CN114743712A - Based on147Pm doped ferroelectric ceramic battery with beta radiation volt effect and preparation method thereof - Google Patents

Based on147Pm doped ferroelectric ceramic battery with beta radiation volt effect and preparation method thereof Download PDF

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CN114743712A
CN114743712A CN202111376529.XA CN202111376529A CN114743712A CN 114743712 A CN114743712 A CN 114743712A CN 202111376529 A CN202111376529 A CN 202111376529A CN 114743712 A CN114743712 A CN 114743712A
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doped
ferroelectric ceramic
lanthanum
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electrode layer
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杨帆
宋志雄
王凯先
薛丽燕
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Mindu Innovation Laboratory
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Abstract

The invention discloses a battery based on a beta radiation volt effect of 147Pm doped ferroelectric ceramic and a preparation method thereof, wherein the battery comprises an upper electrode layer,147A Pm doped ferroelectric ceramic layer and a lower electrode layer; the upper electrode layer, the ferroelectric ceramic layer and the lower electrode layer are sequentially connected. The invention is prepared by147Pm is doped into the ferroelectric ceramic, so that the effective combination of the energy conversion device and the radioactive source is realized, the energy loss caused by the self absorption of the radioactive source and the energy deposition on the surface of the energy conversion material is eliminated, and the energy utilization rate of the battery is greatly improved. Doping in ferroelectric ceramics147Pm, effectively improving the conductivity of the ferroelectric ceramic. And is provided with147Pm is a radioactive element, can emit beta rays in the decay process, and can greatly improve the conductivity of the ferroelectric ceramic and obtain higher conversion efficiency when being doped into the ferroelectric ceramic to realize the integration of a radioactive source and an energy conversion device.

Description

Based on147Pm doped ferroelectric ceramic battery with beta radiation volt effect and preparation method thereof
Technical Field
The invention belongs to the technical field of nuclear energy utilization, relates to a beta radiation volt effect battery, and particularly relates to a beta radiation volt effect battery147A beta radiation volt effect battery using Pm doped ferroelectric ceramic as energy conversion material and a preparation method thereof.
Background
Since the 21 st century, micro-electro-mechanical systems are widely applied, and have the advantages of small size, good stability, multiple functions, low power consumption and the like, are successfully applied to the fields of automobile safety airbag sensors, ink nozzles, unmanned aerial vehicle control and the like at present, and are further applied to the aspects of Internet of things, wearable equipment and the like in the future. In the research of the MEMS, the research on electronic devices such as sensors and actuators is sufficient, but the research on related micro power supplies is relatively lacking. The beta radiation volt effect battery has the advantages of high energy density, long service life, strong environmental adaptability, stable performance, no maintenance, micromation and the like, and is the most potential one of miniature power supplies.
The development of beta radiation volt effect batteries involves mainly three problems: 1. selecting an isotope radioactive source; 2. selecting a transduction material; 3. and (4) designing the energy conversion device. There are two main types of energy transfer devices, p-n junction and schottky. The p-n junction type has higher conversion efficiency than a Schottky type, but the preparation is difficult and the manufacturing cost is high. The principle of the beta radiation volt effect battery is similar to that of a solar battery, and electron-hole pairs are formed inside the beta radiation volt effect battery through external particle bombardment, and then the beta radiation volt effect battery is separated and moves under the action of an electric field built in a p-n junction or a Schottky junction to form current. Because the ferroelectric ceramic forms an electric field inside due to spontaneous polarization, the ferroelectric material has been widely studied in the photovoltaic field, and for the ferroelectric semiconductor, residual polarization and an internal electric field caused by polarization exist in the whole ferroelectric semiconductor region, and the transmission of charges is not limited by diffusion, so that the output photogenerated voltage is not limited by an energy gap and is far higher than the energy gap. Furthermore, since the effective field in ferroelectric semiconductors is an order of magnitude higher than conventional semiconductor p-n junctions, the photovoltaic voltage is several orders of magnitude higher than conventional p-n junctions. However, the ferroelectric ceramic has little application in the field of beta radiation volt effect batteries, and the current output of the ferroelectric ceramic is relatively low, which is also the biggest obstacle to the application of the ferroelectric ceramic in energy conversion at present.
