active layer is 10 cm × 10 cm, and the thickness is 1020 nm.

[0058] (2) Place the component parallel between the top and bottom electrodes, with the bottom electrode in contact with the glass. Keep a 2-cm distance between the perovskite active layer and the top electrode, and place the alternating electrode 2 cm above the top electrode; the materials of the top and bottom electrodes are graphite, with a thickness of 0.5 cm. The carrier electrode body (alternating electrode) of the alternating current is a cylinder with a diameter of 2 mm, and the electrode material is brass.

[0059] (3) Apply a low-frequency and low-effective-value alternating current to the alternating electrode to achieve low-temperature pre-annealing treatment of the perovskite active layer; the mode of the alternating current is a sinusoidal alternating current, the frequency range is 30 kHz, the effective value is 15 A, and the heat treatment time is 30 s.

[0060] (4) Apply a high-frequency and high-effective-value alternating current to the carrier electrode to achieve high-temperature annealing treatment of the perovskite active layer; the mode of the alternating current is a sinusoidal alternating current, the frequency range is 60 kHz, the effective value is 40 A, and the heat treatment time is 90 s.

[0061] (5) Cut off the alternating current applied to the carrier cell to end the annealing process and obtain an annealed perovskite component.

[0062] Measured by a high-temperature thermal imager, during the low-temperature pre-annealing treatment, the surface steady-state average temperature of the MAPbI3 perovskite active layer is 84.6 °C, the temperature extreme difference at multiple measurement points is <5.9 °C, and the temperature rise rate is ≥144 °C / min; during the high-temperature annealing treatment stage, the surface steady-state average temperature of the MAPbI3 perovskite active layer is 168.7 °C, the temperature extreme difference at multiple measurement points is <6.9 °C, and the temperature rise rate is ≥208.2 °C / min.

[0063] Comparative Example 1 (traditional annealing process)

[0064] The MAPbI3 perovskite prepared by the slot coating process in Example 1 was subjected to a conventional annealing treatment, that is, the perovskite active layer was annealed by a hot stage, and the annealing temperature on the surface of the hot stage was set at 160 °C (the recommended value in the literature). The annealing duration was set at 15 min. During the hot stage annealing, the temperature rise rate of the surface of the perovskite active layer before reaching the peak value was 48 °C / min. The surface steady-state average temperature of the MAPbI3 perovskite active layer was 155.3 °C, and the temperature extreme difference of multiple measurement points was <8.6 °C.

[0065] Comparative Example 2 (a comparative example without top and back electrodes)

[0066] The film area of the methylammonium lead iodide (MAPbI3) perovskite active layer was 10 cm × 10 cm, and the thickness was 460 nm. This comparative example was carried out according to the steps in Example 1. The difference from Example 1 was that: the top and back electrodes were removed, only the alternating electrodes were included, and they were placed 1.5 cm above the perovskite active layer.

[0067] Low-temperature pre-annealing treatment of the perovskite active layer; the mode of the alternating current was a sinusoidal alternating current, the frequency range: 20 kHz, the effective value: 10 A, and the heat treatment time was 30 s.

[0068] High-temperature annealing treatment of the perovskite active layer; the mode of the alternating current was a sinusoidal alternating current, the frequency range: 50 kHz, the effective value: 30 A, and the heat treatment time was 90 s.

[0069] Annealing effect

[0070] Measured by a high-temperature thermal imager, during the low-temperature pre-annealing treatment, the surface steady-state average temperature of the MAPbI3 perovskite active layer was 77.6 °C, the temperature extreme difference of multiple measurement points was <8.6 °C, and the temperature rise rate was ≥110 °C / min. During the high-temperature annealing treatment stage, the surface steady-state average temperature of the MAPbI3 perovskite active layer was 160.6 °C, the temperature extreme difference of multiple measurement points was <8.9 °C, and the temperature rise rate was ≥135.7 °C / min.

Claims

1. Annealing method for perovskite component preform, characterized in that, Comprising: In the presence of a first electrode, applying an alternating current to the first electrode and annealing a perovskite component preform to obtain an annealed perovskite component; The perovskite component preform includes a perovskite active layer, a hole transport layer, and FTO glass; The distance between the first electrode and the perovskite active layer > 2 cm; The first electrode is located on the side of the perovskite component preform close to the perovskite active layer; A second electrode is provided between the first electrode and the perovskite active layer; The distance between the second electrode and the perovskite active layer ≥ 2 cm; A third electrode is provided on the side of the perovskite component preform close to the FTO glass.

2. The annealing method of the perovskite component preform according to claim 1, characterized in that The distance between the first electrode and the perovskite active layer is 2 - 5 cm.

3. The annealing method of the perovskite component preform according to claim 1, characterized in that, The annealing treatment includes: Applying a first current to the first electrode alternately to achieve low-temperature pre-annealing treatment of the perovskite active layer; Then applying a second alternating current to the first electrode to achieve high-temperature annealing treatment of the perovskite active layer.

4. The annealing method of the perovskite component preform according to claim 3, wherein, In the low-temperature pre-annealing treatment, the frequency of the first alternating current is 20 - 50 kHz, the effective value is 10 - 30 A, and the treatment time is 30 - 50 s.

5. The annealing method of the perovskite component preform according to claim 3, characterized in that, In the high-temperature annealing treatment, the frequency of the second alternating current is 50 - 100 kHz, the effective value is 30 - 50 A, and the treatment time is 90 - 120 s.

6. An annealed perovskite component obtained by the annealing method of the perovskite component preform according to any one of claims 1 - 5.

7. Battery, characterized in that, Comprising the annealed perovskite component according to claim 6.

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