A ferroelectric porous ceramic-based beta radiation voltaic cell and a method of manufacturing the same

Abstract

The application discloses a beta radiation voltaic effect battery based on ferroelectric porous ceramics and a preparation method thereof. The battery comprises an upper electrode layer, a ferroelectric porous ceramic layer and a lower electrode layer. The upper electrode layer, the ferroelectric porous ceramic layer and the lower electrode layer are sequentially connected and arranged, and the ferroelectric porous ceramic layer is filled with a radioactive source, which is tritium water. The application utilizes the internal electric field formed by the spontaneous polarization of the ferroelectric porous ceramics to separate the electron-hole pairs generated by the beta particle bombardment, and uses the radioactive source tritium water as the beta radiation voltaic effect radioactive source. The beta radiation voltaic effect battery based on the ferroelectric porous ceramics has a special voltaic effect, and the open-circuit voltage of the battery is several times or even dozens of times of the band gap width, and can reach 10 3 ~ 10 4 V.

Description

Technical Field

[0001] The present invention relates to a beta radiation voltaic effect battery, in particular to a beta radiation voltaic effect battery using ferroelectric porous ceramics as energy conversion material and tritium water as a radiation source and a preparation method thereof, belonging to the technical field of nuclear energy utilization. Background Art

[0002] Beta-voltaic batteries convert the energy released by radioactive isotopes during beta decay into electricity. Compared to traditional batteries, beta-voltaic batteries offer advantages such as high energy density, long service life, strong environmental adaptability, stable performance, maintenance-free operation, and miniaturization. They hold significant application value in aerospace, military defense, biomedicine, and polar exploration. They are currently in service in a variety of fields, including military satellites, pacemakers, micro-electromechanical systems, space probes, underwater monitoring, and navigational lights.

[0003] The research and development of β-radiation voltaic effect batteries mainly involves three aspects: 1. The selection of isotope radiation source; 2. The selection of energy conversion materials; 3. The design of energy conversion devices.

[0004] The selection of an isotope radioactive source requires consideration of factors such as safety, half-life, cost, and energy absorption rate. Traditional beta-radiation voltaic effect cell radioactive sources are often solid-state plate structures. This type of reflective source suffers from severe energy loss because the energy conversion material can only accept beta particles emitted in a specific direction; particles radiated in other directions are not collected and utilized. Furthermore, solid-state radioactive sources typically have a high self-absorption coefficient, resulting in relatively low energy utilization.

[0005] Wide-bandgap semiconductors often enable beta-voltaic cells to achieve high energy conversion efficiencies. Consequently, wide-bandgap semiconductors such as SiC, GaN, and ZnO have been widely used in beta-voltaic cells and are a current research hotspot. However, conventional semiconductors generally suffer from shortcomings such as difficulty in preparation and high costs, which severely hinder the large-scale application of beta-voltaic cells.

[0006] There are two main types of energy conversion devices: pn junction and Schottky junction. Due to the asymmetric doping defects found in many wide-bandgap semiconductors, it is difficult to fabricate a high-performance pn junction. The Schottky junction is less efficient at separating electron-hole pairs than the pn junction, but due to its ease of fabrication, it is currently the most widely used type of energy conversion device. While the Schottky junction is slightly less expensive than the pn junction, it also requires precious metals with high work functions, such as gold or platinum, making it more expensive than other battery types. Summary of the Invention

[0007] The present invention addresses the problems existing in the prior art and provides a beta-radiation voltaic effect battery based on ferroelectric porous ceramics. The ferroelectric porous ceramics are simple to prepare and, due to the presence of a built-in electric field inside the ceramics due to spontaneous polarization, can effectively separate electron-hole pairs without relying on a special device form. The prepared battery has a large open-circuit voltage (greater than 80mV) and a high conversion efficiency (greater than 10%).

[0008] To achieve the above object, the technical solution of the present invention is as follows:

[0009] A beta radiation voltaic effect battery comprises an upper electrode layer, a ferroelectric porous ceramic layer and a lower electrode layer; the upper electrode layer, the ferroelectric porous ceramic layer and the lower electrode layer are sequentially connected and the ferroelectric porous ceramic layer is filled with a radioactive source, which is tritium water.

[0010] According to the present invention, the thickness of the upper electrode layer is 150-400 nm, for example, 300 nm.

[0011] According to the present invention, the thickness of the ferroelectric porous ceramic layer is 0.8-1.2 mm, for example, 1 mm.

