Energy conversion device, method of manufacturing the same, and long-term energy supply device

Abstract

The application discloses an energy conversion device and a preparation method thereof and a long-time energy supply device. The energy conversion device comprises a first electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and a second electrode which are arranged in a stack. The passivation layer is covered on the surface of the electron transport layer. The passivation layer prevents water and oxygen in the external environment from invading the perovskite absorption layer, reduces material degradation and performance attenuation caused thereby, and thus improves the long-term stability of the nuclear battery. In the use process of the beta nuclear battery, the energy of the excess beta rays can be deposited in the passivation layer. The passivation layer reduces the damage of high-energy electrons to the electron transport layer, and thus further improves the long-term stability of the nuclear battery. The first electrode, the passivation layer, the electron transport layer, the perovskite absorption layer, the hole transport layer and the second electrode are synergistically used, so that the long-term stability and service life of the energy conversion device are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nuclear batteries, in particular, to an energy conversion device, a preparation method thereof and a long-time energy supply device. BACKGROUND

[0002] In order to reduce the emission of greenhouse gases and cope with global climate change, it is particularly important to find clean and renewable new energy to replace traditional fossil fuels. Radioactive isotope driven nuclear batteries have been widely used in key fields such as medical treatment, military and aerospace due to their advantages of no pollution gas emission, long service life, continuous power supply and high energy density. In the design of nuclear batteries, three types of radiation generated by isotope decay need to be considered: α-rays, β-rays and γ-rays. Especially for α-rays and γ-rays, they have extremely high energy and penetration ability, which will cause a certain degree of damage to the components of the nuclear battery, and then affect the performance and safety of the device. Therefore, it is necessary to further optimize the design of the nuclear battery to reduce the negative effects of these high-energy radiations on the device.

[0003] It should be noted that the above statements are only used to provide background technical information related to the present application, and do not necessarily constitute the prior art. SUMMARY

[0004] In the first aspect of the present application, the present application provides an energy conversion device, comprising: a first electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and a second electrode which are stacked. The passivation layer of the present application covers the surface of the electron transport layer. The passivation layer acts as a barrier to prevent water and oxygen in the external environment from invading the perovskite absorption layer, thereby reducing material degradation and performance decay caused thereby, and improving the long-term stability of the nuclear battery. In addition, during the use of the β-type nuclear battery, the energy of the excess β-rays can be deposited in the passivation layer, and the passivation layer reduces the damage of high-energy electrons to the electron transport layer, thereby further improving the long-term stability of the nuclear battery. Therefore, through the synergistic effect of the first electrode, the passivation layer, the electron transport layer, the perovskite absorption layer, the hole transport layer and the second electrode, the long-term stability and service life of the energy conversion device are improved.

[0005] In some embodiments, the number of layers of the passivation layer comprises at least one layer. In this way, by designing the number of layers of the passivation layer, the protection of the perovskite absorption layer can be enhanced, and the erosion of environmental factors such as water and oxygen can be reduced; at the same time, the energy of the excess β-rays can be deposited in the passivation layer, thereby improving the long-term stability of the energy conversion device.

[0006] In some embodiments, the material of the passivation layer comprises at least one of metal oxides corresponding to Mg, Ni, Cd, Zn, In, Pb, Mo, Sb, Bi, Cu, Ti, Mn, V, and Sn, and at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. Thus, the appropriate passivation layer material is selected to have a high damage threshold, which means that the material can withstand higher energy input without structural damage or performance degradation, and a low atomic number, which means that the material has a lower density and smaller atomic mass, thus reducing the probability of interaction with incident particles (such as beta rays), thereby reducing energy loss and radiation damage, thus helping to improve the long-term stability and service life of the energy conversion device.

[0007] In some embodiments, the material of the perovskite absorption layer satisfies the chemical formula APbX3, where A comprises at least one of MA + , FA + , and Cs + ; and X comprises at least one of Cl - , Br - , and I - . Thus, the appropriate material of the perovskite absorption layer is selected to have better thermal stability and chemical stability, which is conducive to improving the reliability and long-term stability of the energy conversion device in harsh environments.

[0008] In some embodiments, the material of the electron transport layer comprises at least one of [6,6]-phenyl-C-butanoic acid isomethyl ester, fullerene, and derivatives thereof. Thus, the appropriate electron transport layer material is selected to have a high damage threshold, which means that the material can withstand higher energy input without structural damage or performance degradation, and a low atomic number, which means that the material has a lower density and smaller atomic mass, thus reducing the probability of interaction with incident particles (such as beta rays), thereby reducing energy loss and radiation damage, thus helping to improve the long-term stability and service life of the energy conversion device.

[0009] In some embodiments, the material of the hole transport layer comprises at least one of poly(3,4-ethylenedioxythiophene) class materials: polystyrene sulfonate, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), polybis(4-phenyl), poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine), nickel oxide, metal element doped nickel oxide, wherein the metal element in the metal element doped nickel oxide comprises at least one of Ag, Au, Cu, Cs, K. Thus, by selecting a suitable material for the hole transport layer, the hole transport efficiency can be improved, and the energy loss can be reduced.

[0010] In some embodiments, the first electrode comprises a metal electrode.

[0011] In some embodiments, the second electrode comprises a transparent electrode.

[0012] In some embodiments, the thickness of the first electrode layer is 20-80 nm.

[0013] In some embodiments, the thickness of the passivation layer is 5-10 nm.

[0014] In some embodiments, the thickness of the electron transport layer is 10-20 nm.

[0015] In some embodiments, the thickness of the perovskite absorption layer is 500-2000 nm.

