WO2023164873A1 - 放射性钙钛矿及包含其的光伏电池、制备方法 - Google Patents
放射性钙钛矿及包含其的光伏电池、制备方法 Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present application relates to the technical field of photovoltaic cells, and in particular to a radioactive perovskite and a photovoltaic cell containing a perovskite layer made thereof, and a method for preparing the photovoltaic cell.
- the perovskite photovoltaic cells are favored due to their advantages such as high photoelectric conversion efficiency, simple manufacturing process, low production cost and material cost.
- the perovskite photovoltaic cells have With the loss of carriers and lower carrier mobility, the energy conversion efficiency of the battery is reduced.
- the method for improving the energy conversion efficiency of perovskite photovoltaic cells is usually to improve the material and structure of the electron transport layer and the hole transport layer, or to introduce passivation at the interface between the perovskite layer and the electron transport layer and the hole transport layer. layer to effectively passivate defects on the surface of the perovskite layer.
- this method may also cause more interface defects as the number of interfaces increases, and the battery preparation process is complicated and the cost increases.
- the present application was made in view of the above problems, and an object of the present application is to provide a radioactive perovskite, a photovoltaic cell including a perovskite layer made of the radioactive perovskite, and a method for producing the photovoltaic cell.
- the photovoltaic cell has the advantages of high energy conversion efficiency, simple preparation method, and lower cost.
- the first aspect of the present application provides a radioactive perovskite
- the general formula of the perovskite is ABX 3 , wherein, A is selected from the group consisting of methylamine cation MA + , formamidinium cation FA + , At least one of cesium cation Cs + and the first radioactive element cation, B is selected from at least one of lead cation Pb 2+ , tin cation Sn 2+ , nickel cation Ni 2+ and the second radioactive element cation, and X is selected from At least one of chlorine anion Cl - , bromide anion Br - , iodide anion I - , formate anion HCOO - , hydride ion H - and radioactive element anion; and the above general formula ABX 3 comprises the first radioactive element cation, the second At least one of two radioactive element cations and radioactive element anions.
- the radioactive perovskite obtained by introducing radioactive elements into the perovskite can be used as both a light-absorbing material and an energy-supplying material, so when it is applied to a photovoltaic cell, it can generate more carriers and increase the energy of the battery conversion efficiency.
- the first radioactive element cation is selected from at least one of 137 Cs + , 106 Ru + , optionally 137 Cs + ;
- the second radioactive element cation is selected from 63 Ni 2+ , 90 Sr 2+ , At least one of 57 Co 2+ , 60 Co 2+ and 106 Ru 2+ , optionally 63 Ni 2+ and/or 90 Sr 2+ ;
- the radioactive element anion is selected from 125 I - , 131 I - and 3 H At least one of - , optionally 125 I - and/or 3 H - .
- the total molar amount of the first radioactive element cation contained in A relative to A is greater than 0 to less than or equal to 100 mol%, optionally 5-95 mol%, and optionally 15-50mol%.
- the total molar amount of the second radioactive element cation contained in B relative to B is greater than 0 to less than or equal to 100 mol%, optionally 5-95 mol%, and can also be 15-50mol%.
- the radioactive element anion contained in X is greater than 0 to less than or equal to 100 mol% relative to the total molar weight of X, optionally 5-95 mol%, and optionally 15 -65mol%
- the performance of the perovskite photovoltaic cell can be effectively improved, and the energy conversion efficiency can be increased.
- the radioactive perovskite has the formula 137 Cs 63 Ni 3 H 3 , FAPb 125 I 3 , 137 CsPbI 3 , 137 Cs 0.15 FA 0.85 PbI 3 , 137 Cs 0.3 FA 0.7 PbI 3 , 137 Cs 0.5 FA 0.5 PbI 3 , 137 Cs 0.05 FA 0.95 PbI 3 , 137 Cs 0.95 FA 0.05 PbI 3 , FA 63 Ni 0.15 Pb 0.85 I 3 , FA 63 Ni 0.3 Pb 0.7 I 3 , FA 63 Ni 0.5 Pb 0.5 I 3.
- the second aspect of the present application provides a photovoltaic cell, which includes: a first electrode, a first charge transport layer, a perovskite layer, a second charge transport layer, and a second electrode; wherein the perovskite layer comprises The radioactive perovskite, the first electrode is a transparent electrode, and the first and second charge transport layers are not simultaneously electron transport layers or hole transport layers.
- the photovoltaic cell containing the perovskite layer formed by the radioactive perovskite of the present invention can not only absorb the energy of external photons, but also have the decay energy generated by radioactive elements, which is beneficial to generate more carriers and improve battery performance.
- the thickness of the perovskite layer in the photovoltaic cell is 400-600 nm. In any embodiment, the perovskite layer in the photovoltaic cell is formed by a thermal evaporation method or a precursor solution coating method.
- the precursor liquid coating method comprises the following steps:
- step S2 coating the precursor solution obtained in step S1 on the first charge transport layer, and heating to obtain a perovskite layer.
- the AX is selected from at least one of 137 CsI, formamidine iodide FAI, FA 125 I, CsI, methylamine iodide MAI;
- BX 2 is selected from PbI 2 , 63 NiI 2 , 90 SrI 2. At least one of Pb 125 I 2 , wherein at least one of AX and BX 2 is the above compound containing radioactive elements.
- the photovoltaic cell comprising the perovskite layer made of the radioactive perovskite of the present invention is prepared, and the preparation method is simple and low in cost.
- the radioactive perovskite provided can be used not only as an absorber of photons and radiation particles, but also as an energy supplier.
- the photovoltaic cell including the radioactive perovskite of the present invention can not only use external incident light as an energy source, but also use the radioactivity of the perovskite layer in the cell to generate more carriers to improve the performance of the cell. performance, increasing energy conversion efficiency.
- Figure 1 is a schematic structural view of a radioactive perovskite-based photovoltaic cell in an embodiment of the present application. From bottom to top, the first electrode, the first charge transport layer, the radioactive perovskite layer, the second charge transport layer and the first two electrodes. Wherein, the first electrode is a transparent electrode, the first charge transport layer is an electron transport layer, and the second charge transport layer is a hole transport layer; incident light enters the photovoltaic cell from the transparent first electrode below.
- ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-6.
- the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
- the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
- a certain parameter is an integer ⁇ 2
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
- steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
- the “comprising” and “comprising” mentioned in this application mean open or closed.
- the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
- the term "or” is inclusive unless otherwise stated.
- the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
- the perovskite layer In perovskite photovoltaic cells, the perovskite layer generates hole-electron pairs under the irradiation of incident light, and is then separated into holes and electrons under the action of the p-i-n junction electric field or the energy level gradient of each functional layer. These unrecombined electrons and holes are collected by the electron transport layer and the hole transport layer, respectively, that is, the electrons are transported from the perovskite layer to the electron transport layer, and the holes are transported from the perovskite layer to the hole transport layer, and finally are collected by the two sides respectively. Electrode collection.