[0012] According to the present invention, the thickness of the lower electrode layer is 150-400 nm, for example, 300 nm.

[0013] According to the present invention, the pore size distribution of the ferroelectric porous ceramic in the ferroelectric porous ceramic layer is 10-100 nm, and the porosity is 20-40%. The pores of the ferroelectric porous ceramic layer can accommodate more tritium water, providing more energy sources for the beta-radiation voltaic effect battery.

[0014] According to the present invention, the electrode material forming the upper electrode layer and the electrode material forming the lower electrode layer are the same or different, preferably the same.

[0015] According to the present invention, the electrode material forming the upper electrode layer and the electrode material forming the lower electrode layer are the same or different and are independently selected from metals such as silver, aluminum, and copper.

[0016] According to the present invention, the electrode material can form ohmic contact with the ferroelectric porous ceramic, and electrons generated by β particles bombarding the electrode can smoothly enter the ceramic, thereby increasing the carrier concentration and improving the conductivity of the ferroelectric porous ceramic.

[0017] The radioactive source in the present invention uses tritium water. 3 The energy of the beta particles reflected when H decays is between 0 and 18 keV, which is far below the damage threshold of semiconductors. It is a mild beta particle radiation source that cannot penetrate human skin and will not cause harm to the human body. It is safe and reliable and suitable for the preparation of beta radiation voltaic effect batteries. In addition, 3The half-life of H is 12.3 years, theoretically estimated 3 H's beta radiation voltaic effect battery can be used for 24 years. Compared with other isotope radioactive sources, 3 H has obvious cost advantages, and often a considerable level of activity is gathered in the sea area near the nuclear power plant. 3 H, the collection cost is low, while also helping to improve marine water quality, economically and environmentally friendly. Injecting the radioactive source tritium water into the pores of the ferroelectric porous ceramic can absorb the beta particles emitted in all directions by the tritium water. The liquid radioactive source has a low self-absorption coefficient of energy, so the beta radiation voltaic effect cell of the present invention has high energy utilization efficiency.

[0018] According to the present invention, the material forming the ferroelectric porous ceramic layer includes lead zirconate titanate (Pb(Zr 1-y Ti y )O3, where 1>y>0), lanthanum-doped lead zirconate titanate (Pb 1-x La x (Zr 1-y Ti y )O3, where 1>x>0, 1>y>0), barium titanate (BaTiO3), lanthanum-doped barium titanate (Ba 1-x La x TiO3, where 1>x>0), bismuth ferrite (BiFeO3), lanthanum-doped bismuth ferrite (Bi 1-x La x FeO3, wherein 1>x>0) at least one.

[0019] According to the present invention, the open circuit voltage of the battery is 80-110 mV, for example, 100 mV.

[0020] According to the present invention, the short-circuit current of the battery is 5-8 nA, for example, 6 nA.

[0021] The present invention also provides a method for preparing the above-mentioned beta-radiation voltaic effect battery, the method comprising the following steps:

[0022] (1) Preparation of sheet-like ferroelectric porous ceramics;

[0023] (2) depositing metal electrodes on the upper and lower surfaces of the sheet-like ferroelectric porous ceramic by a vacuum thermal evaporation method to form an upper electrode layer and a lower electrode layer;

[0024] (3) performing a DC saturation polarization treatment on the product of step (2) using a ferroelectric tester;

[0025] (4) immersing the polarized product of step (3) in tritium water and allowing it to stand;

[0026] (5) Connecting electrodes to leads and packaging the battery after the product in step (4) is left to stand to prepare the β-radiation voltaic effect battery.

[0027] According to the present invention, in step (1), the material forming the ferroelectric porous ceramic layer includes lead zirconate titanate (Pb(Zr 1-y Ti y )O3, where 1>y>0), lanthanum-doped lead zirconate titanate (Pb 1-x La x (Zr 1-y Ti y )O3, where 1>x>0, 1>y>0), barium titanate (BaTiO3), lanthanum-doped barium titanate (Ba 1-x La x TiO3, where 1>x>0), bismuth ferrite (BiFeO3), lanthanum-doped bismuth ferrite (Bi 1- x La x FeO3, wherein 1>x>0) at least one.