The existing beta radiation volt-effect battery mainly adopts a structure form that a radioactive source is separated from an energy conversion device, and the structure has very large energy loss. First, the radiation source absorbs a portion of the energy when it emits beta radiation, a phenomenon known as self-absorption by the radiation source, and the larger the volume of the radiation source, the more severe the self-absorption. Secondly, the surface of the energy conversion material forms an energy deposition layer with a certain thickness during the use process, and the thickness of the deposition layer is directly related to the density of the energy conversion device.
Disclosure of Invention
Aiming at the problems in the prior art and based on the special advantages of the ferroelectric ceramics in the aspect of energy conversion, the invention provides a ferroelectric ceramic based on147The Pm doped ferroelectric ceramic beta radiation volt effect battery realizes the integrated combination of a radioactive source and an energy conversion device, obtains the energy conversion efficiency of 7 percent, simultaneously leads the battery structure to be more compact and realizes the miniaturization to a greater extent.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a beta-radiation volt-effect cell, the cell comprising an upper electrode layer,147A Pm doped ferroelectric ceramic layer and a lower electrode layer; the upper electrode layer, the ferroelectric ceramic layer and the lower electrode layer are sequentially connected.
According to the invention, the thickness of the upper electrode layer is 150-400 nm, such as 300 nm.
According to the invention, the147The thickness of the Pm doped ferroelectric ceramic layer is 0.8-1.2 mm, for example 1 mm.
According to the invention, the thickness of the lower electrode layer is 150-400 nm, for example 300 nm.
According to the invention, the147Pm doped ferroelectric ceramic layer147The doping amount of Pm is 0.5-10%, exemplarily 1%, 1.5%, 2%, 5%, 8%, 10%.
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.
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 at least one of metals such as silver, aluminum, copper, magnesium, and the like.
According to the invention, the electrode material can form ohmic contact with the ferroelectric ceramic, and electrons generated by beta particle bombardment of the electrode can smoothly enter the ferroelectric ceramic, so that the carrier concentration is improved, and the conductivity of the ferroelectric ceramic is improved.
The radioactive source in the invention is doped in the ferroelectric ceramic147Pm, the ferroelectric ceramic can effectively absorb the radiated beta rays, prevent beta particles from dissipating and effectively ensure the safety of the battery in the use process.
According to the present invention, the ferroelectric material forming the ferroelectric ceramic layer includes lead zirconate titanate (Pb (Zr)1-yTiy)O3Wherein 1 is>y>0) Lanthanum-doped lead zirconate titanate (Pb)1-xLax(Zr1-yTiy)O3Wherein 1 is>x>0、1>y>0) Barium titanate (BaTiO)3) Lanthanum-doped barium titanate (Ba)1-xLaxTiO3Wherein 1 is>x>0) Bismuth ferrite (BiFeO)3) Lanthanum-doped bismuth ferrite (Bi)1-xLaxFeO3Wherein 1 is>x>0) At least one of (1).
According to the present invention, the battery further includes an electrode lead and a battery package structure. The locations where the electrode leads and the battery package structure are disposed are known in the art.
According to the invention, the open-circuit voltage of the battery is 80-110 mV, for example 100 mV.
According to the invention, the short-circuit current of the battery is 5-8 nA, for example 6 nA.
The invention also provides a preparation method of the beta radiation volt effect battery, which comprises the following steps:
(1) preparation of147Pm doped ferroelectric ceramic;
(2) prepared in step (1) by using a vacuum thermal evaporation method147Depositing metal electrodes on the upper surface and the lower surface of the Pm-doped ferroelectric ceramic to form an upper electrode layer and a lower electrode layer;
(3) performing direct current saturation polarization treatment on the product prepared in the step (2) by using a ferroelectric tester;
(4) and (4) carrying out electrode lead wire connection and battery packaging on the product prepared in the step (3) to prepare the beta radiation volt effect battery.
According to the present invention, in the step (1), the ferroelectric ceramic is a ferroelectric ceramic of a lamellar structure.
