Energy conversion device, preparation method thereof and long-time energy supply device

Abstract

The invention discloses an energy conversion device, 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 stacked. According to the invention, the passivation layer covers the surface of the electron transmission layer, and the passivation layer is used as a barrier to prevent water and oxygen in an external environment from invading the perovskite absorption layer, thereby reducing material degradation and performance degradation caused by the invasion, and improving the long-term stability of the nuclear battery. And in the use process of the beta-type nuclear battery, redundant beta-ray energy can be deposited in the passivation layer, and the passivation layer reduces the damage of high-energy electrons to the electron transport layer, so that the long-term stability of the nuclear battery is further improved. 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 of the energy conversion device is improved, and the service life of the energy conversion device is prolonged.

Description

Technical Field

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

[0002] In order to reduce greenhouse gas emissions and cope with global climate change, it is particularly important to find clean, renewable new energy sources to replace traditional fossil fuels. Radioisotope-driven nuclear batteries have been widely used in key fields such as medicine, military and aerospace due to their advantages such as no pollution gas emissions, long service life, continuous power supply and high energy density. In the design of nuclear batteries, three types of radiation produced by isotope decay need to be considered: alpha rays, beta rays and gamma rays. Especially for alpha rays and gamma rays, they have extremely high energy and penetration ability, which will cause a certain degree of damage to nuclear battery components, thereby affecting the performance and safety of the equipment. Therefore, the design of nuclear batteries needs to be further optimized to reduce the negative impact of these high-energy radiation on the equipment.

[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 prior art. Summary of the invention

[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 arranged in a stacked manner. The passivation layer of the present application 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, thereby reducing the material degradation and performance attenuation caused thereby, thereby improving the long-term stability of the nuclear battery; and 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, the present application improves the long-term stability and service life of the energy conversion device 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.

[0005] In some embodiments, the number of layers of the passivation layer includes at least one layer. Thus, 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 promoted to 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 includes at least one of Mg, Ni, Cd, Zn, In, Pb, Mo, Sb, Bi, Cu, Ti, Mn, V, and metal oxides corresponding to Sn, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. Thus, a suitable passivation layer material is selected to have a high damage threshold and a low atomic number. A high damage threshold means that the material can withstand a high energy input without structural damage or performance degradation, which helps to protect the operating 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, thereby reducing the probability of interaction with incident particles (such as beta rays), thereby reducing energy loss and radiation damage, and 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 absorber layer satisfies the chemical formula APbX3, wherein A includes MA + , FA + , Cs + At least one of; X includes Cl - Br - ,I - Thus, by selecting a perovskite absorption layer of appropriate material, the perovskite absorption layer has better thermal stability and chemical stability, which is beneficial 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 includes at least one of [6,6]-phenyl-C-butyric acid isomethyl ester, fullerene and its derivatives. Thus, a suitable electron transport layer material is selected to have a high damage threshold and a low atomic number. A high damage threshold means that the material can withstand a high energy input without structural damage or performance degradation, which helps to protect the operating 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, thereby reducing the probability of interaction with incident particles (such as beta rays), thereby reducing energy loss and radiation damage, and 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 includes at least one of poly(3,4-ethylenedioxythiophene) 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, and 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, and K. Thus, by selecting a hole transport layer of suitable material, 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 nm-80 nm.

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

[0014] In some embodiments, the electron transport layer has a thickness of 10 nm to 20 nm.

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

[0016] In some embodiments, the hole transport layer has a thickness of 20 nm to 50 nm.

[0017] In some embodiments, the second electrode has a thickness of 100 nm-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 enhances the long-term stability of the energy conversion device by orderly constructing each functional layer; at the same time, the manufacturing process is simplified, which helps to achieve mass 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 liquid spin coating method, a magnetron sputtering method, and a precursor liquid scraping method.

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

[0021] In some embodiments, the method for forming the electron transport layer includes at least one of a precursor liquid spin coating method, a magnetron sputtering method, a precursor liquid scraping method, and a thermal evaporation co-evaporation method.

[0022] 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.