[0028] According to the present invention, in step (1), when the material forming the ferroelectric porous ceramic layer is barium titanate or lanthanum-doped barium titanate, the method for preparing the sheet-like ferroelectric porous ceramic comprises the following steps:

[0029] Barium titanate powder with a particle size of 300-400 nm, polyvinyl butyral and optionally lanthanum trioxide nanopowder are ball-milled and mixed uniformly, dried at 60-80° C. for 1-2 hours, pressed into 0.8-1.2 mm thin sheets using a tablet press at a pressure of 10-25 MPa, and then sintered at 600-700° C. for 8-12 hours using a muffle furnace; and then sintered at 1150-1250° C. for 3-8 hours to obtain sheet-like barium titanate or lanthanum-doped barium titanate porous ceramics.

[0030] The amount of polyvinyl butyral added is 1-5 wt% of the total mass of the mixture, exemplified by 1 wt%, 2 wt%, 3 wt%, 4 wt%, and 5 wt%.

[0031] Among them, according to n(Ba 2+ ):n(La 3+ )=1-x: x is added to barium titanate powder and lanthanum trioxide nanopowder, wherein 1>x>0, preferably, 0.5>x>0.001, and illustratively x=0.002.

[0032] According to the present invention, in step (1), when the material forming the ferroelectric porous ceramic layer is lead zirconate titanate or lanthanum-doped lead zirconate titanate, the method for preparing the sheet-like ferroelectric porous ceramic comprises the following steps:

[0033] Nanopowders of PbO, ZrO2, TiO2 and optionally La2O3 are mixed evenly, and then resin balls are added, and the mixture is evenly mixed by ball milling. After drying at 60-80°C for 1-2 hours, a tablet press is used to press the mixture into 0.8-1.2 mm thin sheets at a pressure of 10-25 MPa, and the mixture is further heated at 100-180°C for 1-2 hours in a resistance furnace to fully burn the resin and form pores in the thin sheets. After cooling, the mixture is sintered in a muffle furnace at 1000-1200°C for 3-8 hours to obtain flaky lead zirconate titanate or lanthanum-doped lead zirconate titanate porous ceramics.

[0034] The molar ratio of the nano powders of PbO, ZrO2 and TiO2 is such that 1-y Ti y )O3, wherein the stoichiometric ratio is 1>y>0.

[0035] The molar ratio of the nano powders of PbO, ZrO2, TiO2 and La2O3 is such that 1-x La x (Zr 1-y Ti y )O3, wherein the stoichiometric ratio is 1>x>0, 1>y>0.

[0036] According to the present invention, in step (1), when the material forming the ferroelectric porous ceramic layer is bismuth ferrite or lanthanum-doped bismuth ferrite, the method for preparing the sheet-like ferroelectric porous ceramic comprises the following steps:

[0037] Bi2O3, Fe2O3 and optionally La2O3 are mixed and NaCl and KCl are added and mixed evenly. The evenly mixed powder is placed in a muffle furnace and sintered at 600-800°C for 1-5 hours. Water is added to the cooled mixture to remove NaCl and KCl therein, and the mixture is washed and dried to prepare a flaky bismuth ferrite or lanthanum-doped bismuth ferrite porous ceramic.

[0038] According to the present invention, in step (2), the sheet-like ferroelectric porous ceramic is placed in anhydrous ethanol and ultrasonically cleaned for 20 minutes.

[0039] According to the present invention, in step (2), vacuum thermal evaporation equipment is used to deposit metal electrodes on the upper and lower surfaces of the sheet-like ferroelectric porous ceramic at an evaporation rate of 5-20 mg / s (such as 6-10 mg / s, such as 8.61 mg / s).

[0040] According to the present invention, in step (3), the model of the ferroelectric tester is TF2000.

[0041] According to the present invention, in step (3), a ferroelectric tester is used to perform DC saturation polarization treatment on the sheet-like ferroelectric porous ceramic, and the polarization voltage is 100 to 3000 V / mm, preferably the polarization voltage is 200-1000 V / mm, and exemplarily 100 V / mm, 200 V / mm, 500 V / mm, 800 V / mm, 1000 V / mm, 2000 V / mm, and 3000 V / mm.

[0042] According to the present invention, in step (3), the voltage rate of the DC saturation polarization treatment of the ferroelectric ceramic using a ferroelectric tester is 0.3-0.5KV / mm / min, exemplified by 0.3KV / mm / min, 0.4KV / mm / min, and 0.5KV / mm / min.