- the method to improve energy conversion efficiency is usually to passivate the electron transport layer and the hole transport layer, thereby reducing the instability of the electron transport layer/perovskite layer interface and the hole transport layer/perovskite layer interface, effectively Passivate the defects on the surface of the perovskite layer; or improve the composition of the perovskite layer, such as introducing semiconductor organic small molecules with Lewis acid/base functional groups at the perovskite grain boundaries, by improving the perovskite and small molecule The energy level matching between them will help to enhance the defect passivation and improve the carrier mobility. It can be seen that these methods all focus on passivating or weakening the defects on the surface of the perovskite layer to improve the efficiency of the battery. However, solutions for improving the perovskite itself are rare.
- perovskite itself is radioactive
- introducing radioactive elements into perovskite can generate more carriers and improve the energy conversion efficiency of perovskite photovoltaic cells.
- the first aspect of the present application provides a radioactive perovskite
- the general formula of the above-mentioned perovskite is ABX 3 , wherein, A is selected from methylamine cation MA + , formamidinium cation FA + , cesium cation Cs + and at least one of the first radioactive element cations, B is selected from at least one of lead cations Pb 2+ , tin cations Sn 2+ , nickel cations Ni 2+ and at least one of the second radioactive element cations, X is selected from chloride anions At least one of Cl - , bromide anion Br - , iodide anion I - , formate anion HCOO - , hydride ion H - and radioactive element anion; and the above general formula ABX 3 includes the first radioactive element cation, the second radioactive element At least one of a cation and an anion of a radioactive element.
- radioelement refers to the Elements that emit particles or rays (such as ⁇ -rays, ⁇ -rays, ⁇ -rays, etc.) from the unstable nucleus, release energy at the same time, and finally decay to form stable atoms and stop emitting, also known as radionuclides. This property is called radioactivity, and the process is called radioactive decay.
- radioactive element cation refers to a positively charged radioactive element
- first radioactive element cation refers to a positively monovalent radioactive element
- second radioactive element cation refers to a positive divalent radioactive element
- radioactive element anion refers to a negatively charged radioactive element, for example, a negative monovalent radioactive element.
- the present inventors found that when the radioactive perovskite satisfies the general formula ABX 3 , wherein the general formula ABX 3 comprises at least one of the first radioactive element cation, the second radioactive element cation and the radioactive element anion; in other words, A, B and at least one of X contains ions of radioactive elements, then the radioactive perovskite can not only absorb photons, but also radiate particles, so the radioactive perovskite is excited and its own excitation generates more carriers , so that the energy conversion efficiency of photovoltaic cells based on the radioactive perovskite layer can be improved.
- the type of the radioactive element is not particularly limited, and any element suitable for constituting the perovskite may be used.
- radioactive elements in the first radioelement cation, the second radioelement cation, and the radioelement anion include, but are not limited to: 210 Po, 228 Th, 235 U, 238 Pu, 241 Am, 242 Cm, 244 Cm, 3 H, 125 I, 131 I, 14 C, 35 S, 63 Ni, 90 Sr, 99 Tc, 106 Ru, 137 Cs, 144 Ce, 147 Pm, 151 Sm, 226 Ra, 55 Fe, 57 Co, 60 Co or 75 Se .
- the first radioactive element cation is selected from at least one of 137 Cs + , 106 Ru + , optionally 137 Cs + ;
- the second radioactive element cation is selected from 63 Ni 2 + , at least one of 90 Sr 2+ , 57 Co 2+ , 60 Co 2+ and 106 Ru 2+ , optionally 63 Ni 2+ and/or 90 Sr 2+ ;
- radioactive element anions are selected from 125 I - , at least one of 131 I - and 3 H - , optionally 125 I - and/or 3 H - .
- radioactive elements into perovskite aims to make perovskite radioactive, so that the energy released by the decay of radioactive elements can be used to increase the energy conversion efficiency of photovoltaic cells.
- the total molar amount of the first radioactive element cation contained in A relative to A is greater than 0 to less than or equal to 100 mol%, optionally 5-95 mol% , and can be selected as 15-50mol%.
- the total molar amount of the second radioactive element cation contained in B relative to B is greater than 0 to less than or equal to 100 mol%, optionally 5-95 mol% , and can be selected as 15-50mol%.
- the total molar amount of radioactive element anions contained in X relative to X is greater than 0 to less than or equal to 100 mol%, optionally 5-95 mol%, and Optionally 15-65mol%.
- At least one of A, B and X may be composed only of ions of radioactive elements without containing any ions of non-radioactive elements; it may also be composed of ions of radioactive elements and ions of non-radioactive elements.
- the total molar amount of the ions of the radioactive elements is relative to the total molar amount of the respective corresponding ions (A, B or X) When the ratio of the amount is in the range of 5-95mol%, the photovoltaic cell made has better energy conversion efficiency.
- the molar proportion of the first radioactive element cation contained in A is 15-50 mol%
- the molar proportion of the second radioactive element cation contained in B is 15-50 mol%
- the molar proportion of the radioactive element anion contained in X is 15-65mol%
- the general formula of the radioactive perovskite is 137 Cs 63 Ni 3 H 3 , FAPb 125 I 3 , 137 CsPbI 3 , 137 Cs 0.15 FA 0.85 PbI 3 , 137 Cs 0.3 FA 0.7 PbI 3 , 137 Cs 0.5 FA 0.5 PbI 3 , 137 Cs 0.05 FA 0.95 PbI 3 , 137 Cs 0.95 FA 0.05 PbI 3 , FA 63 Ni 0.15 Pb 0.85 I 3 , FA 63 Ni 0.3 Pb 0.7 I 3 , FA 63 Ni 0.
- the second aspect of the present application provides a photovoltaic cell, which includes: a first electrode, a first charge transport layer, a perovskite layer, a second charge transport layer, and a second electrode; wherein the perovskite layer contains the radioactive For perovskite, the first electrode is a transparent electrode, and the first and second charge transport layers are not simultaneously electron transport layers or hole transport layers.
- This photovoltaic cell including the radioactive perovskite layer of the present invention can use external incident light as an energy source, and can also utilize high-energy radiation particles (KeV) released by the radioactive elements in the perovskite layer inside the cell to generate self-excited More carriers, thus improving the energy conversion performance of the battery through this joint action.
- KeV high-energy radiation particles
- the electrode material is an organic or inorganic or organic-inorganic mixed conductive material.
- Organic conductive materials such as conductive polymers (PEDOT, polythiophene, polyacetylene, etc.); inorganic conductive materials, such as transparent conductive oxides (FTO, ITO, AZO, etc.), metals, carbon derivatives, etc.
- the first electrode is a transparent electrode for light incident.
- a transparent conductive oxide is used.
- the transparent conductive oxide is composed of a glass substrate and a thin film oxide (TCO for short) conductive layer.
- TCOs include indium tin oxide (ITO) and fluorine-doped tin oxide (FTO), but the present application is not limited thereto.
- ITO indium tin oxide
- FTO fluorine-doped tin oxide
- the conductive glass needs to be cleaned before use, for example, ultrasonically cleaned with cleaning agents (including but not limited to surfactants), ethanol, acetone, isopropanol and deionized water.
- the second electrode is used to collect carriers and is selected from metal or carbon derivatives.
- the preparation method is a technical method known in the art, such as thermal evaporation, and the thickness is 20 to 1000 nm.