[0016] In some embodiments, the thickness of the hole transport layer is 20-50 nm.

[0017] In some embodiments, the thickness of the second electrode is 100-200 nm.

[0018] In the second aspect of the present application, the present application provides a method for preparing an energy conversion device, forming a hole transport layer on one side of a second electrode; forming a perovskite absorption layer on the side of the hole transport layer away from the second electrode; forming an electron transport layer on the side of the perovskite absorption layer away from the hole transport layer; forming a passivation layer on the side of the electron transport layer away from the perovskite absorption layer; and forming the first electrode on the side of the passivation layer away from the electron transport layer. Thus, the energy conversion device is constructed in an orderly manner, which enhances the long-term stability of the energy conversion device; at the same time, the manufacturing process is simplified, which is helpful for realizing batch production and cost control of the energy conversion device.

[0019] In some embodiments, the method for forming the hole transport layer comprises at least one of a precursor solution spin coating method, a magnetron sputtering method, and a precursor solution doctor blade coating method.

[0020] In some embodiments, the method of forming the perovskite absorption layer comprises a precursor solution spin coating method.

[0021] In some embodiments, the method of forming the electron transport layer comprises at least one of a precursor solution spin coating method, a magnetron sputtering method, a precursor solution doctor blade coating method, and a thermal evaporation co-evaporation method.

[0022] In some embodiments, the method of forming the passivation layer comprises at least one of a spin coating method and a thermal evaporation co-evaporation method.

[0023] In some embodiments, the method of forming the first electrode comprises at least one of a thermal evaporation co-evaporation method and a magnetron sputtering method.

[0024] In a third aspect of the present application, a long-time energy supply device is provided, comprising the aforementioned energy conversion device or the energy conversion device obtained by the aforementioned energy conversion device preparation method, and a beta-type radiation source located close to the first electrode. The working principle of the long-time energy supply device of the present application is as follows: beta rays (high-energy electrons) are incident from the first electrode, and in the process of passing through the first electrode, the passivation layer, and the electron transport layer in turn, the high-energy electrons collide with the materials in the layers, and a part of the energy of the high-energy electrons is lost; the remaining high-energy electrons collide with the atoms inside the perovskite absorption layer after reaching the perovskite absorption layer, causing the electrons in the valence band of the atoms to be excited to the conduction band to form electron-hole pairs, and the drift and diffusion motion of the electron-hole pairs through the PIN junction form free carriers, which are led out through the electrodes on both sides of the energy conversion device to form an electric current to supply power to external equipment. This kind of long-time energy supply device can effectively convert the energy of beta rays into electrical energy, thereby realizing long-term stable power output of the long-time energy supply device.

[0025] In some embodiments, the beta-type radiation source comprises at least one of 3 H and its compounds, 14 C and its compounds, 35 S and its compounds, 63 Ni and its compounds, 85 Kr and its compounds, 90 Sr and its compounds, 90 Y and its compounds. Thus, the radiation source used in the present application is a pure beta-ray isotope source, which has a longer half-life and smaller radiation energy, thereby increasing the service life and safety of the nuclear battery. BRIEF DESCRIPTION OF DRAWINGS

[0026] The above and / or additional aspects and advantages of the present application will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:

[0027] Figure 1Fig. 1 is a schematic diagram of a structure of a long-time power supply device according to an embodiment of the present application.

[0028] Explanation of Reference Numerals

[0029] 1: radiation source; 2: metal electrode; 3: passivation layer; 4: electron transport layer; 5: perovskite absorption layer; 6: hole transport layer; 7: transparent electrode. DETAILED DESCRIPTION

[0030] Hereinafter, embodiments of an energy conversion device, a method for manufacturing the same, and a long-time power supply device according to the present application will be described in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed description is omitted. For example, there will be cases where detailed description of matters that are well known and repeated description of substantially identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0031] The ranges disclosed herein are defined by their lower and upper limits, and are inclusive of the ranges explicitly recited. Ranges are provided as a shorthand for describing a group of sub-ranges, as well as individual sub-ranges, each sub-range being between the upper limit of a range and the lower limit of another range, as if each sub-range is explicitly recited. For example, if a range of 60-120 and a range of 80-110 are listed, it is understood that a range of 60-110 and a range of 80-120 are also explicitly recited. Furthermore, if a minimum range value of 1 and 2 are listed, and if a maximum range value of 3, 4, and 5 are listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise indicated, a numerical range "a-b" is intended to indicate any and all sub-ranges of the same, including the end values and excluding the end values, as inherently anted by the terms. For example, a numerical range "0-5" is intended to indicate the full set of "0-5" as all the individual numbers between the two values, inclusive of the values. Additionally, when a parameter is stated to be an integer ≥ 2, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.

[0032] All embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, unless otherwise specified.

[0033] All technical features and optional technical features of the present application can be combined with each other to form new technical solutions, unless otherwise specified.

[0034] Unless otherwise defined, 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; the terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting upon the scope of the application; and any parameters recited herein are measured using the various measurement methods as are commonly employed by those of ordinary skill in the art (e.g., can be tested according to the methods given in the examples of the present application), unless otherwise indicated.

[0035] In the description of the present application, the terms "first", "second" are only for the purpose of description and can not be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. The "first feature", "second feature" can include one or more of the features.

[0036] In the description of the present application, "A and / or B" can include any one of the case of A alone, the case of B alone, the case of A and B, where A, B are only for example, which can be any technical feature connected by "and / or" in the present application.