According to the present invention, in the step (1), the material for forming the ferroelectric ceramic of the lamellar structure comprises lead zirconate titanate (Pb (Zr)1- yTiy)O3Wherein 1 is>y>0) Lanthanum-doped lead zirconate titanate (Pb)1-xLax(Zr1-yTiy)O3Wherein 1 is>x>0、1>y>0) Barium titanate (BaTiO)3) Lanthanum-doped barium titanate (Ba)1-xLaxTiO3Wherein 1 is>x>0) Bismuth ferrite (BiFeO)3) Lanthanum-doped bismuth ferrite (Bi)1- xLaxFeO3Wherein 1 is>x>0) At least one of (a).
According to the present invention, in the step (1), the material for forming the ferroelectric ceramic layer is147Pm doped barium titanate or147When the lanthanum-doped barium titanate is doped with Pm,147the preparation method of the Pm doped ferroelectric ceramic comprises the following steps:
a1) barium hydroxide, titanium dioxide and optionally lanthanum oxide are used as precursors and are dropwise added147Pm(NO3)3Incorporation of147Pm, carrying out hydrothermal reaction for 6 hours at 180 ℃ to obtain the doped147Pm barium titanate or147Pm blendDoped lanthanum barium titanate powder;
b1) mixing the mixture obtained in step a1)147Pm barium titanate or147Mixing Pm-doped lanthanum-doped barium titanate powder with a binder polyvinyl alcohol, drying for 1-2 hours at the temperature of 60-80 ℃, pressing into a sheet with the thickness of 0.8-1.2 mm by using a tablet press under the pressure of 10-25 MPa, and sintering for 8-12 hours at the temperature of 600-700 ℃; then sintering for 3-8 hours at the temperature of 1150-1250 ℃ to prepare the doped material147Pm barium titanate or147Pm doped lanthanum-doped barium titanate ceramic.
According to the present invention, in the step (1), the material for forming the ferroelectric ceramic layer is147Pm-doped lead zirconate titanate or147When the lead zirconate titanate is doped with lanthanum and mixed with Pm,147the preparation method of the Pm doped ferroelectric ceramic comprises the following steps:
mixing PbO and ZrO2、TiO2、147Pm2O3And optionally La2O3Mixing the nano powder, adding the resin pellets, performing ball milling and mixing uniformly, drying for 1-2 hours at the temperature of 60-80 ℃, pressing into a 0.8-1.2 mm thin sheet by using a tablet press under the pressure of 10-25 MPa, and continuously heating for 1-2 hours at the temperature of 100-180 ℃ by using a resistance furnace to combust the resin, so that holes are formed in the thin sheet; cooling and sintering at 1000-1200 ℃ for 3-8 hours to obtain147Pm-doped lead zirconate titanate or147Pm doped lanthanum-doped lead zirconate titanate ceramic.
According to the present invention, in the step (1), the material for forming the ferroelectric ceramic layer is147Pm doped bismuth ferrite or147When the lanthanum-doped bismuth ferrite is doped with Pm,147the preparation method of the Pm doped ferroelectric ceramic comprises the following steps:
adding Bi2O3、Fe2O3、147Pm2O3And optionally La2O3Mixing and adding NaCl and KCl, mixing uniformly, sintering the uniformly mixed powder at 600-800 ℃ for 1-5 h, adding water into the cooled mixture to remove NaCl and KCl, washing, drying, and preparing to obtain the product147Pm-doped bismuth ferrite or lanthanum-doped bismuth ferrite ceramic.
According to the invention, in the step (2), the method also comprises the step of mixing the product obtained in the step (1)147And (3) putting the Pm-doped ferroelectric ceramic into absolute ethyl alcohol, and carrying out ultrasonic cleaning.
According to the present invention, in step (2), metal electrodes are deposited on the upper and lower surfaces of the ferroelectric ceramic at an evaporation rate of 5 to 20mg/s (e.g., 6 to 10mg/s, e.g., 8.61mg/s) using a vacuum thermal evaporation apparatus.
According to the invention, in the step (3), the model of the ferroelectric tester is TF 2000.
According to the invention, in the step (3), the ferroelectric ceramic is subjected to direct current saturation polarization treatment by using a ferroelectric tester, wherein the polarization voltage is 100-3000V/mm, preferably 200-1000V/mm, and is exemplified by 100V/mm, 200V/mm, 500V/mm, 800V/mm, 1000V/mm, 2000V/mm and 3000V/mm.