- metallic silver is the second electrode, which is made by vapor deposition, and has a thickness of 50-120 nm.
- the first and second charge transport layers are not simultaneously electron transport layers or hole transport layers.
- the hole transport layer is used to collect and extract holes from the perovskite layer.
- the material of the hole transport layer is at least one of the following materials and their derivatives: imide compounds, quinone compounds, fullerenes and their derivatives, 2,2',7,7'-tetra(N, N-methoxyanilino)-9,9'-spirobifluorene (Spiro-OMeTAD), methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), poly[bis(4-phenyl)(2 ,4,6-trimethylphenyl)amine] (PTAA), poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid mixture (PEDOT:PSS), poly 3-hexylthiophene (P3HT) , Triphenylamine (H101) with triptycene as the nucleus, 3,4-ethylenedioxythiophene-methoxytriphenylamine
- the electron transport layer is used to collect and extract electrons from the perovskite layer.
- the material of the electron transport layer is at least one of the following materials and derivatives thereof: the material of the charge transport layer is; metal oxide (metal element is selected from Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb , Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, or Cr), silicon oxide (SiO 2 ), strontium titanate (SrTiO 3 ), calcium titanate (CaTiO 3 ), lithium fluoride (LiF), calcium fluoride (CaF 2 ), cuprous thiocyanate (CuSCN), and tin dioxide (SnO 2 ); in the present invention, tin dioxide (SnO 2 ) is used as the electron transport layer.
- metal oxide metal element is selected from Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb , Bi
- the preparation method of the electron transport layer or the hole transport layer is a conventional technical means in the art, selected from chemical vapor deposition method, physical epitaxial growth method, thermal evaporation method, atomic layer deposition method, magnetron sputtering method, spin coating method at least one of the The thickness of the electron transport layer is 5-300nm, and the thickness of the hole transport layer is 5-500nm.
- the electron transport layer and the hole transport layer are made by spin coating, the thickness of the electron transport layer is 20-100 nm, and the thickness of the hole transport layer is 120-180 nm.
- the perovskite layer is prepared using the radioactive perovskite of the present invention.
- the perovskite layer is prepared by conventional technical means in the field, selected from chemical bath deposition method, electrochemical deposition method, chemical vapor deposition method, physical epitaxial growth method, thermal evaporation co-evaporation method, atomic layer deposition method, magnetron sputtering method , at least one of a precursor liquid spin coating method, a precursor liquid slit coating method, a precursor liquid blade coating method, and a mechanical pressing method.
- the perovskite layer is formed by a thermal evaporation method or a precursor solution coating method.
- the precursor liquid coating method comprises the following steps:
- step S2 coating the precursor solution obtained in step S1 on the first charge transport layer, and heating to obtain a perovskite layer.
- AX and BX 2 each independently represent a compound or a mixture. At least one of AX and BX 2 includes a radioactive source (containing radioactive elements).
- the radiation source is at least one of an ⁇ -type radiation source, a ⁇ -type radiation source, and a ⁇ -ray radiation source; wherein, the ⁇ -type radiation source is selected from 210 Po, 228 Th, and 235 U in the form of simple substances or compounds.
- the ⁇ -type radiation source is selected from 3 H, 125 I, 131 I, Ti 3 H 4 , 14 C, 35 S, 63 Ni in the form of simple substances or compounds , 90 Sr, 99 Tc, 106 Ru, 137 Cs, 144 Ce, 147 Pm, 151 Sm or 226 Ra, or a compound containing (C 4 H 3 3 H 5 -) n or 90 Sr/ 90 Y in coexistence form;
- the ⁇ -ray radiation source is selected from 55 Fe, 57 Co, 60 Co, and 75 Se in the form of simple substances or compounds; optionally, the compounds are selected from halogen compounds.
- the precursor solution is prepared by the following method: Weigh the raw materials for preparing the perovskite precursor, for example, formamidine iodide (FAI, FA 125 I), lead iodide (PbI 2 , Pb 125 I 2 ), methylamine chloride (MACl), methylamine iodide (MAI), cesium iodide (CsI, 137 CsI), nickel iodide (NiI 2 , 63 NiI 2 ), strontium iodide (SrI 2 , 90 SrI 2 ) etc., dissolved in a solvent (for example, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc.), and stirred evenly, it is the precursor solution of the radioactive perovskite of the present invention.
- a solvent for example, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc.
- step S2 the precursor solution obtained in step S1 is covered on the prepared electron transport layer, and the covering method can be spin-coated by using a homogenizer, wherein the rotation speed can be 500-5000rpm/s, and the spin-coating time can be 10- 50 seconds; then placed on a constant temperature hot stage, heated at 70 to 170° C. for 15 to 60 minutes, and cooled to room temperature to form the perovskite of the present invention with a thickness of 300 to 1000 nm. In some embodiments, the thickness of the perovskite layer is 400-600 nm.
- step S1 the total molar amount of AX used and the total molar amount of BX 2 used are 1:(1-1.2), optionally 1:1.
- AX is selected from at least one of 137 CsI, formamidine iodide FAI, FA 125 I, CsI, methylamine iodide MAI;
- BX 2 is selected from PbI 2 , 63 NiI 2. At least one of 90 SrI 2 , Pb 125 I 2 , wherein at least one of AX and BX 2 is the above compound containing radioactive elements.
- the inventive photovoltaic cell based on the inventive radioactive perovskite layer can be prepared by the method described above.
- the cell not only uses external incident light as an energy source, but also uses the decay radiation of radioactive elements contained in the perovskite layer as an energy source, thereby further improving the energy conversion efficiency of the photovoltaic cell.
- the 2.0cm ⁇ 2.0cm FTO conductive glass surface was cleaned twice with acetone and isopropanol in sequence, then immersed in deionized water for 10 minutes and ultrasonically treated, then dried in a blast drying oven, and then placed Standby in the glove box ( N2 atmosphere), this is the first electrode.
- Preparation of the first charge transport layer use a homogenizer (LEBO EZ6-S, the same below) to spin-coat 3% by weight of SnO 2 nanocolloid aqueous solution on the FTO layer, and the spin-coating time is 30 seconds. After that, it was heated at 150° C. for 15 minutes on a constant temperature heating stage to obtain a first charge transport layer with a thickness of 30 nm, which is an electron transport layer.
- a homogenizer LEBO EZ6-S, the same below
- (ii) Forming a perovskite layer use a homogenizer to spin-coat the precursor solution of the above-mentioned 137 CsI-FAI- PbI on the obtained first charge transport layer at a speed of 4500 rpm, the spin-coating volume is 60 microliters, spin The coating time is 30 seconds. Afterwards, it was moved to a constant temperature heating stage, heated at 100° C. for 30 minutes, and cooled to room temperature to form a perovskite layer of 137 Cs 0.15 FA 0.85 PbI 3 with a thickness of 500 nm.
- the second charge transport layer is a hole transport layer.
- the preparation of the first electrode, the first charge transport layer, the second charge transport layer and the second electrode is the same as in Example 1, except that the perovskite layer is prepared.