[0037] The core components of a nuclear battery are a radiation source and an energy conversion device. Compared with nuclear batteries using alpha rays and gamma rays as radiation sources, nuclear batteries using beta rays exhibit higher safety factors, smaller radiation damage, and better working stability. The working principle of a beta-type nuclear battery is that beta particles collide with atoms to generate electron-hole pairs, and these carriers are then converted into an electric current, thereby realizing the conversion of nuclear energy into electrical energy. However, in the practical application of beta-type nuclear batteries, the traditional PN or PIN junction device structure has some limitations. These structures have a narrow space charge region, which limits the effective separation of excited electron-hole pairs, increases the probability of electron and hole recombination, and thus reduces the energy conversion efficiency of the nuclear battery. In order to improve the separation rate of electron-hole pairs, one possible solution is to use high-energy beta particles, but high-energy beta particles can cause damage to the materials in the nuclear battery, affecting the long-term stability of the nuclear battery and thus affecting its service life. Therefore, developing an energy conversion device with long-term stability has become a problem to be solved.

[0038] In a first aspect of the present application, the present application provides an energy conversion device, comprising: a first electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer, and a second electrode which are stacked.

[0039] The passivation layer covers the surface of the electron transport layer, and the passivation layer acts as a barrier to prevent water and oxygen in the external environment from invading the perovskite absorption layer, reducing material degradation and performance decay caused thereby, thereby improving the long-term stability of the nuclear battery; and during use of the beta-type nuclear battery, the energy of the excess beta rays can be deposited in the passivation layer, and the passivation layer reduces the damage of high-energy electrons to the electron transport layer, thereby further improving the long-term stability of the nuclear battery. Therefore, through the synergistic effect of the first electrode, the passivation layer, the electron transport layer, the perovskite absorption layer, the hole transport layer, and the second electrode, the long-term stability and service life of the energy conversion device are improved.

[0040] In some embodiments, the number of layers of the passivation layer includes at least one layer. Specifically, the passivation layer includes but is not limited to 1 layer, 2 layers, 3 layers, or 4 layers. In this way, by designing the number of layers of the passivation layer, the protection of the perovskite absorption layer can be enhanced, and the erosion of environmental factors such as water and oxygen can be reduced; at the same time, the energy of the excess beta rays can be deposited in the passivation layer, thereby improving the long-term stability of the energy conversion device.

[0041] In some embodiments, the material of the passivation layer includes at least one of Mg, Ni, Cd, Zn, In, Pb, Mo, Sb, Bi, Cu, Ti, Mn, V, and Sn corresponding metal oxides, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). In this way, by selecting a suitable passivation layer material, it has a high damage threshold and a low atomic number, a high damage threshold means that the material can withstand a higher energy input without structural damage or performance degradation, which helps to protect the operation stability of the energy conversion device in a high-energy radiation environment; a material with a low atomic number has a lower density and a smaller atomic mass, so the probability of interaction with incident particles (such as beta rays) is reduced, thereby reducing energy loss and radiation damage, and thus helping to improve the long-term stability and service life of the energy conversion device.

[0042] In some embodiments, the material of the perovskite absorption layer satisfies the chemical formula APbX3, wherein A includes at least one of MA + , FA + , and Cs + ; X includes at least one of Cl - , Br - , and I - . In this way, the perovskite absorption layer has better thermal stability and chemical stability, which helps to improve the reliability and long-term stability of the energy conversion device in harsh environments.

[0043] In some embodiments, when A is Cs + , the perovskite is a mixed anion type all-inorganic perovskite.

[0044] In some embodiments, when A is FA a Cs 1-a-b MA b , 1 > 1 - a - b > 0, the perovskite is a mixed anion-cation organic-inorganic hybrid perovskite material.

[0045] In some embodiments, the material of the electron transport layer includes at least one of [6,6]-phenyl-C-butanoic acid isomethyl ester (PCBM), fullerene and derivatives thereof. Thereby, the electron transport layer material is selected to have a high damage threshold and a low atomic number, the high damage threshold means that the material can withstand higher energy input without structural damage or performance degradation, which helps to protect the energy conversion device from running stability in high energy radiation environment; the material with low atomic number has lower density and smaller atomic mass, so as to reduce the interaction probability with incident particles (such as beta rays), thereby reducing energy loss and radiation damage, thus helping to improve the long-term stability and service life of the energy conversion device.

[0046] In some embodiments, the PCBM includes but is not limited to PC 61 BM or PC 71 BM.

[0047] In some embodiments, the fullerene and derivatives thereof include at least one of C 60 , C 70 .

[0048] In some embodiments, the material of the hole transport layer includes at least one of poly(3,4-ethylenedioxythiophene) material: polystyrene sulfonate (PEDOT: PSS), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl) phenylamine), polybis(4-phenyl), poly(bis(4-phenyl)(2,4,6-trimethylphenyl) amine) (PTAA), nickel oxide, metal element doped nickel oxide; wherein the metal element in the metal element doped nickel oxide includes at least one of Ag, Au, Cu, Cs, K. Thereby, the hole transport layer with appropriate material can improve the hole transport efficiency and reduce the energy loss.

[0049] In some embodiments, the first electrode includes a metal electrode.

[0050] In some embodiments, the material of the metal electrode includes at least one of Ag, Au, Ge, Ni. Thereby, the first electrode with appropriate material can improve the conductivity of the first electrode.

[0051] In some embodiments, the second electrode includes a transparent electrode.

[0052] In some embodiments, the material of the transparent electrode comprises at least one of ITO, FTO, AZO.

[0053] In some embodiments, the thickness of the first electrode layer is 20-80 nm.

[0054] As an example, the thickness of the first electrode can be 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, or 80 nm.