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

[0024] In the third aspect of the present application, the present application provides a long-term energy supply device, including the aforementioned energy conversion device, or the energy conversion device obtained by the aforementioned energy conversion device preparation method, and a β-type radiation source located near the first electrode. The working principle of the long-term energy supply device of the present application is: β 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 layer, and the energy of the high-energy electrons will be lost in part; after the remaining high-energy electrons reach the perovskite absorption layer, they collide with the atoms inside the perovskite absorption layer, so that the electrons in the valence band of the atoms are excited to the conduction band, forming electron-hole pairs, and the electron-hole pairs form free carriers through the drift diffusion movement of the PIN junction, and the carriers are drawn out through the electrodes on both sides of the energy conversion device to form a current to power the external device. This kind of long-term energy supply device can effectively convert the energy of the β rays into electrical energy, thereby realizing long-term and stable power output of the long-term energy supply device.

[0025] In some embodiments, the beta-radiation source comprises 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 At least one of Y and its compounds. Therefore, the radiation source used in the present application is a pure β-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 THE DRAWINGS

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

[0027] Figure 1It is a schematic structural diagram of a long-time energy supply device in one embodiment of the present application.

[0028] Description 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] Below, an energy conversion device, a method for preparing the same, and an implementation method of a long-time energy supply device of the present application are specifically disclosed with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following descriptions are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0031] " Scope " disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be to include end values ​​or not include end values, and can be combined arbitrarily, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 listed, and if the maximum range values ​​3,4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0032] If not otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0033] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0034] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by technicians in the technical field to which this application belongs; the terms used in this application are only for the purpose of describing specific embodiments and are not intended to limit this application; unless otherwise specified, the numerical values ​​of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of this application).

[0035] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. "First feature" and "second feature" may include one or more of the features.

[0036] In the description of the present application, "A and / or B" may include the case of A alone, the case of B alone, or any of the cases of A and B, where A and B are only used for examples and may be any technical feature connected by "and / or" in the present application.

[0037] The core components of nuclear batteries are radiation sources and energy conversion devices. Compared with nuclear batteries that use α rays and γ rays as radiation sources, nuclear batteries that use β rays show higher safety factors, less irradiation damage, and better working stability. The working principle of β-type nuclear batteries is that β particles collide with atoms to produce electron-hole pairs, and these carriers are then converted into current, thereby realizing the conversion of nuclear energy into electrical energy. However, in the practical application of β-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 recombination probability of electrons and holes, and thus reduces the energy conversion efficiency of nuclear batteries. In order to improve the separation rate of electron-hole pairs, a possible solution is to use high-energy β particles, but high-energy β particles will damage the materials in the nuclear battery, affect the long-term stability of the nuclear battery, and then affect its service life. Therefore, the development of an energy conversion device with long-term stability has become an urgent 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 arranged in a stacked manner.

[0039] 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, reducing the material degradation and performance decay caused thereby, thereby improving the long-term stability of the nuclear battery; and 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, the present application improves the long-term stability and service life of the energy conversion device 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.

[0040] In some embodiments, the number of passivation layers includes at least one layer. Specifically, the passivation layer includes but is not limited to 1 layer, 2 layers, 3 layers or 4 layers. Thus, by designing the number of passivation layers, 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 excess beta rays can be promoted to 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 metal oxides corresponding to Sn, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Thus, a suitable passivation layer material is selected to have a high damage threshold and a low atomic number. A high damage threshold means that the material can withstand a high energy input without structural damage or performance degradation, which helps to protect the operating 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, thereby reducing the probability of interaction with incident particles (such as beta rays), 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 absorber layer satisfies the chemical formula APbX3, wherein A includes MA + , FA + , Cs + At least one of; X includes Cl - Br - ,I - As a result, the perovskite absorption layer has better thermal stability and chemical stability, which is beneficial to improving the reliability and long-term stability of the energy conversion device in harsh environments.

[0043] In some embodiments, when A is Cs + When , 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 , when 1>1-ab>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-butyric acid isomethyl ester (PCBM), fullerene and its derivatives. Thus, a suitable electron transport layer material is selected to have a high damage threshold and a low atomic number. A high damage threshold means that the material can withstand a high energy input without structural damage or performance degradation, which helps to protect the operating 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, thereby reducing the probability of interaction with incident particles (such as beta rays), thereby reducing energy loss and radiation damage, and thus helping to improve the long-term stability and service life of the energy conversion device.