According to the present invention, in the step (3), the ferroelectric ceramic is subjected to the direct current saturation polarization treatment using the ferroelectric tester at a pressurization rate of 0.3 to 0.5KV/mm/min, illustratively 0.3KV/mm/min, 0.4KV/mm/min, 0.5 KV/mm/min.
The invention has the beneficial effects that:
the invention provides a ferroelectric ceramic-based battery with beta radiation volt effect and a preparation method thereof; the invention is characterized in that147Pm is doped into the ferroelectric ceramic, so that the effective combination of the energy conversion device and the radioactive source is realized, the energy loss caused by self absorption of the radioactive source and energy deposition on the surface of the energy conversion material is eliminated, and the energy utilization rate of the battery is greatly improved. Doping in ferroelectric ceramics147Pm, effectively improving the conductivity of the ferroelectric ceramic. And is147Pm is a radioactive element, can emit beta rays in the decay process, and can greatly improve the conductivity of the ferroelectric ceramic and obtain higher conversion efficiency when being doped into the ferroelectric ceramic to realize the integration of a radioactive source and an energy conversion device.
Drawings
FIG. 1 is a graph based on147Schematic diagram of Pm doped ferroelectric ceramic beta radiation volt effect battery, middle curve representing147The Pm decays to emit beta rays, and the filled circle and the open circle respectively represent the quiltElectrons and holes generated by beta particle bombardment. The upper and lower elliptical spheres represent electric dipoles generated by separation of charge centers due to spontaneous polarization in the ferroelectric ceramic, electron-hole pairs are separated under the action of an internal electric field of the ferroelectric ceramic, holes move upward, and electrons move downward, thereby generating current.
FIG. 2 is a graph based on147A p-radiation volt effect cell package side view of a Pm doped ferroelectric ceramic, wherein: 1 is a lead-containing radiation-proof glass box, 2 is an upper electrode, and 3 is147Pm doped ferroelectric ceramic, 4 is a lower electrode, and 5 and 6 are lead terminals.
FIG. 3 is a graph of induced current versus radiation source switching for the material of example 3.
FIG. 4 is a constant voltage test plot of the material of example 3.
FIG. 5 is a plot of resistivity versus material of example 3147And (3) a change graph of the doping amount of the Pm.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1: based on mixing147The preparation method of the Pm barium titanate beta radiation volt effect battery comprises the following steps:
(1) titanium oxide and barium hydroxide were weighed in a molar ratio of 1:1.194, and 1M in concentration was added dropwise147Pm(NO3)3To ensure147Pm(NO3)3The molar ratio of the barium hydroxide to the barium hydroxide is 0.995:0.005, the mixture is placed in the inner liner of a polytetrafluoroethylene hydrothermal kettle, and the mixture is reacted for 6 hours in an oven at the temperature of 180 ℃ to obtain the doped barium hydroxide147Pm barium titanate powder;
(2) centrifugally washing the powder prepared in the step (1) for three times, and drying the powder for 10 hours at the temperature of 80 ℃. Placing the mixture into a mortar, adding 5 wt% of polyvinyl alcohol, mixing, grinding for 15 minutes, and continuously drying at the temperature of 80 ℃ for 2 hours;
(3) and (3) pressing the dried powder in the step (2) into a 1mm slice by using a tablet press under the pressure of 15 MPa. Sintering at 700 deg.C for 10 hr in muffle furnace, removing plastic, sintering at 1150 deg.C for 5 hr, cutting and trimming to obtain flake Ba0.995 147Pm0.005TiO3Ceramics (length 10mm x width 10mm x thickness 0.5 mm);
(4) the flake Ba prepared in the step (3) is added0.995 147Pm0.005TiO3Immersing the ceramic into absolute ethyl alcohol, ultrasonically cleaning for 20min, and drying the surface of the ceramic by using a blower. Using vacuum thermal evaporation equipment, setting an evaporation speed of 8.61mg/s, and respectively depositing silver film electrodes with the thickness of 300nm on the upper surface and the lower surface of the flaky ceramic;
(5) using TF2000 standard ferroelectric tester for testing Ba flakes0.995 147Pm0.005TiO3Carrying out 30min polarization treatment on the ceramic, wherein the polarization voltage is 1000V/mm, and the pressurizing rate is 0.4 KV/mm/min;
(6) processed flake Ba0.995 147Pm0.005TiO3Ceramic inlay 12X 1.5mm3In the lead-containing radiation-proof glass box, a terminal lead is connected and sealed.