[0055] In some embodiments, the thickness of the passivation layer is 5-10 nm.

[0056] As an example, the thickness of the passivation layer can be 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.

[0057] In some embodiments, the thickness of the electron transport layer is 10-20 nm.

[0058] As an example, the thickness of the electron transport layer can be 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, or 20 nm.

[0059] In some embodiments, the thickness of the perovskite absorption layer is 500-2000 nm.

[0060] As an example, the thickness of the perovskite absorption layer can be 500 nm, 700 nm, 900 nm, 1100 nm, 1300 nm, 1500 nm, 1700 nm, 1900 nm, or 2000 nm.

[0061] In some embodiments, the thickness of the hole transport layer is 20-50 nm.

[0062] As an example, the thickness of the hole transport layer can be 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm.

[0063] In some embodiments, the thickness of the second electrode is 100-200 nm.

[0064] As an example, the thickness of the second electrode can be 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, or 200 nm.

[0065] In the second aspect of the present application, the present application provides a method for preparing an energy conversion device, forming a hole transport layer on one side of a second electrode; forming a perovskite absorption layer on the side of the hole transport layer away from the second electrode; forming an electron transport layer on the side of the perovskite absorption layer away from the hole transport layer; forming a passivation layer on the side of the electron transport layer away from the perovskite absorption layer; and forming a first electrode on the side of the passivation layer away from the electron transport layer. Thus, the energy conversion device is prepared by orderly constructing each functional layer, which enhances the long-term stability of the energy conversion device; at the same time, the manufacturing process is simplified, which is helpful to realize the batch production and cost control of the energy conversion device.

[0066] In some embodiments, the second electrode needs to be cleaned before use, and after the cleaning treatment is completed, it is placed in an oxygen plasma environment for treatment.

[0067] In some embodiments, the cleaning treatment includes, in sequence, a dishwashing liquid solution cleaning treatment, a deionized water cleaning treatment, an ethanol cleaning treatment, and an isopropanol cleaning treatment.

[0068] In some embodiments, the oxygen plasma environment treatment time is 10-20 min.

[0069] For example, the oxygen plasma environment treatment time can be 10 min, 12 min, 14 min, 16 min, 18 min, or 20 min.

[0070] In some embodiments, the method for forming the hole transport layer includes at least one of a precursor solution spin coating method, a magnetron sputtering method, and a precursor solution blade coating method.

[0071] In some embodiments, the precursor solution spin coating method includes: after the precursor solution is spin coated on the surface of the second electrode, annealing treatment is performed, and the hole transport layer is obtained after the annealing treatment is completed.

[0072] In some embodiments, the concentration of the precursor solution is 1.8-2.6 mg / mL.

[0073] For example, the concentration of the precursor solution can be 1.8 mg / mL, 2.0 mg / mL, 2.2 mg / mL, 2.4 mg / mL, or 2.6 mg / mL.

[0074] In some embodiments, the spin coating speed of the precursor solution is 4000-8000 rpm.

[0075] For example, the spin coating speed of the precursor solution can be 4000 rpm, 5000 rpm, 6000 rpm, 7000 rpm, or 8000 rpm.

[0076] In some embodiments, the annealing temperature is 80-120°C.

[0077] As an example, the annealing temperature can be 80°C, 90°C, 100°C, 110°C, or 120°C.

[0078] In some embodiments, the annealing time is 8-12 min.

[0079] As an example, the annealing time can be 8 min, 9 min, 10 min, 11 min, or 12 min.

[0080] In some embodiments, the method of forming the perovskite absorption layer comprises a precursor solution spin coating method.

[0081] In some embodiments, the precursor solution spin coating method comprises: after spin coating the precursor solution on the surface of the hole transport layer, performing annealing treatment, and obtaining the perovskite absorption layer after the annealing is completed.

[0082] In some embodiments, the concentration of the precursor solution is 1-2 mg / mL.

[0083] As an example, the concentration of the precursor solution can be 1 mg / mL, 1.2 mg / mL, 1.4 mg / mL, 1.6 mg / mL, 1.8 mg / mL, or 2 mg / mL.

[0084] In some embodiments, the precursor solution needs to be stirred for 10-16 h before spin coating.

[0085] As an example, the stirring time can be 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, or 16 h.

[0086] In some embodiments, an anti-solvent is added on the surface of the precursor solution after spin coating. In this way, the formation of the perovskite film is promoted. In some embodiments, the anti-solvent comprises at least one of chlorobenzene, dimethyl ethyl carbonate, ethyl acetate, toluene.

[0087] In some embodiments, the annealing temperature is 80-200°C.

[0088] As an example, the annealing temperature can be 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, or 200°C.

[0089] In some embodiments, the annealing time is 10-30 min.

[0090] As an example, the annealing time can be 10 min, 15 min, 20 min, 25 min, or 30 min.

[0091] In some embodiments, the precursor solution comprises a precursor powder and a solvent.

[0092] In some embodiments, the solvent comprises at least one of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol, isopropyl ketone.

[0093] In some embodiments, the method for preparing the precursor powder comprises mixing AX and PbX powders, and then preparing the precursor powder by a ball milling method or a manual grinding method, A comprises at least one of MA + , FA + , Cs + .

[0094] In some embodiments, the method for forming the electron transport layer comprises at least one of a precursor solution spin coating method, a magnetron sputtering method, a precursor solution doctor blade coating method, and a thermal evaporation co-evaporation method.

[0095] In some embodiments, the precursor solution spin coating method comprises the following steps: spin coating the precursor solution on the surface of the perovskite absorption layer, and then performing annealing treatment, and obtaining the electron transport layer after the annealing treatment is completed.