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

[0047] In some embodiments, fullerenes and their derivatives include C 60 , C 70 At least one of .

[0048] In some embodiments, the material of the hole transport layer includes at least one of poly(3,4-ethylenedioxythiophene) materials: polystyrene sulfonate (PEDOT:PSS), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), polybis(4-phenyl), poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA), nickel oxide, and 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, and K. Thus, selecting a hole transport layer of suitable material can improve hole transport efficiency and reduce energy loss.

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

[0050] In some embodiments, the material of the metal electrode includes at least one of Ag, Au, Ge, and Ni. Thus, selecting a first electrode of a suitable 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 includes at least one of ITO, FTO, and AZO.

[0053] In some embodiments, the first electrode layer has a thickness of 20 nm to 80 nm.

[0054] As an example, the thickness of the first electrode may 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 nm to 10 nm.

[0056] As an example, the thickness of the passivation layer may 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 nm to 20 nm.

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

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

[0060] As an example, the thickness of the perovskite absorber layer may 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 nm to 50 nm.

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

[0063] In some embodiments, the second electrode has a thickness of 100 nm to 200 nm.

[0064] As an example, the thickness of the second electrode may 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 prepared enhances the long-term stability of the energy conversion device by orderly constructing each functional layer; at the same time, the manufacturing process is simplified, which helps to achieve mass production and cost control of energy conversion devices.

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

[0067] In some embodiments, the cleaning process includes a detergent solution cleaning process, a deionized water cleaning process, an ethanol cleaning process, and an isopropyl alcohol cleaning process in sequence.

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

[0069] As an example, the duration of the oxygen plasma environment treatment may be 10 min, 12 min, 14 min, 16 min, 18 min or 20 min.

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

[0071] In some embodiments, the steps of the precursor solution spin coating method include: spin coating the precursor solution on the surface of the second electrode, and then performing annealing treatment, and obtaining a hole transport layer after the annealing is completed.

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

[0073] As an example, the concentration of the precursor solution may 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 rpm-8000 rpm.

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

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

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

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

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

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

[0081] In some embodiments, the steps of the precursor solution spin coating method include: spin coating the precursor solution on the surface of the hole transport layer, and then 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 mg / mL-2 mg / mL.

[0083] As an example, the concentration of the precursor solution may 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 before spin coating, and the stirring time is 10 hours to 16 hours.

[0085] As an example, the stirring time may 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 dropwise to the surface of the precursor solution after spin coating, thereby promoting the formation of the perovskite film. In some embodiments, the anti-solvent includes at least one of chlorobenzene, dimethyl ethyl carbonate, ethyl acetate, and toluene.

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

[0088] As an example, the annealing temperature may 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 min-30 min.

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

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

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

[0093] In some embodiments, the preparation method of the precursor powder is: after mixing AX and PbX powders, the precursor powder is prepared by ball milling or manual grinding, wherein A includes MA + , FA + , Cs + At least one of .

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

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

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

[0097] As an example, the concentration of the precursor solution may 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] As an example, the spin coating speed of the precursor solution may 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] As an example, the annealing temperature may 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] As an example, the annealing time may be 5 min, 6 min, 7 min, 8 min, 9 min or 10 min.

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

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

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

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

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

[0109] In some embodiments, the evaporation rate is

[0110] As an example, the evaporation rate can be

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

[0112] As an example, the evaporation time may be 3 min, 10 min, 20 min, 50 min, 70 min, 100 min or 120 min.

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

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

[0115] In some embodiments, the evaporation rate is

[0116] As an example, the evaporation rate can be

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

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

[0119] In the third aspect of the present application, the present application provides a long-term energy supply device, including the aforementioned energy conversion device, or an energy conversion device obtained by the aforementioned energy conversion device preparation method, and a β-type radiation source located on one side close to the first electrode.