[0043] According to the present invention, in step (3), the temperature of performing DC saturation polarization treatment on the ferroelectric ceramic using a ferroelectric tester is 20-120°C, exemplified by 40°C, 60°C, 80°C, 100°C, and 120°C.

[0044] According to the present invention, in step (4), the standing time is 12 to 48 hours, and the purpose of the standing time is to allow the ferroelectric porous ceramic to be completely filled with tritiated water.

[0045] Beneficial effects of the present invention:

[0046] The present invention provides a battery based on the beta-radiovoltaic effect of ferroelectric porous ceramics and a preparation method thereof. The present invention utilizes the internal electric field formed by the spontaneous polarization of the ferroelectric porous ceramics to separate electron-hole pairs generated by beta particle bombardment, and uses tritium water as a radioactive source for the beta-radiovoltaic effect.

[0047] Furthermore, the present invention can improve the conductivity of ferroelectric porous ceramics by doping them with rare earth elements. By using metals with low work functions as electrodes, while forming ohmic contacts, electrons generated by beta-bombarding the electrodes can also smoothly enter the ferroelectric porous ceramics, increasing the carrier concentration and further improving the conductivity of the ferroelectric porous ceramics.

[0048] In summary, the battery based on the beta-radiation voltaic effect of ferroelectric porous ceramics of the present invention has the characteristics of high energy utilization, high conversion efficiency, low cost, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 This is the principle diagram of the β-radiation voltaic effect battery based on ferroelectric porous ceramics. The middle curve represents 3Beta rays emitted by H decay. The solid and hollow circles represent electrons and holes, respectively, generated by beta particle bombardment. The upper and lower ellipsoids represent electric dipoles generated by spontaneous polarization and charge center separation in ferroelectric ceramics. Electron-hole pairs separate under the influence of the internal electric field of the ferroelectric ceramic, with holes moving upward and electrons moving downward, thus generating current.

[0050] Figure 2 This is a side view of the beta-radiation voltaic effect battery package based on ferroelectric porous ceramics, where 1 is a lead-containing radiation-proof glass box, 2 is the upper electrode, 3 is the ferroelectric porous ceramic, 4 is the lower electrode, 5 is tritium water, and 6 and 7 are lead terminals.

[0051] Figure 3 This is a graph showing how the induced current of the material in Example 1 changes with the switching of the radiation source.

[0052] Figure 4 This is a constant voltage test diagram of the material in Example 1.

[0053] Figure 5 The resistivity of the material in Example 1 changes with La 3+ Variation of doping amount. DETAILED DESCRIPTION

[0054] The present invention will be described in further detail below with reference to specific examples. It should be understood that the following examples are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0055] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; the reagents, materials, etc. used in the following examples are all commercially available unless otherwise specified.

[0056] Example 1: A beta-radiation voltaic effect cell based on lanthanum-doped barium titanate porous ceramics, the preparation method of which comprises the following steps:

[0057] 5 g of barium titanate powder with a particle size of 300-400 nm, 0.014 g of nano-lanthanum trioxide powder with a particle size of 20-100 nm and 0.1 g of polyvinyl butyral were mixed and ball-milled uniformly, and then the mixed powder was placed in an oven set at 80° C. and dried for 2 hours.

[0058] The dried powder was pressed into 1mm thin slices under a pressure of 15MPa using a tablet press. The powder was sintered at 700℃ for 10 hours in a muffle furnace to fully remove the plastic, and then sintered at 1150℃ for 5 hours. The flake Ba was cut and trimmed to obtain 0.998 La 0.002 TiO3 porous ceramics (10×10×1.2mm3 ), wherein the flake Ba 0.998 La 0.002 The porosity of the TiO3 porous ceramic is 30%, and the pore size distribution is 50-100 nm.

[0059] The prepared flake Ba 0.998 La 0.002 The porous TiO3 ceramic was immersed in anhydrous ethanol and ultrasonically cleaned for 20 minutes. The ceramic surface was then dried using a hair dryer. Using a vacuum thermal evaporation device at an evaporation rate of 8.61 mg / s, 300 nm thick silver thin film electrodes were deposited on both the top and bottom surfaces of the ceramic sheet.

[0060] The TF2000 standard ferroelectric tester was used to measure the 0.998 La 0.002 The TiO3 porous ceramics were polarized for 30 min with a polarization voltage of 1000 V / mm and a pressing rate of 0.4 KV / mm / min.