[0096] In some embodiments, the concentration of the precursor solution is 1 mg / mL-25 mg / mL.

[0097] For example, the concentration of the precursor solution can be 1 mg / mL, 5 mg / mL, 10 mg / mL, 15 mg / mL, 20 mg / mL, or 25 mg / mL.

[0098] In some embodiments, the spin coating speed of the precursor solution is 4000 rpm-6000 rpm.

[0099] For example, the spin coating speed of the precursor solution can be 4000 rpm, 4500 rpm, 5000 rpm, 5500 rpm, or 6000 rpm.

[0100] In some embodiments, the annealing temperature is 80°C-120°C.

[0101] For example, the annealing temperature can be 80°C, 90°C, 100°C, 110°C, or 120°C.

[0102] In some embodiments, the annealing time is 5 min-10 min.

[0103] For example, the annealing time can be 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min.

[0104] In some embodiments, the method for forming the passivation layer comprises at least one of a spin coating method and a thermal evaporation co-evaporation method.

[0105] In some embodiments, the step of spin-coating method comprises spin-coating the solution-gel on the surface of the electron transport layer to obtain the passivation layer.

[0106] In some embodiments, the spin-coating speed of the solution-gel is 1000 rpm-2000 rpm.

[0107] For example, the spin-coating speed of the solution-gel can be 1000 rpm, 1200 rpm, 1400 rpm, 1600 rpm, 1800 rpm or 2000 rpm.

[0108] In some embodiments, the step of thermal evaporation co-evaporation method comprises evaporating BCP on the surface of the electron transport layer in a thermal evaporation vacuum chamber to form the passivation layer.

[0109] In some embodiments, the evaporation rate is

[0110] For example, the evaporation rate can be

[0111] In some embodiments, the evaporation time is 3 min-120 min.

[0112] For example, the evaporation time can be 3 min, 10 min, 20 min, 50 min, 70 min, 100 min or 120 min.

[0113] In some embodiments, the method for forming the first electrode comprises at least one of the thermal evaporation co-evaporation method, the magnetron sputtering method.

[0114] In some embodiments, the step of thermal evaporation co-evaporation method comprises evaporating a metal thin film on the surface of the passivation layer to obtain the first electrode.

[0115] In some embodiments, the evaporation rate is

[0116] For example, the evaporation rate can be

[0117] In some embodiments, the evaporation time is 3 min-140 min.

[0118] For example, the evaporation time can be 3 min, 10 min, 20 min, 50 min, 70 min, 100 min, 120 min or 140 min.

[0119] In a third aspect, the present application provides a long-term energy supply device comprising the energy conversion device described above, or the energy conversion device prepared by the method described above, and a beta-type radiation source located close to the first electrode.

[0120] The working principle of the long-term energy supply device of the present application is as follows: beta rays (high-energy electrons) are incident from the first electrode, and in the process of passing through the first electrode, the passivation layer and the electron transport layer in sequence, the high-energy electrons collide with the materials in the layers, and a part of the energy of the high-energy electrons is lost; the remaining high-energy electrons collide with the atoms inside the perovskite absorption layer after reaching the perovskite absorption layer, causing the electrons in the valence band of the atoms to be excited to the conduction band to form electron-hole pairs, and the electron-hole pairs form free carriers through the drift and diffusion motion of the PIN junction, and the carriers are led out through the electrodes on both sides of the energy conversion device to form an electric current to supply power to external equipment. The long-term energy supply device can effectively convert the energy of beta rays into electrical energy, thereby realizing long-term stable power output.

[0121] In some embodiments, the beta-type radiation source comprises at least one of 3 H and its compounds, 14 C and its compounds, 35 S and its compounds, 63 Ni and its compounds, 85 Kr and its compounds, 90 Sr and its compounds, 90 Y and its compounds. Thus, the radiation source used in the present application is a pure beta-ray isotope source. Compared with alpha rays and gamma rays, the radiation source used in the present application has a longer half-life and a smaller radiation energy. The longer half-life means that the atomic nucleus of the isotope remains stable for a longer period of time, thereby providing continuous energy output. The smaller radiation energy means that the beta particles have lower kinetic energy when they decay, which helps to reduce the damage of the beta particles to the surrounding materials. Therefore, the longer half-life and the smaller radiation energy increase the long-term stability and safety of the nuclear battery.

[0122] The scheme of the present application will be described below through specific examples. It should be noted that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. If the specific technology or condition is not specified in the examples, the technology or condition described in the literature or according to the product manual is used. If the reagent or instrument is not specified by the manufacturer, it is a conventional product that can be obtained by purchase.

[0123] Example 1

[0124] A long-term energy supply device, referring to Figure 1From top to bottom, successively include beta isotope radiation source 1, metal electrode 2, passivation layer 3, electron transport layer 4, perovskite absorption layer 5, hole transport layer 6, transparent electrode 7.

[0125] Specifically, the preparation process of a long-time energy supply device is as follows:

[0126] The ITO-coated glass substrate is sequentially placed in a detergent solution, deionized water, ethanol and isopropanol for ultrasonic cleaning, each for 20 min; after cleaning, the solution on the surface of the ITO-coated glass substrate is blown off with a nitrogen gun; finally, the ITO-coated glass substrate is placed in an oxygen plasma environment for 10 min; ITO is used as the transparent electrode 7, and the thickness of the transparent electrode 7 is 120 nm.