[0120] The working principle of the long-term energy supply device of the present application is as follows: β 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 layer, and a part of the energy of the high-energy electrons will be lost; after the remaining high-energy electrons reach the perovskite absorption layer, they collide with the atoms inside the perovskite absorption layer, so that the electrons in the valence band of the atoms are excited to the conduction band, forming electron-hole pairs, and the electron-hole pairs form free carriers through the drift diffusion movement of the PIN junction, and the carriers are led out through the electrodes on both sides of the energy conversion device to form a current to power the external device. This kind of long-term energy supply device can effectively convert the energy of β rays into electrical energy, thereby achieving long-term and stable power output.

[0121] In some embodiments, the beta radiation source comprises 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 At least one of Y and its compounds. Therefore, the radiation source used in the present application is a pure β-ray isotope source. Compared with α-rays and γ-rays, the radiation source used in the present application has a longer half-life and a smaller radiation energy. A longer half-life means that the nucleus of the isotope remains stable for a longer time, thereby providing continuous energy output; a smaller radiation energy means that the β particles have lower kinetic energy when decaying, which helps to reduce the damage of the β particles to the surrounding materials. Therefore, a longer half-life and a smaller radiation energy increase the long-term stability and safety of the nuclear battery.

[0122] The scheme of the present application is described below by specific examples. It should be noted that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If no specific technology or conditions are specified in the examples, the technology or conditions described in the literature in this area or the product instructions are used. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be obtained commercially.

[0123] Example 1

[0124] A long-term energy supply device, reference Figure 1, from top to bottom, it includes a β-isotope radiation source 1, a metal electrode 2, a passivation layer 3, an electron transport layer 4, a perovskite absorption layer 5, a hole transport layer 6, and a transparent electrode 7.

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

[0126] The ITO coated glass substrate was placed in a detergent solution, deionized water, ethanol and isopropanol for ultrasonic cleaning in turn, with each ultrasonic cleaning lasting 20 minutes. After cleaning, the solution on the surface of the ITO coated glass substrate was blown away with a nitrogen gun. Finally, the ITO coated glass substrate was placed in an oxygen plasma environment for treatment for 10 minutes. ITO was used as the transparent electrode 7, and the thickness of the transparent electrode 7 was 120 nm.

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

[0128] The powders of MAI and PbI2 with a molar ratio of 1:1 and MABr and PbBr2 with a molar ratio of 1:1 were placed in a ball mill to synthesize MAPbI3 and MAPbBr3 powders at room temperature. Then, the powders of MAPbI3 and MAPbBr3 with a molar ratio of 1:4 were placed in a ball mill to prepare MAPb(I 0.2 Br 0.8 )3 powder; then prepare MAPb (I 0.2 Br 0.8 )3 solution (the solvent is a mixed solution of DMF and DMSO); MAPb(I 0.2 Br 0.8 )3 After the solution is stirred for 12 hours, it is spin-coated on the surface of the hole transport layer 6. At the same time, an appropriate amount of anti-solvent toluene is added to the surface of the perovskite solution to induce rapid crystallization to form a uniform perovskite film. The glass substrate is then quickly placed on a hot plate at 110°C and annealed for 20 minutes to obtain a perovskite absorption layer 5 with a thickness of 1000 nm.

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

[0130] The glass substrate is transferred to the thermal evaporation vacuum chamber. The BCP thin film was evaporated on the surface of the electron transport layer 4 at a rate of 20 minutes to obtain a passivation layer 3 with a thickness of 10 nm.

[0131] by A Ag thin film was evaporated on the surface of the passivation layer 3 at a deposition rate of 20 min to obtain a metal electrode 2 with a thickness of 50 nm.

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

[0133] The radiation source 13 H is placed above the energy conversion device ( Figure 1 The middle arrow is the incident direction of the β ray), that is, above the metal electrode 2, and is fixed with a metal frame, and finally packaged with a radiation-proof material, thereby obtaining the long-term energy supply device of Example 1.

[0134] Example 2

[0135] A long-time energy supply device 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, a preparation process of a long-term energy supply device is as follows:

[0137] The ITO coated glass substrate was placed in a detergent solution, deionized water, ethanol and isopropanol for ultrasonic cleaning in turn, with each ultrasonic cleaning lasting 20 minutes. After cleaning, the solution on the surface of the ITO coated glass substrate was blown away with a nitrogen gun. Finally, the ITO coated glass substrate was placed in an oxygen plasma environment for treatment for 10 minutes. ITO was used as a transparent electrode with a thickness of 120 nm.