[0061] The polarized Ba 0.998 La 0.002 TiO3 porous ceramics are immersed in tritium water for 24 hours to ensure that the flake Ba 0.998 La 0.002 The pores of TiO3 porous ceramics can be fully filled with tritium water. 0.998 La 0.002 TiO3 porous ceramics are placed in 12×12×1.5mm 3 The device is placed in a lead-containing radiation-proof glass box, the terminal leads are connected, and the package is sealed.

[0062] Example 2: Beta-radiation voltaic effect battery based on lanthanum-doped lead zirconate titanate porous ceramics.

[0063] The other operations are the same as those in Example 1. The only difference is the preparation method of the ferroelectric porous ceramic and the polarization step: the synthesis of lanthanum-doped lead zirconate titanate Pb 0.998 La 0.002 (Zr 0.5 Ti 0.5)O3, according to the molar ratio of Pb:La:Zr:Ti=0.998:0.002:0.5:0.5, high-purity PbO, La2O3, ZrO2, TiO2 nanopowders (particle size range of 100-200nm) are mixed, and then methacrylic resin balls with a particle size of 300nm are added and ball milled to mix them evenly. The mixed powder is placed in an oven, the temperature is set to 80℃, and dried for 12 hours. Use a tablet press to press the powder into a thin sheet with a thickness of 1mm under a pressure of 10MPa. Continue to heat at 150℃ for 1 hour in a resistance furnace to fully burn the resin and form holes in the sheet. After cooling, use a muffle furnace to sinter, heat to 1000℃ at a heating rate of 100℃ / h and sinter for 3 hours to obtain flaky Pb 0.998 La 0.02 (Zr 0.5 Ti 0.5 )O3 porous ceramics, with a porosity of 50% and a pore size of 10 to 30 nm.

[0064] The TF2000 standard ferroelectric tester was used to measure the 0.998 La 0.002 (Zr 0.5 Ti 0.5 )O3 porous ceramics were polarized for 20 minutes to 0.998 La 0.02 (Zr 0.5 Ti 0.5 )O3 porous ceramics were placed in silicone oil at 110°C with a polarization voltage of 3000 V / mm and a pressurization rate of 0.4 KV / mm / min.

[0065] Example 3: Beta-radiation voltaic effect battery based on lanthanum-doped bismuth ferrite porous ceramics

[0066] The other operations are the same as those in Example 1, except that the preparation method of the ferroelectric porous ceramic is different and the polarization step is different: Bi2O3~2.7925g, La2O3~0.8335g, Fe2O3~1.3741g are weighed according to the molar ratio of Bi:La:Fe=0.7:0.3:1, and 21.9714g of NaCl and 28.0286g of KCl are added. The raw materials and salt are placed in a ball mill, 110g of ball stone and 35ml of ethanol are added, and the ball mill is carried out at a speed of 400r / min for 6h. After drying, a fine and uniformly mixed powder is obtained. The powder is then placed in a muffle furnace, sintered at 750℃ and kept warm for 2h at a temperature of 3℃ per minute. Ultrapure water is added to the cooled mixture to remove the NaCl and KCl therein, and the mixture is repeatedly washed at 80℃ for 9-10 times, then filtered and dried at 80℃ for 12h to obtain Bi2O3. 0.7 La 0.3 FeO3 powder.

[0067] The powder was pressed into a disc sample with a diameter of 10 mm and a thickness of 1 mm using a tablet press, and heated to 880°C at a temperature rise rate of 2°C / min and kept warm for 1 hour to obtain a sheet-like lanthanum-doped bismuth ferrite porous ceramic with a porosity of 30% and a pore size distribution of 50 to 100 nm.

[0068] The TF2000 standard ferroelectric tester was used to test the Bi 0.7 La 0.3 FeO3 porous ceramics were polarized for 10 min to 0.7 La 0.3 The FeO3 porous ceramics were placed in silicone oil at room temperature with a polarization voltage of 2000 V / mm and a pressurization rate of 0.4 KV / mm / min.

[0069] Test example:

[0070] Place the packaged beta-radiation voltaic effect battery on the low-temperature probe station TTPX low-temperature vacuum probe station, and make sure the probe is well connected to the battery lead.