[0127] A PATT solution with a concentration of 2.2 mg / mL (solvent: chlorobenzene) is prepared, and the PATT solution is spin-coated on the ITO layer of the transparent electrode 7 at a speed of 6000 rpm; then the glass substrate is placed on a hot stage at 100°C for annealing for 10 min, to obtain a hole transport layer 6 with a thickness of 40 nm.

[0128] MAI and PbI2 powders with a molar ratio of 1:1 and MABr and PbBr2 powders with a molar ratio of 1:1 are respectively placed in a ball mill to synthesize MAPbI3 and MAPbBr3 powders at room temperature; then, MAPbI3 and MAPbBr3 powders with a molar ratio of 1:4 are placed in a ball mill to prepare MAPb(I 0.2 Br 0.8 )3 powders at room temperature; then a MAPb(I 0.2 Br 0.8 )3 solution with a concentration of 1.5 mol / L (solvent: a mixed solution of DMF and DMSO) is prepared; after the MAPb(I 0.2 Br 0.8 )3 solution is stirred for 12 h, it is spin-coated on the surface of the hole transport layer 6, and at the same time, an appropriate amount of anti-solvent toluene is added dropwise on the surface of the perovskite solution to induce rapid crystallization to form a uniform perovskite film; then the glass substrate is quickly placed on a hot stage at 110°C for annealing for 20 min, to obtain a perovskite absorption layer 5 with a thickness of 1000 nm.

[0129] A PC 61 BM solution with a concentration of 20 mg / mL (solvent: chlorobenzene) is prepared, and the PC 61 BM solution is spin-coated on the surface of the perovskite absorption layer 5 at a speed of 5000 rpm; then the glass substrate is placed on a hot stage at 100°C for annealing for 5 min, to obtain an electron transport layer 4 with a thickness of 18 nm.

[0130] The glass substrate is transferred to a thermal evaporation vacuum chamber, and a 100 nm thick Ag layer is evaporated on the surface of the electron transport layer 4 as a metal electrode 2. A BCP film is evaporated on the surface of the electron transport layer 4 at a rate of 0.1 nm / min for 20 min to obtain a passivation layer 3 with a thickness of 10 nm.

[0131] A Ag film is evaporated on the surface of the passivation layer 3 at a rate of 0.5 nm / min for 20 min to obtain a metal electrode 2 with a thickness of 50 nm.

[0132] Thus, the energy conversion device of Example 1 is obtained.

[0133] A radiation source 13 H is placed above the energy conversion device (the arrow is the incident direction of the beta rays), i.e. above the metal electrode 2, and is fixed using a metal frame, and finally is encapsulated using a radiation-proof material, thus obtaining the long-time energy supply device of Example 1. Figure 1

[0134] Example 2

[0135] A long-time energy supply device sequentially comprises, from top to bottom, a beta isotope radiation source, a metal electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer and a transparent electrode.

[0136] Specifically, the preparation process of a long-time energy supply device is as follows:

[0137] The ITO-coated glass substrate is sequentially placed in a detergent solution, deionized water, ethanol and isopropanol for ultrasonic cleaning, each for 20 min; after cleaning, the solution on the surface of the ITO-coated glass substrate is blown off using a nitrogen gun; finally, the ITO-coated glass substrate is placed in an oxygen plasma environment for 10 min, and ITO is used as a transparent electrode with a thickness of 120 nm.

[0138] The glass substrate is placed in a magnetron sputtering chamber, and a NiO x film is sputtered on the ITO layer using a radio frequency magnetron sputtering method to obtain a hole transport layer with a thickness of 40 nm.

[0139] The powders of CsI and PbI2 with a molar ratio of 1:1 are placed in a mortar and ground to prepare CsPbI3 powder, and then a CsPbI3 solution with a concentration of 1.7 mol / L (the solvent is a mixed solution of DMF and DMSO) is prepared; after the CsPbI3 solution is stirred for 12 h, it is spin-coated on the surface of the hole transport layer to form a uniform perovskite film, and then the glass substrate is quickly placed on a hot stage at 180°C for annealing for 30 min to obtain a perovskite absorption layer with a thickness of 1000 nm.

[0140] A C 60 solution with a concentration of 3 mg / mL (the solvent is chlorobenzene) is prepared, and the C 60 ​​The solution was spin-coated on the surface of the perovskite absorption layer at a speed of 4000 rpm, and then the glass substrate was placed on a hot stage at 100℃ for annealing for 10 min to obtain an electron transport layer with a thickness of 10 nm.

[0141] SnCl4·5H2O was mixed with a solution of tetramethylammonium hydroxide, and then heated at 100℃ for 12 h to obtain SnO2 sol-gel; the SnO2 sol-gel was spin-coated on the surface of the electron transport layer at a speed of 2000 rpm to obtain a passivation layer with a thickness of 10 nm.

[0142] Au thin film was deposited on the surface of the passivation layer at a deposition rate of 0.1 nm / s for 20 min to obtain a metal electrode with a thickness of 50 nm.

[0143] Thus, the energy conversion device of Example 2 was obtained.

[0144] A radiation source 63 Ni was placed above the energy conversion device, i.e. above the metal electrode, and was fixed by a metal frame, and finally was encapsulated by a radiation-proof material, thus obtaining the long-time energy supply device of Example 2.

[0145] Example 3

[0146] A long-time energy supply device sequentially comprises, from top to bottom, a beta isotope radiation source, a metal electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer, and a transparent electrode.