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

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

[0140] Prepare C at a concentration of 3 mg / mL 60 Solution (the solvent is chlorobenzene), C 60The 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°C for annealing for 10 minutes to obtain an electron transport layer with a thickness of 10 nm.

[0141] SnCl4·5H2O and tetramethylammonium hydroxide solution were mixed and heated at 100°C for 12 hours to prepare 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] by Au thin film was evaporated on the surface of the passivation layer at a deposition rate of 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] The radiation source 63 Ni is placed above the energy conversion device, that is, above the metal electrode, and fixed with a metal frame, and finally packaged with radiation protection material, thereby obtaining the long-term energy supply device of Example 2.

[0145] Example 3

[0146] A long-time energy supply device 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, a preparation process of a long-term energy supply device is as follows:

[0148] The ITO coated glass substrate was placed in a detergent solution, deionized water, ethanol and isopropanol for ultrasonic cleaning in turn, with each ultrasonic cleaning lasting 20 minutes. After cleaning, the solution on the surface of the ITO coated glass substrate was blown away with a nitrogen gun. Finally, the ITO coated glass substrate was placed in an oxygen plasma environment for treatment for 10 minutes. 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 plate at 100° C. and annealed for 10 min to obtain a hole transport layer with a thickness of 40 nm.

[0150] FAI and PbI2 powders with a molar ratio of 1:1, and MABr and PbBr2 powders with a molar ratio of 1:1 were placed in a ball mill to synthesize FAPbI3 and MAPbBr3 powders at room temperature. Then, FAPbI3 and MAPbBr3 powders with a molar ratio of 3:7 were placed in a ball mill to prepare FA 0.3 MA0.7 Pb(I 0.3 Br 0.7 )3 powder; then prepare FA with a concentration of 2 mol / L 0.3 MA 0.7 Pb(I 0.3 Br 0.7 )3 solution (the solvent is a mixed solution of DMF and DMSO); FA 0.3 MA 0.7 Pb(I 0.3 Br 0.7 )3 After the solution was stirred for 12 hours, it was spin-coated on the surface of the hole transport layer. At the same time, an appropriate amount of anti-solvent toluene was dropped on the surface of the perovskite solution to induce rapid crystallization to form a uniform perovskite film. The glass substrate was then quickly placed on a hot plate at 110°C and annealed for 20 minutes to obtain a perovskite absorption layer with a thickness of 1000 nm.

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

[0152] The glass substrate is transferred to the thermal evaporation vacuum chamber. The BCP thin film was evaporated on the surface of the electron transport layer at a rate of 20 minutes to obtain a passivation layer with a thickness of 10 nm.

[0153] by Au thin film was evaporated on the surface of the passivation layer at a deposition rate of 20 min to obtain a metal electrode with a thickness of 50 nm.

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

[0155] The radiation source 85 Kr is placed above the energy conversion device, that is, above the metal electrode, and fixed with a metal frame, and finally packaged with radiation-proof material, thereby obtaining the long-term 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, and the two passivation layers are respectively a first passivation layer and a second passivation layer.

[0158] Specifically, the preparation method of the first passivation layer is: after mixing SnCl4·5H2O with tetramethylammonium hydroxide solution, heating at 100°C for 12h to prepare SnO2 sol-gel; spin-coating the SnO2 sol-gel on the surface of the electron transport layer at a speed of 2000rpm to obtain a passivation layer with a thickness of 5nm.

[0159] The second passivation layer is prepared by transferring the glass substrate to a thermal evaporation vacuum chamber. The BCP film was evaporated on the surface of the first passivation layer at a rate of to obtain a passivation layer with a thickness of 5 nm.

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

[0161] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that no passivation layer is provided.