- the above-mentioned FAPbI 3 precursor solution was spin-coated on the obtained first charge transport layer at a speed of 4500 rpm using a homogenizer, with a spin-coating volume of 60 microliters and a spin-coating time of 30 seconds. Then move to a constant temperature hot stage, heat at 100°C for 30min, and cool to room temperature to form a non-radioactive perovskite layer with a thickness of 500nm.
- the preparation of the first electrode, the first charge transport layer, the second charge transport layer and the second electrode is the same as in Example 1, except that the perovskite layer is prepared.
- the above-mentioned mixed precursor solution of 137 CsCl and FAPbI 3 was spin-coated on the obtained first charge transport layer at a speed of 4500 rpm using a homogenizer, with a spin-coating volume of 60 microliters and a spin-coating time of 30 seconds. Then move to a constant temperature hot stage, heat at 100°C for 30min, and cool to room temperature to form a mixed radioactive perovskite layer of 137 CsCl-FAPbI 3 with a thickness of 500nm.
- the energy conversion efficiency is calculated as follows:
- Pout, Popt, Vmpp, and Jmpp are the working output power of the battery, the incident light power, the voltage at the maximum power point of the battery, and the current at the maximum power point, respectively.
- the present application is not limited to the above-mentioned embodiments.
- the above-mentioned embodiments are merely examples, and within the scope of the technical solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects are included in the technical scope of the present application.
- various modifications conceivable by those skilled in the art are added to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application. .
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Abstract
本发明提供了一种放射性钙钛矿，其通式为ABX3，A选自甲胺根、甲脒根、铯阳离子和第一放射性元素阳离子中的至少一种，B选自铅阳离子、锡阳离子、镍阳离子和第二放射性元素阳离子中的至少一种，X选自氯阴离子、溴阴离子、碘阴离子、甲酸根、氢阴离子和放射性元素阴离子中的至少一种；以及，上述通式ABX3包含第一放射性元素阳离子、第二放射性元素阳离子和放射性元素阴离子中的至少一个。本发明还提供包含由其制成的钙钛矿层的光伏电池以及制备方法，具有高的能量转化效率以及制备方法简单、成本更低等优点。
Description
本申请涉及光伏电池技术领域，尤其涉及一种放射性钙钛矿以及包含由其制成的钙钛矿层的光伏电池、和该光伏电池的制备方法。
随着新能源领域的快速发展，光伏电池凭借其较高的光电转换效率、简单的制作工艺、低的生产成本和材料成本等优势而备受青睐。目前，钙钛矿光伏电池由于其中钙钛矿层表面的结构缺陷，钙钛矿异质结结构的不稳定，以及钙钛矿层与电子传输层、空穴传输层的界面处的结构缺陷，造成了载流子的损失和较低的载流子迁移率，电池的能量转换效率降低。用于提高钙钛矿光伏电池的能量转化效率的方法通常是改进电子传输层、空穴传输层的材料以及结构，或者在钙钛矿层与电子传输层、空穴传输层的界面处引入钝化层，以有效地钝化钙钛矿层表面的缺陷。然而，这种方式也可能会随着界面数量的增加而引起更多的界面缺陷，而且电池制备的工艺复杂、成本提高。
因此，仍然需要，对于钙钛矿光伏电池的性能进行进一步提高，以及简化制备工艺和降低成本。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种放射性钙钛矿以及包含由其制成的钙钛矿层的光伏电池，以及该光伏电池的制备方法。上述光伏电池具有高的能量转化效率以及制备方法简单、成本更低等优点。
为了实现上述目的，本申请的第一方面提供了一种放射性钙钛矿，上述钙钛矿的通式为ABX
3，其中，A选自甲胺根阳离子MA
+、甲脒根阳离子FA
+、铯阳离子Cs
+和第一放射性元素阳离子中的至少一种， B选自铅阳离子Pb
2+、锡阳离子Sn
2+、镍阳离子Ni
2+和第二放射性元素阳离子中的至少一种，X选自氯阴离子Cl
-、溴阴离子Br
-、碘阴离子I
-、甲酸根阴离子HCOO
-、氢阴离子H
-和放射性元素阴离子中的至少一种；以及上述通式ABX
3包含第一放射性元素阳离子、第二放射性元素阳离子和放射性元素阴离子中的至少一个。
通过在钙钛矿中引入放射性元素得到的放射性钙钛矿，其既可以作为吸光材料也可以作为供能材料，因此可以在应用于光伏电池时，产生更多的载流子，提高电池的能量转换效率。
在任意实施方式中，第一放射性元素阳离子选自
137Cs
+、
106Ru
+中的至少一种，可选为
137Cs
+；第二放射性元素阳离子选自
63Ni
2+、
90Sr
2+、
57Co
2+、
60Co
2+和
106Ru
2+中的至少一种，可选为
63Ni
2+和/或
90Sr
2+；放射性元素阴离子选自
125I
-、
131I
-和
3H
-中的至少一种，可选为
125I
-和/或
3H
-。由此，钙钛矿层可以利用放射性元素衰变所放出的能量，从而增加载流子的数量，提高钙钛矿光伏电池的性能。
在任意实施方式中，在通式ABX
3中，A中包含的第一放射性元素阳离子相对于A的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-50mol％。