[0147] Specifically, the preparation process of a long-time energy supply device is as follows:

[0148] The ITO-coated glass substrate was sequentially placed in a detergent solution, deionized water, ethanol, and isopropanol for ultrasonic cleaning, each for 20 min; after cleaning, the solution on the surface of the ITO-coated glass substrate was blown off by a nitrogen gun; finally, the ITO-coated glass substrate was placed in an oxygen plasma environment for 10 min, and ITO was used as a transparent electrode with a thickness of 120 nm.

[0149] The PEDOT:PSS solution was spin-coated on the ITO layer at a speed of 6000 rpm; then the glass substrate was placed on a hot stage at 100℃ for annealing for 10 min to obtain a hole transport layer with a thickness of 40 nm.

[0150] FAPbI3 and MAPbBr3 powders were synthesized by placing molar ratio of 1:1 of FAI and PbI2, and molar ratio of 1:1 of MABr and PbBr2 powders in a ball mill at room temperature, respectively; then, molar ratio of 3:7 of FAPbI3 and MAPbBr3 powders were placed in a ball mill to prepare FA 0.3 MA​0.7 Pb(I 0.3 Br 0.7 )3 powder; then prepare FA 0.3 MA 0.7 Pb(I 0.3 Br 0.7 )3 solution (solvent is a mixed solution of DMF and DMSO); after stirring the FA 0.3 MA 0.7 Pb(I 0.3 Br 0.7 )3 solution for 12 h, spin it on the surface of the hole transport layer, at the same time, drop a proper amount of anti-solvent toluene on the surface of the perovskite solution to induce rapid crystallization to form a uniform perovskite film, then quickly place the glass substrate on a hot stage at 110°C to anneal for 20 min, and obtain a perovskite absorption layer with a thickness of 1000 nm.

[0151] Prepare a PC 71 BM solution (solvent is chlorobenzene) with a concentration of 20 mg / mL, and spin the PC 71 BM solution on the surface of the perovskite absorption layer at a speed of 5000 rpm, then place the glass substrate on a hot stage at 100°C to anneal for 5 min, and obtain an electron transport layer with a thickness of 18 nm.

[0152] Transfer the glass substrate to a thermal evaporation vacuum chamber, and evaporate a BCP film on the surface of the electron transport layer at a rate of 0.1 nm / min for 20 min, and obtain a passivation layer with a thickness of 10 nm.

[0153] Evaporate an Au film on the surface of the passivation layer at a rate of 0.1 nm / min for 20 min, and obtain a metal electrode with a thickness of 50 nm.

[0154] Thus, the energy conversion device of Example 3 is obtained.

[0155] Place a radiation source 85 Kr above the energy conversion device, i.e. above the metal electrode, and fix it with a metal frame, and finally encapsulate it with a radiation-proof material, and thus obtain the long-time energy supply device of Example 1.

[0156] Example 4

[0157] The difference between Example 4 and Example 1 is that two passivation layers are provided, which are a first passivation layer and a second passivation layer.

[0158] Specifically, the preparation method of the first passivation layer is as follows: SnCl4·5H2O is mixed with a tetramethylammonium hydroxide solution, and then SnO2 sol-gel is prepared by heating at 100 ℃ for 12 h; the SnO2 sol-gel is spin-coated on the surface of the electron transport layer at a speed of 2000 rpm to obtain a passivation layer with a thickness of 5 nm.

[0159] The preparation method of the second passivation layer is as follows: the glass substrate is transferred into a thermal evaporation vacuum chamber, and a BCP thin film is evaporated on the surface of the first passivation layer at a rate of 0.1 nm / s to obtain a passivation layer with a thickness of 5 nm.

[0160] Example 5: Example 5 differs from Example 4 in that the first passivation layer and the second passivation layer are interchanged.

[0161] Comparative Example 1: Comparative Example 1 differs from Example 1 in that no passivation layer is provided.

[0162] Comparative Example 2: Comparative Example 2 differs from Example 1 in that a long-time energy supply device comprises, from top to bottom, a beta isotope radiation source, a metal electrode, an electron transport layer, a passivation layer, a perovskite absorption layer, a hole transport layer, and a transparent electrode.

[0163] Comparative Example 3: Comparative Example 3 differs from Example 1 in that a long-time energy supply device comprises, from top to bottom, a beta isotope radiation source, a metal electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, a passivation layer, and a transparent electrode.

[0164] The long-time energy supply devices of Examples 1-5 and Comparative Examples 1-3 are subjected to performance testing, and the performance testing method is as follows: a 3.05 nA electron beam is incident from the metal electrode side at gradually increasing acceleration voltages, the U-I characteristic curve of the nuclear battery is measured, and the maximum radiation damage threshold is calculated.

[0165] The performance test results of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.

[0166] Table 1

[0167]

[0168] As shown in Table 1, in Examples 1-5, a passivation layer is provided between the electron transport layer and the metal electrode, the passivation layer not only protects the perovskite absorption layer, but also absorbs excess beta ray energy, so that the energy deposited by the electron transport layer is reduced, thereby reducing the degree of radiation damage to the electron transport layer, and thus Examples 1-5 have a higher radiation damage threshold.

[0169] ​The comparative example 1 does not set the passivation layer, so it cannot fully isolate the water and oxygen in the external environment, resulting in the water and oxygen invading the perovskite layer and reacting with the perovskite, causing the perovskite absorption layer to degrade; at the same time, the energy deposited in the electron transport layer is relatively large, causing the macrostructure and phase composition of the electron transport layer to change, resulting in a large degree of radiation damage to the electron transport layer, causing the energy conversion device to fail to work normally under a lower energy β-ray radiation, and the energy conversion efficiency to decrease by more than 90%, so the comparative example 1 has a lower radiation damage threshold.