[0071] Connect the probe station to the 4200-SCS semiconductor characterization tester. Use the photovoltaic test module of the 4200-SCS semiconductor characterization tester (Keithley Klckstart test software) to collect the battery's electrical output data. The test data is as follows:

[0072] The open circuit voltage of the β-radiation voltaic effect battery based on lanthanum-doped barium titanate porous ceramics prepared in Example 1 is 90 mV and the short circuit current is 3.6 nA; the open circuit voltage of the β-radiation voltaic effect battery based on lanthanum-doped lead zirconate titanate porous ceramics prepared in Example 2 is 100 mV and the short circuit current is 6.5 nA; the open circuit voltage of the β-radiation voltaic effect battery based on lanthanum-doped bismuth ferrite porous ceramics prepared in Example 3 is 80 mV and the short circuit current is 5.52 nA.

[0073] Figure 3 This is a graph showing the change in induced current of the material of Example 1 as the radiation source is switched on and off. As shown in the It curve, the energy conversion device of the present invention has a significant radiovoltaic effect.

[0074] Figure 4 This is a constant voltage test graph of the material of Example 1. As shown in the Vt curve, under irradiation from a radiation source, the energy conversion device of the present invention has the ability to output a stable voltage for a long time.

[0075] Figure 5 The resistivity of the material in Example 1 changes with La 3+ The graph of the change of doping amount. It can be seen from the graph that rare earth elements 147The incorporation of Pm can effectively reduce the resistivity of bismuth ferrite.

[0076] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A beta radiation voltaic effect battery, characterized in that: The battery is composed of an upper electrode layer, a ferroelectric porous ceramic layer and a lower electrode layer; the upper electrode layer, the ferroelectric porous ceramic layer and the lower electrode layer are sequentially connected, and the ferroelectric porous ceramic layer is filled with a radioactive source, which is tritium water; The thickness of the upper electrode layer is 150-400 nm; The thickness of the lower electrode layer is 150-400 nm; The thickness of the ferroelectric porous ceramic layer is 0.8-1.2 mm; The material forming the ferroelectric porous ceramic layer includes lead zirconate titanate Pb (Zr 1-y Ti y )O3, where 1>y>0, lanthanum-doped lead zirconate titanate Pb 1-x La x (Zr 1-y Ti y )O3, where 1>x>0, 1>y>0, barium titanate BaTiO3, lanthanum-doped barium titanate Ba 1-x La x TiO3, where 1>x>0, bismuth ferrite BiFeO3, lanthanum-doped bismuth ferrite Bi 1-x La x FeO3, wherein at least one of 1>x>0.

2. The battery according to claim 1, wherein The ferroelectric porous ceramic in the ferroelectric porous ceramic layer has a pore size distribution of 10-100 nm and a porosity of 20-40%.

3. The battery according to claim 1, wherein The electrode material forming the upper electrode layer and the electrode material forming the lower electrode layer are the same or different and are independently selected from silver, aluminum, and copper metals.

4. The battery according to any one of claims 1 to 3, characterized in that The open circuit voltage of the battery is 80-110 mV; And / or, the short-circuit current of the battery is 5-8 nA.

5. The method for preparing a beta-radiation voltaic effect battery according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: (1) Preparation of sheet-like ferroelectric porous ceramics; (2) Using vacuum thermal evaporation to deposit metal electrodes on the upper and lower surfaces of the sheet-like ferroelectric porous ceramic to form an upper electrode layer and a lower electrode layer; (3) using a ferroelectric tester to perform a DC saturation polarization treatment on the product of step (2); (4) Immerse the product of step (3) that has undergone polarization treatment in tritium water and allow it to stand; (5) The product after standing in step (4) is subjected to electrode connection and battery packaging to prepare the β-radiation voltaic effect battery.

6. The preparation method according to claim 5, wherein In step (1), when the material forming the ferroelectric porous ceramic layer is barium titanate, the preparation method of the sheet-like ferroelectric porous ceramic comprises the following steps: Barium titanate powder with a particle size of 300-400 nm and polyvinyl butyral are mixed uniformly by ball milling, dried at 60-80°C for 1-2 hours, pressed into 0.8-1.2 mm thin sheets using a tablet press at a pressure of 10-25 MPa, and then sintered at 600-700°C for 8-12 hours in a muffle furnace; and then sintered at 1150-1250°C for 3-8 hours to obtain sheet-like barium titanate porous ceramics. Wherein, the added amount of the polyvinyl butyral is 1-5wt% of the total mass of the mixture.