在任意实施方式中，在通式ABX
3中，B中包含的第二放射性元素阳离子相对于B的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-50mol％。
在任意实施方式中，在通式ABX
3中，X中包含的放射性元素阴离子相对于X的总摩尔量计为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-65mol％
在所述钙钛矿中，放射性元素的含量在上述范围内时，可以有效地提高钙钛矿光伏电池的性能，增加能量转换效率。
在任意实施方式中，放射性钙钛矿的化学式为
137Cs
63Ni
3H
3、FAPb
125I
3、
137CsPbI
3、
137Cs
0.15FA
0.85PbI
3、
137Cs
0.3FA
0.7PbI
3、
137Cs
0.5FA
0.5PbI
3、
137Cs
0.05FA
0.95PbI
3、
137Cs
0.95FA
0.05PbI
3、FA
63Ni
0.15Pb
0.85I
3、FA
63Ni
0.3Pb
0.7I
3、FA
63Ni
0.5Pb
0.5I
3、FA
63Ni
0.05Pb
0.95I
3、FA
63Ni
0.95Pb
0.05I
3、 FAPb(
125I
0.15I
0.85)
3、FAPb(
125I
0.5I
0.5)
3、FAPb(
125I
0.65I
0.35)
3、FAPb(
125I
0.05I
0.95)
3、FAPb(
125I
0.95I
0.05)
3、
137Cs
0.05FA
0.95
63Ni
0.05Pb
0.95I
3、
137Cs
0.15FA
0.85
63Ni
0.15Pb
0.85I
3、
137Cs
0.3FA
0.7
63Ni
0.3Pb
0.7I
3、
137Cs
0.95FA
0.05
63Ni
0.95Pb
0.05I
3、
137Cs
0.3FA
0.7Pb(
125I
0.5I
0.5)
3、
137Cs
0.3FA
0.7
63Ni
0.3Pb
0.7(
125I
0.5I
0.5)
3或FA
63Ni
0.3Pb
0.7(
125I
0.5I
0.5)
3。这些包含放射性元素的钙钛矿有利于提高光伏电池的能量转换效率。
本申请的第二方面提供了一种光伏电池，其包括：第一电极、第一电荷传输层、钙钛矿层、第二电荷传输层、第二电极；其中，钙钛矿层包含本发明所述的放射性钙钛矿，第一电极为透明电极，第一、第二电荷传输层不同时为电子传输层或空穴传输层。
根据本发明，包含本发明的放射性钙钛矿形成的钙钛矿层的光伏电池，不仅可以吸收外界光子的能量，同时也具有放射性元素产生的衰变能量，有利于生成更多的载流子，提高电池的性能。
在任意实施方式中，光伏电池中的钙钛矿层的厚度为400-600nm。在任意实施方式中，光伏电池中的钙钛矿层通过热蒸镀方法或前驱液涂布方法形成。
在任意实施方式中，前驱液涂布方法包括以下步骤：
S1：将AX与BX
2溶于极性溶剂中，制备本发明所述的放射性钙钛矿的前驱体溶液；
S2：将步骤S1得到的前驱体溶液涂布在第一电荷传输层上，加热得到钙钛矿层。
在任意实施方式中，所述AX选自
137CsI、碘化甲脒FAI、FA
125I、CsI、碘化甲胺MAI中的至少一种；BX
2选自PbI
2、
63NiI
2、
90SrI
2、Pb
125I
2中的至少一种，其中AX与BX
2中的至少一种是上述包含放射性元素的化合物。
由此制备得到本发明的包含由本发明的放射性钙钛矿制成的钙钛矿层的光伏电池，而且该制备方法简单、成本低。
根据本发明，提供的放射性钙钛矿既可以作为光子、辐射粒子的吸收体，也可以作为供能体。进一步地，本发明的包括所述放射性钙 钛矿的光伏电池，既可以利用外界入射光作为能量来源，也可以利用电池内的钙钛矿层的放射性，生成更多的载流子，以提高电池性能，增加能量转换效率。
图1为本申请一实施方式中的基于放射性钙钛矿的光伏电池的结构示意图，从下到上依次为第一电极、第一电荷传输层、放射性钙钛矿层、第二电荷传输层和第二电极。其中，第一电极为透明电极、第一电荷传输层为电子传输层、第二电荷传输层为空穴传输层；入射光从下面透明第一电极进入该光伏电池。
以下，适当地参照附图详细说明具体公开了本申请的光伏电池的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-6。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。 另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
在钙钛矿光伏电池中，钙钛矿层在入射光的照射下，产生空穴-电子对，然后在p-i-n结电场或各功能层能级梯度的作用下，被分离成空穴和电子。这些未复合的电子和空穴分别被电子传输层和空穴传输层收集，即电子从钙钛矿层传输到电子传输层，空穴从钙钛矿层传输到空穴传输层，最后分别被两侧电极收集。当然，在这些过程中总不免伴随着一些载流子的损失，如电子传输层的电子与钙钛矿层空穴的可逆复合、电子传输层的电子与空穴传输层的空穴的复合(钙钛矿 层不致密的情况)、钙钛矿层的电子与空穴传输层的空穴的复合。因此，造成电池的能量损失，降低电池的能量转换效率。
目前，提高能量转换效率的方法通常是：利用电子传输层和空穴传输层进行钝化，从而减少电子传输层/钙钛矿层界面和空穴传输层/钙钛矿层界面的不稳定性，有效地钝化钙钛矿层表面的缺陷；或者改进钙钛矿层的组成，例如在钙钛矿晶界处引入带有路易斯酸/碱功能基团的半导体有机小分子，通过提升钙钛矿与小分子间的能级匹配度，将有助于增强缺陷钝化作用，提高载流子迁移率。可见，这些方法均集中于钝化或弱化钙钛层表面的缺陷，来提高电池的效率。然而，对于钙钛矿本身进行改进的解决方案，并不多见。
在实践中，本申请发明人发现，在钙钛矿中引入放射性元素，即钙钛矿本身具有放射性，可以产生更多的载流子，提高钙钛矿光伏电池的能量转化效率。
因此，本申请的第一方面提供了一种放射性钙钛矿，上述钙钛矿的通式为ABX
3，其中，A选自甲胺根阳离子MA
+、甲脒根阳离子FA
+、铯阳离子Cs
+和第一放射性元素阳离子中的至少一种，B选自铅阳离子Pb
2+、锡阳离子Sn
2+、镍阳离子Ni
2+和第二放射性元素阳离子中的至少一种，X选自氯阴离子Cl
-、溴阴离子Br
-、碘阴离子I
-、甲酸根阴离子HCOO
-、氢阴离子H
-和放射性元素阴离子中的至少一种；以及上述通式ABX
3包含第一放射性元素阳离子、第二放射性元素阳离子和放射性元素阴离子中的至少一个。
在本文中，所用的术语“放射性元素”，以及包含在这些术语“第一放射性元素阳离子”、“第二放射性元素阳离子”和“放射性元素阴离子”中的“放射性元素”，是指能够自发地从不稳定的原子核内部放出粒子或射线(如α射线、β射线、γ射线等)，同时释放出能量，最终衰变形成稳定的原子而停止放射的元素，也称为放射性核素。这种性质称为放射性，这一过程叫做放射性衰变。
在本文中，所用的术语“放射性元素阳离子”是指带有正电荷的放射性元素；“第一放射性元素阳离子”是指正一价的放射性元素。术语“第二放射性元素阳离子”是指正二价的放射性元素。
在本文中，所用的术语“放射性元素阴离子”是指带有负电荷的放射性元素，例如，负一价的放射性元素。
本发明人发现，在放射性钙钛矿满足通式ABX
3时，其中通式ABX
3包含第一放射性元素阳离子、第二放射性元素阳离子和放射性元素阴离子中的至少一个；换句话说，A、B和X中的至少一个包含放射性元素的离子，则所述放射性钙钛矿，不仅可以吸收光子，也可以辐射粒子，因此放射性钙钛矿受到激发以及其自身的激发，产生更多的载流子，从而使基于该放射性钙钛矿层的光伏电池的能量转换效率得以提升。