[0170] In the comparative example 2, the metal electrode and the electron transport layer are not provided with a passivation layer between them, and the energy deposited in the electron transport layer is relatively large, causing the macrostructure and phase composition of the electron transport layer to change, resulting in a large degree of radiation damage to the electron transport layer, thereby causing the comparative example 2 to have a lower radiation damage threshold.

[0171] In the comparative example 3, the β-ray is absorbed by the perovskite absorption layer after passing through the metal electrode and the hole transport layer in turn, and there is no passivation layer to absorb the excess energy, causing a large degree of radiation damage to the hole transport layer and the perovskite layer, resulting in the comparative example 3 having a lower radiation damage threshold.

[0172] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and embodiments having the same technical idea and substantially the same function and effect as the technical solution of the present application are all included in the technical scope of the present application. In addition, within the scope of the main idea of the present application, various modifications of the embodiments that can be thought of by those skilled in the art, and other ways constructed by combining part of the constituent elements of the embodiments are also included in the scope of the present application.

Claims

1. A long-term power supply device, characterized in that, It includes an energy conversion device and a β-type radiation source located near the first electrode; The energy conversion device includes: a first electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer, and a second electrode stacked together. The passivation layer covers the surface of the electron transport layer; during the use of the β-type nuclear battery, the energy of the β-rays is deposited in the passivation layer; the energy conversion device is used in conjunction with a β-type radiation source located near the first electrode, and the β-rays are incident from the first electrode, pass through the first electrode, the passivation layer, and the electron transport layer in sequence, and then reach the perovskite absorption layer; The passivation layer comprises at least one layer; and / or, The passivation layer material includes at least one of Mg, Ni, Cd, Zn, In, Pb, Mo, Sb, Bi, Cu, Ti, Mn, V, and the metal oxide corresponding to Sn, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; thus, the passivation layer material has a high damage threshold and a low atomic number. The thickness of the first electrode is 20nm-80nm; By designing the number of layers in the passivation layer, the protection of the perovskite absorption layer is enhanced, and the erosion by environmental factors is reduced; at the same time, the energy of excess β rays is promoted to be deposited in the passivation layer.

2. The long-term power supply device according to claim 1, characterized in that, The material of the perovskite absorber layer satisfies the chemical formula APbX3, where A includes MA. + FA + Cs + At least one of them; X includes Cl - ,Br - I - At least one of them.

3. The long-term power supply device according to claim 1, characterized in that, The electron transport layer is made of at least one of fullerenes and their derivatives; and / or, The hole transport layer is made of at least one of the following materials: poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine), nickel oxide, and nickel oxide doped with a metal element; wherein the metal element in the nickel oxide doped with a metal element includes at least one of Ag, Au, Cu, Cs, and K.

4. The long-term power supply device according to claim 1, characterized in that, The first electrode includes a metal electrode; and / or, The second electrode includes a transparent electrode.

5. The long-term power supply device according to claim 1, characterized in that, The passivation layer has a thickness of 5nm-10nm; and / or, The thickness of the electron transport layer is 10nm-20nm; and / or, The thickness of the perovskite absorber layer is 500 nm-2000 nm; and / or, The thickness of the hole transport layer is 20nm-50nm; and / or, The thickness of the second electrode is 100nm-200nm.

6. The long-term power supply device according to claim 1, characterized in that, The β-type radioactive source includes 3 H and its compounds, 14 C and its compounds, 35 S and its compounds, 63 Ni and its compounds, 85 Kr and its compounds, 90 Sr and its compounds, 90 Y and at least one of its compounds.

7. A method for preparing an energy conversion device for a long-term power supply device as described in any one of claims 1-6, characterized in that, include: A hole transport layer is formed on one side of the second electrode; A perovskite absorption layer is formed on the side of the hole transport layer away from the second electrode; An electron transport layer is formed on the side of the perovskite absorber layer away from the hole transport layer; A passivation layer is formed on the side of the electron transport layer away from the perovskite absorption layer; The first electrode is formed on the side of the passivation layer away from the electron transport layer; The passivation layer covers the surface of the electron transport layer; during the use of the β-type nuclear battery, the energy of the β-rays is deposited in the passivation layer; the energy conversion device is used in conjunction with a β-type radiation source located near the first electrode, and the β-rays are incident from the first electrode, pass through the first electrode, the passivation layer, and the electron transport layer in sequence, and then reach the perovskite absorption layer; The passivation layer comprises at least one layer; and / or, The passivation layer material includes at least one of Mg, Ni, Cd, Zn, In, Pb, Mo, Sb, Bi, Cu, Ti, Mn, V, and the metal oxide corresponding to Sn, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; thus, the passivation layer material has a high damage threshold and a low atomic number. The thickness of the first electrode is 20nm-80nm; By designing the number of layers in the passivation layer, the protection of the perovskite absorption layer is enhanced, and the erosion by environmental factors is reduced; at the same time, the energy of excess β rays is promoted to be deposited in the passivation layer.

8. The method according to claim 7, characterized in that, The method for forming the hole transport layer includes at least one of the following: spin coating of precursor liquid, magnetron sputtering, and blade coating of precursor liquid; and / or The method for forming the perovskite absorber layer includes a precursor solution spin coating method; and / or... The method for forming the electron transport layer includes at least one of the following: spin coating with a precursor solution, magnetron sputtering, blade coating with a precursor solution, and thermal evaporation co-evaporation; and / or, The method for forming the passivation layer includes at least one of spin coating, thermal evaporation co-evaporation, and / or... The method for forming the first electrode includes at least one of thermal evaporation co-evaporation and magnetron sputtering.

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