7. The preparation method according to claim 5, wherein In step (1), when the material forming the ferroelectric porous ceramic layer is lanthanum-doped barium titanate, the preparation method of the sheet-like ferroelectric porous ceramic comprises the following steps: Barium titanate powder with a particle size of 300-400 nm, polyvinyl butyral and lanthanum trioxide nanopowder are mixed uniformly by ball milling, dried at 60-80°C for 1-2 hours, pressed into 0.8-1.2 mm thin sheets using a tablet press at a pressure of 10-25 MPa, and then sintered at 600-700°C for 8-12 hours in a muffle furnace; and then sintered at 1150-1250°C for 3-8 hours to obtain sheet-like lanthanum-doped barium titanate porous ceramics. Among them, according to n(Ba 2+ ):n(La 3+ )=1-x: x is added to barium titanate powder and lanthanum trioxide nanopowder, wherein 1>x>0.

8. The preparation method according to claim 5, wherein In step (1), when the material forming the ferroelectric porous ceramic layer is lead zirconate titanate, the preparation method of the sheet-like ferroelectric porous ceramic comprises the following steps: The nanopowders of PbO, ZrO2 and TiO2 are mixed evenly, and then resin balls are added and mixed evenly by ball milling. After drying at 60-80°C for 1-2 hours, the thin sheets of 0.8-1.2 mm are pressed into the thin sheets at a pressure of 10-25 MPa using a tablet press. The thin sheets are then heated at 100-180°C for 1-2 hours using a resistance furnace to fully burn the resin and form pores in the thin sheets. After cooling, the thin sheets are sintered in a muffle furnace at 1000-1200°C for 3-8 hours to obtain a sheet-like porous lead zirconate titanate ceramic. The molar ratio of the nano powders of PbO, ZrO2 and TiO2 is such that 1-y Ti y )O3, wherein the stoichiometric ratio is 1>y>0; When the material forming the ferroelectric porous ceramic layer is lanthanum-doped lead zirconate titanate, the preparation method of the sheet-shaped ferroelectric porous ceramic comprises the following steps: The nanopowders of PbO, ZrO2, TiO2 and La2O3 are mixed evenly, and then resin balls are added and mixed evenly by ball milling. After drying at 60-80°C for 1-2 hours, the thin sheets of 0.8-1.2 mm are pressed into the thin sheets at a pressure of 10-25 MPa using a tablet press. The thin sheets are then heated at 100-180°C for 1-2 hours using a resistance furnace to fully burn the resin and form pores in the thin sheets. After cooling, the thin sheets are sintered in a muffle furnace at 1000-1200°C for 3-8 hours to obtain flaky lanthanum-doped lead zirconate titanate porous ceramics. The molar ratio of the nano powders of PbO, ZrO2, TiO2 and La2O3 is such that 1-x La x (Zr 1-y Ti y )O3, wherein the stoichiometric ratio is 1>x>0, 1>y>0.

9. The preparation method according to claim 5, wherein In step (1), when the material forming the ferroelectric porous ceramic layer is bismuth ferrite, the preparation method of the sheet-like ferroelectric porous ceramic comprises the following steps: Bi2O3 and Fe2O3 are mixed and NaCl and KCl are added, mixed evenly, the mixed powder is placed in a muffle furnace, sintered at 600-800°C for 1-5 hours, water is added to the cooled mixture to remove NaCl and KCl, washed, and dried to prepare a sheet-like bismuth ferrite porous ceramic; When the material forming the ferroelectric porous ceramic layer is lanthanum-doped bismuth ferrite, the preparation method of the sheet-shaped ferroelectric porous ceramic includes the following steps: mixing Bi2O3, Fe2O3 and La2O3 and adding NaCl and KCl, mixing evenly, placing the evenly mixed powder into a muffle furnace, sintering at 600-800°C for 1-5 hours, adding water to the cooled mixture to remove NaCl and KCl therefrom, washing, and drying to prepare the sheet-shaped lanthanum-doped bismuth ferrite porous ceramic.

10. The preparation method according to any one of claims 5 to 7, characterized in that: In step (2), a vacuum thermal evaporation device is used to deposit metal electrodes on the upper and lower surfaces of the sheet-like ferroelectric porous ceramic at an evaporation rate of 5-20 mg / s.

11. The preparation method according to any one of claims 5 to 7, characterized in that: In step (3), a ferroelectric tester is used to perform a DC saturation polarization treatment on the sheet-like ferroelectric porous ceramic, and the polarization voltage is 100~3000V / mm.

Images