任选地，所述放射性元素的类型没有特别地限定，适用于组成钙钛矿的均可。第一放射性元素阳离子、第二放射性元素阳离子和放射性元素阴离子中的放射性元素的实例包括但不限于：
210Po、
228Th、
235U、
238Pu、
241Am、
242Cm、
244Cm、
3H、
125I、
131I、
14C、
35S、
63Ni、
90Sr、
99Tc、
106Ru、
137Cs、
144Ce、
147Pm、
151Sm、
226Ra、
55Fe、
57Co、
60Co或
75Se。
在一些实施方式中，在通式ABX
3中，第一放射性元素阳离子选自
137Cs
+、
106Ru
+中的至少一种，可选为
137Cs
+；第二放射性元素阳离子选自
63Ni
2+、
90Sr
2+、
57Co
2+、
60Co
2+和
106Ru
2+中的至少一种，可选为
63Ni
2+和/或
90Sr
2+；放射性元素阴离子选自
125I
-、
131I
-和
3H
-中的至少一种，可选为
125I
-和/或
3H
-。
在钙钛矿中引入放射性元素，旨在使钙钛矿具有放射性，从而可以利用放射性元素衰变所放出的能量，来增加光伏电池的能量转换效率。
在一些实施方式中，在通式为ABX
3的钙钛矿中，A中包含的第一放射性元素阳离子相对于A的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-50mol％。
在一些实施方式中，在通式为ABX
3的钙钛矿中，B中包含的第二放射性元素阳离子相对于B的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-50mol％。
在一些实施方式中，在通式为ABX
3的钙钛矿中，X中包含的放射性元素阴离子相对于X的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-65mol％。
在通式为ABX
3的钙钛矿中，A、B和X中的至少一个可以是仅由放射性元素的离子组成，不包含任何不具有放射性的元素的离子；也可以是由放射性元素的离子和不具有放射性的元素的离子组成。可选地，在由放射性元素的离子和不具有放射性的元素的离子组成的情形下，所述放射性元素的离子的摩尔总量相对于各自所对应的离子(A、B或X)的摩尔总量之比，在5-95mol％范围内，所制成的光伏电池具有较好的能量转换效率。尤其是，A中包含的第一放射性元素阳离子的摩尔比例为15-50mol％、B中包含的第二放射性元素阳离子的摩尔比例为15-50mol％且X中包含的放射性元素阴离子的摩尔比例为15-65mol％，则由此类钙钛矿制成的光伏电池的能量转换效率更为优异。
在一些实施方式中，所述放射性钙钛矿的通式为
137Cs
63Ni
3H
3、FAPb
125I
3、
137CsPbI
3、
137Cs
0.15FA
0.85PbI
3、
137Cs
0.3FA
0.7PbI
3、
137Cs
0.5FA
0.5PbI
3、
137Cs
0.05FA
0.95PbI
3、
137Cs
0.95FA
0.05PbI
3、FA
63Ni
0.15Pb
0.85I
3、FA
63Ni
0.3Pb
0.7I
3、FA
63Ni
0.5Pb
0.5I
3、FA
63Ni
0.05Pb
0.95I
3、FA
63Ni
0.95Pb
0.05I
3、FAPb(
125I
0.15I
0.85)
3、FAPb(
125I
0.5I
0.5)
3、FAPb(
125I
0.65I
0.35)
3、FAPb(
125I
0.05I
0.95)
3、FAPb(
125I
0.95I
0.05)
3、
137Cs
0.05FA
0.95
63Ni
0.05Pb
0.95I
3、
137Cs
0.15FA
0.85
63Ni
0.15Pb
0.85I
3、
137Cs
0.3FA
0.7
63Ni
0.3Pb
0.7I
3、
137Cs
0.95FA
0.05
63Ni
0.95Pb
0.05I
3、
137Cs
0.3FA
0.7Pb(
125I
0.5I
0.5)
3、
137Cs
0.3FA
0.7
63Ni
0.3Pb
0.7(
125I
0.5I
0.5)
3或FA
63Ni
0.3Pb
0.7(
125I
0.5I
0.5)
3。这些钙钛矿因为包含放射性元素，所以能够释放出衰变能量，可以作为供能体，提高光伏电池的能量转换效率。
本申请的第二方面提供了一种光伏电池，其包括：第一电极、第一电荷传输层、钙钛矿层、第二电荷传输层、第二电极；其中，钙钛矿层包含本发明的放射性钙钛矿，第一电极为透明电极，第一、第二电荷传输层不同时为电子传输层或空穴传输层。
这种包括本发明的放射性钙钛矿层的光伏电池，既可以利用外界入射光作为能量来源，也可以利用电池内部的钙钛矿层中的放射性元素所释放的高能辐射粒子(KeV)而自激生成更多的载流子，由此通过这种共同作用以提升电池的能量转换性能。
第一电极和第二电极
电极材料为有机或无机或有机无机混合的导电材料。有机导电材料，例如，导电聚合物(PEDOT、聚噻吩、聚乙炔等)；无机导电材料，例如，透明导电氧化物(FTO、ITO、AZO等)、金属、碳衍生物等。
第一电极为透明电极，用于光入射。通常采用透明导电氧化物。一般地，所述透明导电氧化物由玻璃基底和氧化物薄膜(简称TCO)导电层组成。常规使用的TCO有氧化铟锡(ITO)和掺氟的氧化锡(FTO)，但本申请不限于此。导电玻璃在使用前需清洗，例如用清洗剂(例如包括但不限于表面活性剂)、乙醇、丙酮、异丙醇和去离子水等超声清洗。
第二电极用于收集载流子，选自金属或碳衍生物，制备方法为本领域已知的技术方法，如热蒸镀法，厚度为20至1000nm。在本发明的一个具体实施例中，金属银为第二电极，通过蒸镀方法制成，厚度为50-120nm。
第一与第二电荷传输层
第一、第二电荷传输层不同时为电子传输层或空穴传输层。
空穴传输层用于收集和提取来自钙钛矿层的空穴。空穴传输层的材料为以下材料及其衍生物中的至少一种：酰亚胺化合物、醌类化合物、富勒烯及其衍生物、2,2',7,7'-四(N,N-对甲氧苯胺基)-9,9'-螺二芴(Spiro-OMeTAD)、甲氧基三苯胺-氟代甲脒(OMeTPA-FA)、 聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚(3,4-乙烯二氧噻吩)与聚苯乙烯磺酸混合物(PEDOT:PSS)、聚3-已基噻吩(P3HT)、三蝶烯为核的三苯胺(H101)、3,4-乙烯二氧噻吩-甲氧基三苯胺(EDOT-OMeTPA)、N-(4-苯胺)咔唑-螺双芴(CzPAF-SBF)、聚噻吩；在本发明中，使用2,2',7,7'-四(N,N-对甲氧苯胺基)-9,9'-螺二芴(Spiro-OMeTAD)作为空穴传输层。
电子传输层用于收集和提取来自钙钛矿层的电子。电子传输层的材料为以下材料及其衍生物中的至少一种：电荷传输层的材料为；金属氧化物(金属元素选自Mg、Ni、Cd、Zn、In、Pb、Mo、W、Sb、Bi、Cu、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、Sr、Ga、或者Cr)、氧化硅(SiO
2)、钛酸锶(SrTiO
3)、钛酸钙(CaTiO
3)、氟化锂(LiF)、氟化钙(CaF
2)、硫氰酸亚铜(CuSCN)、以及二氧化锡(SnO
2)；在本发明中，使用二氧化锡(SnO
2)作为电子传输层。