[0162] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is that a long-term energy supply device includes, from top to bottom, a β-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: The difference between Comparative Example 3 and Example 1 is that a long-term energy supply device includes, from top to bottom, a β-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 were subjected to performance tests. The performance test method was as follows: a 3.05nA electron beam was incident from one side of the metal electrode with a gradually increasing acceleration voltage, the UI characteristic curve of the nuclear battery was measured, and the maximum radiation damage threshold was 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, a passivation layer is provided between the electron transport layer and the metal electrode in Examples 1-5. The passivation layer not only protects the perovskite absorption layer, but also absorbs excess β-ray energy, thereby reducing the energy deposited by the electron transport layer, thereby reducing the degree of radiation damage to the electron transport layer. Therefore, Examples 1-5 have a higher radiation damage threshold.

[0169] Comparative Example 1 does not provide a passivation layer, and therefore cannot fully isolate water and oxygen in the external environment, causing water and oxygen to invade the perovskite layer and react with the perovskite, resulting in degradation of the perovskite absorption layer; at the same time, the electron transport layer deposits more energy, causing the macroscopic structure and phase composition of the electron transport layer to change, resulting in a greater degree of radiation damage to the electron transport layer, causing the energy conversion device to be unable to work normally under lower energy β-ray radiation, and the energy conversion efficiency to drop by more than 90%. Therefore, Comparative Example 1 has a lower radiation damage threshold.

[0170] In Comparative Example 2, no passivation layer is provided between the metal electrode and the electron transport layer, and the electron transport layer deposits more energy, which causes changes in the macroscopic structure and phase composition of the electron transport layer, resulting in a greater degree of radiation damage to the electron transport layer, thereby causing Comparative Example 2 to have a lower radiation damage threshold.

[0171] In Comparative Example 3, the β rays are absorbed by the perovskite absorption layer after passing through the metal electrode and the hole transport layer in sequence. There is no passivation layer to absorb the excess energy, which causes a large degree of radiation damage to the hole transport layer and the perovskite layer, resulting in a lower radiation damage threshold for Comparative Example 3.

[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 the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. An energy conversion device, characterized in that: include: A first electrode, a passivation layer, an electron transport layer, a perovskite absorption layer, a hole transport layer, and a second electrode are stacked.

2. The energy conversion device according to claim 1, characterized in that: The number of layers of the passivation layer includes at least one layer; and / or, The material of the passivation layer includes at least one of metal oxides corresponding to Mg, Ni, Cd, Zn, In, Pb, Mo, Sb, Bi, Cu, Ti, Mn, V, and Sn, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.

3. The energy conversion device according to claim 1 or 2, characterized in that: The material of the perovskite absorption layer satisfies the chemical formula APbX3, wherein A includes MA + , FA + , Cs + At least one of; X includes Cl - Br - ,I - At least one of .

4. The energy conversion device according to claim 1 or 2, characterized in that: The material of the electron transport layer includes at least one of [6,6]-phenyl-C-butyric acid isomethyl ester, fullerene and its derivatives; and / or, The material of the hole transport layer includes at least one of poly(3,4-ethylenedioxythiophene) 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, and 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, and K.

5. The energy conversion device according to claim 1 or 2, characterized in that: The first electrode comprises a metal electrode; and / or, The second electrode includes a transparent electrode.

6. The energy conversion device according to claim 1, characterized in that: The thickness of the first electrode layer is 20nm-80nm; and / or, The thickness of the passivation layer is 5nm-10nm; and / or, The thickness of the electron transport layer is 10nm-20nm; and / or, The thickness of the perovskite absorption layer is 500nm-2000nm; and / or, The thickness of the hole transport layer is 20nm-50nm; and / or, The thickness of the second electrode is 100nm-200nm.

7. A method for preparing an energy converter according to any one of claims 1 to 6, characterized in that: include: forming a hole transport layer on one side of the second electrode; forming a perovskite absorption layer on a side of the hole transport layer away from the second electrode; forming an electron transport layer on a side of the perovskite absorption layer away from the hole transport layer; forming a passivation layer on a side of the electron transport layer away from the perovskite absorption layer; The first electrode is formed on a side of the passivation layer away from the electron transport layer.

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

9. A long-term energy supply device, characterized in that: The invention comprises the energy conversion device according to any one of claims 1 to 6, or the energy conversion device prepared by the method according to any one of claims 7 to 8, and a beta-type radiation source located near the first electrode.

10. The long-term energy supply device according to claim 9, characterized in that: The beta-type radiation source comprises 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 At least one of Y and compounds thereof.

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