电子传输层或空穴传输层的制备方法为本领域的常规技术手段，选自化学气相沉积方法、物理外延生长方法、热蒸镀方法、原子层沉积方法、磁控溅射方法、旋涂法中的至少一种。电子传输层的厚度为5-300nm，空穴传输层的厚度为5-500nm。在本发明的一个具体实施例中，电子传输层和空穴传输层通过旋涂法制成，电子传输层的厚度为20-100nm，空穴传输层的厚度为120-180nm。
钙钛矿层
使用本发明的放射性钙钛矿制备钙钛矿层。
钙钛矿层采用本领域常规技术手段制备，选自化学浴沉积方法、电化学沉积方法、化学气相沉积方法、物理外延生长方法、热蒸镀共蒸方法、原子层沉积方法、磁控溅射方法、前驱液旋涂方法、前驱液狭缝涂布方法、前驱液刮涂方法、机械压合方法中至少一种。在一些实施方式中，所述钙钛矿层通过热蒸镀方法或前驱液涂布方法形成。
其中，所述前驱液涂布方法包括以下步骤：
S1：将AX与BX
2溶于极性溶剂中，制备本发明的放射性钙钛矿的前驱体溶液；
S2：将步骤S1得到的前驱体溶液涂布在第一电荷传输层上，加热得到钙钛矿层。
在步骤S1中，其中AX和BX
2各自独立地表示化合物或混合物。AX和BX
2中的至少一种包括放射源(含有放射性元素)。所述放射源是α型辐射源、β型辐射源、γ射线辐射源中的至少一种；其中，所述α型辐射源选自以单质或化合物形式存在的
210Po、
228Th、
235U、
238Pu、
241Am、
242Cm或
244Cm；所述β型辐射源选自以单质或化合物形式存在的
3H、
125I、
131I、Ti
3H
4、
14C、
35S、
63Ni、
90Sr、
99Tc、
106Ru、
137Cs、
144Ce、
147Pm、
151Sm或
226Ra，或者包含(C
4H
3
3H
5-)
n或共存形式的
90Sr/
90Y的化合物；γ射线辐射源选自以单质或化合物形式存在的
55Fe、
57Co、
60Co、
75Se；可选地，所述化合物选自卤素化合物。
在步骤S1中，所述前驱体溶液采用以下方法制备：称取制备钙钛矿前驱体的原料，例如，碘化甲脒(FAI、FA
125I)、碘化铅(PbI
2、Pb
125I
2)、氯甲胺(MACl)、碘甲胺(MAI)、碘化铯(CsI、
137CsI)、碘化镍(NiI
2、
63NiI
2)、碘化锶(SrI
2、
90SrI
2)等，溶于溶剂(例如，二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等)中，搅拌均匀，即为本发明的放射性钙钛矿的前驱体溶液。
步骤S2中，将骤S1得到的前驱体溶液覆盖在制备好的电子传输层上，覆盖方式可采用匀胶机进行旋涂，其中转速可为500-5000rpm/s，旋涂时间可为10-50秒；然后放置在恒温热台上，在70至170℃下加热15至60min，冷却至室温，形成本发明的钙钛矿，厚度为300至1000nm。在一些实施方式中，所述钙钛矿层的厚度为400-600nm。
在步骤S1中，所用的AX的摩尔总量与BX
2的摩尔总量为1：(1-1.2)，可选1:1。
在一些实施方式中，所述步骤S1中，AX选自
137CsI、碘化甲脒FAI、FA
125I、CsI、碘化甲胺MAI中的至少一种；BX
2选自PbI
2、
63NiI
2、
90SrI
2、Pb
125I
2中的至少一种，其中AX与BX
2中的至少一种是上述包含放射性元素的化合物。
通过上述方法可以制备本发明的基于本发明放射性钙钛矿层的光伏电池。该电池不仅利用外界入射光作为能量来源，也利用钙钛矿层中包含的放射性元素的衰变辐射作为能量来源，从而进一步提高光伏电池的能量转换效率。
实施例
下面通过实施例来详细说明本申请，该说明是非限制性的。实施例为示例性，仅用于解释本申请，而不能理解为对本申请的限制。
实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
1.第一电极制备：将2.0cm×2.0cm的FTO导电玻璃表面，依次用丙酮和异丙醇清洗2次，然后浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥，随后放置在手套箱中(N
2氛围)待用，此为第一电极。
2.第一电荷传输层制备：使用匀胶机(LEBO EZ6-S，下同)在FTO层上旋涂3重量％的SnO
2纳米胶体水溶液，旋涂时间为30秒。之后在恒温热台上以150℃加热15min，得到厚度为30nm的第一电荷传输层，该第一电荷传输层为电子传输层。
3.钙钛矿层制备：
(i)合成前驱体溶液：将0.225mol
137CsI、1.275mol FAI与1.5mol PbI
2加入到1L的DMF与DMSO混合溶剂(DMF：DMSO体积比＝9:1)中，搅拌充分溶解，得到
137CsI-FAI-PbI
2的前驱体溶液。
(ii)形成钙钛矿层：使用匀胶机以4500rpm的速度在所得到的第一电荷传输层上旋涂上述
137CsI-FAI-PbI
2的前驱体溶液，旋涂体积为60微升，旋涂时间为30秒。之后移至恒温热台上，以100℃加热30min，冷却至室温后，形成
137Cs
0.15FA
0.85PbI
3的钙钛矿层，厚度为500nm。
4.第二电荷传输层的制备：
使用匀胶机以5000rpm的速度在所得到的钙钛矿层上旋涂73mg/mL的Spiro-OMeTAD的氯苯溶液，旋涂时间为20秒，得到第二电荷传输层，厚度为150nm，该第二电荷传输层为空穴传输层。
5.第二电极的制备
将已经形成有第一电极、第一电荷传输层、钙钛矿层和第二电荷传输层的样品放入真空镀膜机(中科TCCP II)，在5×10
-4Pa的真空条件下，以0.2埃/s蒸镀速率，在所得到的第二电荷传输层表面上蒸镀Ag，得到厚度为80nm的Ag电极，将其作为第二电极。
由此得到实施例1的钙钛矿光伏电池。
实施例2-22
重复实施例1，改变钙钛矿层的制备中步骤(i)合成前驱体材料的原料的种类和用量。
比较例1
第一电极、第一电荷传输层、第二电荷传输层和第二电极的制备与实施例1的相同，不同之处在于钙钛矿层的制备。
3.钙钛矿层的制备
将1.5mol FAI与1.5mol PbI
2加入到1L的DMF与DMSO混合溶剂(DMF：DMSO体积比＝9:1)中，搅拌充分溶解，得到FAPbI
3的前驱体溶液。
使用匀胶机以4500rpm的速度在所得到的第一电荷传输层上旋涂上述FAPbI
3的前驱体溶液，旋涂体积为60微升，旋涂时间为30秒。之后移至恒温热台上，以100℃加热30min，冷却至室温后，形成无放射性钙钛矿层，厚度为500nm。
由此得到比较例1的钙钛矿光伏电池。
比较例2
第一电极、第一电荷传输层、第二电荷传输层和第二电极的制备与实施例1的相同，不同之处在于钙钛矿层的制备。
3.钙钛矿层制备：
将1.5mol FAI与1.5mol PbI
2加入到1L的DMF与DMSO混合溶剂(DMF：DMSO体积比＝9:1)中，搅拌充分溶解，得到1.5mol/L的FAPbI
3的前驱体溶液；接着，在该前驱体溶液中加入0.15mol
137CsCl，搅拌充分溶解，其中
137CsCl与FAPbI
3的摩尔比为1：10，得到
137CsCl与FAPbI
3的混合前驱体溶液。
使用匀胶机以4500rpm的速度在所得到的第一电荷传输层上旋涂上述
137CsCl与FAPbI
3的混合前驱体溶液，旋涂体积为60微升，旋涂时间为30秒。之后移至恒温热台上，以100℃加热30min，冷却至室温后，形成
137CsCl-FAPbI
3的混合放射性钙钛矿层，厚度为500nm。
由此得到比较例2的钙钛矿光伏电池。
二、钙钛矿光伏电池的性能评价
能量转换效率的测定方法
对于实施例1-8和比较例1-2的钙钛矿光伏电池测定能量转换效率。具体地，在大气环境下，采用太阳光源模拟测试系统(KA5000，Enlitech)，其中使用AM1.5G标准光源作为太阳光模拟光源，使用四通道数字源表(Keithley 2440)测量在所述光源照射下电池的伏安特性曲线，得到电池的开路电压Voc、短路电流密度Jsc、填充因子FF(Fill Factor)，由此计算电池的能量转换效率Eff(Efficiency)。
能量转换效率如下计算：
Eff＝Pout/Popt
＝Voc×Jsc×(Vmpp×Jmpp)/(Voc×Jsc)
＝Voc×Jsc×FF
其中Pout、Popt、Vmpp、Jmpp分别为电池工作输出功率、入射光功率、电池最大功率点电压及最大功率点电流。
根据上述结果可知，实施例1-22，均取得了良好的效果，能量转换效率较高。而相对于此，对比例1和2，在能量转换效率方面，未取得有效提高。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。
Claims (11)
- 一种放射性钙钛矿，其特征在于，所述钙钛矿的通式为ABX 3，其中，A选自甲胺根阳离子MA +、甲脒根阳离子FA +、铯阳离子Cs +和第一放射性元素阳离子中的至少一种，B选自铅阳离子Pb 2+、锡阳离子Sn 2+、镍阳离子Ni 2+和第二放射性元素阳离子中的至少一种，X选自氯阴离子Cl -、溴阴离子Br -、碘阴离子I -、甲酸根阴离子HCOO -、氢阴离子H -和放射性元素阴离子中的至少一种；以及，上述通式ABX 3包含所述第一放射性元素阳离子、所述第二放射性元素阳离子和所述放射性元素阴离子中的至少一个。
- 根据权利要求1所述的放射性钙钛矿，其特征在于，所述第一放射性元素阳离子选自 137Cs +、 106Ru +中的至少一种，可选为 137Cs +；所述第二放射性元素阳离子选自 63Ni 2+、 90Sr 2+、 57Co 2+、 60Co 2+和 106Ru 2+中的至少一种，可选为 63Ni 2+和/或 90Sr 2+；所述放射性元素阴离子选自 125I -、 131I -和 3H -中的至少一种，可选为 125I -和/或 3H -。
- 根据权利要求1或2所述的放射性钙钛矿，其特征在于，在通式ABX 3中，A中包含的所述第一放射性元素阳离子相对于A的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-50mol％。
- 根据前述权利要求中任一项的放射性钙钛矿，其特征在于，在通式ABX 3中，B中包含的所述第二放射性元素阳离子相对于B的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-50mol％。
- 根据前述权利要求中任一项的放射性钙钛矿，其特征在于，在通式ABX 3中，X中包含的所述放射性元素阴离子相对于X的总摩尔量为大于0至小于等于100mol％，可选为5-95mol％，又可选为15-65mol％。
- 根据前述权利要求中任一项的放射性钙钛矿，其特征在于，所述放射性钙钛矿的化学式为 137Cs 63Ni 3H 3、FAPb 125I 3、 137CsPbI 3、 137Cs 0.15FA 0.85PbI 3、 137Cs 0.3FA 0.7PbI 3、 137Cs 0.5FA 0.5PbI 3、 137Cs 0.05FA 0.95PbI 3、 137Cs 0.95FA 0.05PbI 3、FA 63Ni 0.15Pb 0.85I 3、FA 63Ni 0.3Pb 0.7I 3、FA 63Ni 0.5Pb 0.5I 3、 FA 63Ni 0.05Pb 0.95I 3、FA 63Ni 0.95Pb 0.05I 3、FAPb( 125I 0.15I 0.85) 3、FAPb( 125I 0.5I 0.5) 3、FAPb( 125I 0.65I 0.35) 3、FAPb( 125I 0.05I 0.95) 3、FAPb( 125I 0.95I 0.05) 3、 137Cs 0.05FA 0.95 63Ni 0.05Pb 0.95I 3、 137Cs 0.15FA 0.85 63Ni 0.15Pb 0.85I 3、 137Cs 0.3FA 0.7 63Ni 0.3Pb 0.7I 3、 137Cs 0.95FA 0.05 63Ni 0.95Pb 0.05I 3、 137Cs 0.3FA 0.7Pb( 125I 0.5I 0.5) 3、 137Cs 0.3FA 0.7 63Ni 0.3Pb 0.7( 125I 0.5I 0.5) 3或FA 63Ni 0.3Pb 0.7( 125I 0.5I 0.5) 3。
- 一种光伏电池，其包括：第一电极、第一电荷传输层、钙钛矿层、第二电荷传输层、第二电极；其中，所述钙钛矿层包含权利要求1至6中任一项所述的放射性钙钛矿，所述第一电极为透明电极，所述第一、第二电荷传输层不同时为电子传输层或空穴传输层。
- 根据权利要求7所述的光伏电池，其中所述钙钛矿层的厚度为400-600nm。
- 制备权利要求7或8所述的光伏电池的方法，其中所述钙钛矿层通过热蒸镀方法或前驱液涂布方法形成。
- 根据权利要求9所述的制备光伏电池的方法，其中所述前驱液涂布方法包括以下步骤：S1：将AX与BX 2溶于极性溶剂中，制备权利要求1至7中任一项所述的放射性钙钛矿的前驱体溶液；S2：将步骤S1得到的前驱体溶液涂布在第一电荷传输层上，加热得到钙钛矿层。
- 根据权利要求10所述的制备光伏电池的方法，其特征在于，所述AX选自 137CsI、碘化甲脒FAI、FA 125I、CsI、碘化甲胺MAI中的至少一种；所述BX 2选自PbI 2、 63NiI 2、 90SrI 2、Pb 125I 2中的至少一种，其中所述AX与所述BX 2中的至少一种是上述包含放射性元素的化合物。
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| US20170053746A1 (en) * | 2015-08-18 | 2017-02-23 | Massachusetts Institute Of Technology | Planar mixed-metal perovskites for optoelectronic applications |
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| CN109563108A (zh) * | 2016-07-21 | 2019-04-02 | 洛桑联邦理工学院 | 混合的阳离子钙钛矿固态太阳能电池及其制造 |
| CN111430554A (zh) * | 2020-03-25 | 2020-07-17 | 杭州纤纳光电科技有限公司 | 添加三碘化物的钙钛矿薄膜和电池的制备方法及其电池 |
| WO2021252601A1 (en) * | 2020-06-09 | 2021-12-16 | Ohio State Innovation Foundation | Charge or electricity generating devices and methods of making and use thereof |
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| CN106328813A (zh) * | 2015-06-29 | 2017-01-11 | 清华大学 | 一种高稳定性掺铯钙钛矿型太阳能电池及其制备方法 |
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| WWE | Wipo information: entry into national phase |
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