Example 2: based on mixing147Pm lanthanum-doped lead zirconate titanate beta radiation volt effect battery.
The other operations are the same as example 1, except that the ferroelectric ceramic preparation method and the polarization step are different: synthetic blend147Pm lanthanum-doped lead zirconate titanate Pb0.975La0.02 147Pm0.005(Zr0.5Ti0.5)O3Weighing PbO and La according to the molar ratio of 0.975:0.01:0.0025:0.5:0.5:32O3、147Pm2O、ZrO2、TiO23And methacrylic resin pellets, and then adding PbO and La2O3、147Pm2O、ZrO2、TiO23Mixing the nano powder (the particle size range is 100-200 nm), adding methacrylic resin balls with the particle size of 300nm, and performing ball milling to uniformly mix the methacrylic resin balls. The mixed powder was placed in an oven and dried at 80 ℃ for 12 hours. The powder was compressed into a sheet having a thickness of 1mm using a tablet press under a pressure of 10 MPa. The heating was continued for 1 hour at 150 ℃ in a resistance furnace to sufficiently burn the resin and form holes in the sheet. Cooling, sintering in a muffle furnace, heating to 1200 deg.C at a heating rate of 100 deg.C/h, and sintering for 3 hr to obtain flaky Pb0.975La0.02 147Pm0.005(Zr0.5Ti0.5)O3A ceramic;
using TF2000 standard ferroelectric tester for flaky Pb0.975La0.02 147Pm0.005(Zr0.5Ti0.5)O3Subjecting the ceramic to 20min polarization treatment to obtain flaky Pb0.975La0.02 147Pm0.005(Zr0.5Ti0.5)O3The ceramic was placed in silicone oil at 110 ℃ with a polarization voltage of 3000V/mm and a pressing rate of 0.4 KV/mm/min.
Example 3: based on mixing147Pm lanthanum-doped bismuth ferrite beta radiation volt effect battery.
The other operations are the same as example 1, except that the ferroelectric ceramic preparation method and the polarization step are different: preparation of doped salt by molten salt method using NaCl-KCl mixed salt as molten salt system147Pm lanthanum-doped bismuth ferrite.
According to the ratio of Bi to La:147fe (Pm) in a stoichiometric ratio of 0.697:0.297:0.005:1, and taking Bi as a raw material2O3～2.7925g、La2O3～0.8335g、147Pm2O3～0.01457g、Fe2O3About 1.3741g, adding 21.9714g of NaCl and 28.0286g of KCl, putting the raw materials and salt into a ball milling tank, adding 110g of ball stone and 35ml of ethanol, then carrying out ball milling for 6h at the rotating speed of 400r/min, drying to obtain fine and uniformly mixed powder, then putting the powder into a muffle furnace, and adopting a temperature rising method of 3 ℃/min per minuteSintering at 750 ℃ and keeping the temperature for 2 h. Adding ultrapure water into the cooled mixture to remove NaCl and KCl in the mixture, repeatedly washing the mixture at 80 ℃ for 9-10 times, performing suction filtration, and drying the mixture at 80 ℃ for 12 hours to obtain Bi0.697La0.297 147Pm0.005FeO3And (3) powder.
Pressing the powder into a wafer-shaped sample with the diameter of 10mm and the thickness of 1mm by using a tablet press, heating to 880 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h to obtain a bismuth ferrite ceramic chip, and coating silver paste on two ends of the ceramic chip to prepare an electrode.
Use TF2000 standard ferroelectric tester to slice Bi0.695La0.3 147Pm0.005FeO3Subjecting the ceramic to polarization treatment for 10min to obtain sheet Bi0.695La0.3 147Pm0.005FeO3The ceramic was placed in silicone oil at room temperature with a polarization voltage of 2000V/mm and a pressing rate of 0.4 KV/mm/min.
Test example
The packaged beta radiant volt-effect cell is placed on a cryogenic probe station (TTPX cryogenic vacuum probe station) with good connection between the probe and the cell lead.
The probe station was connected to a 4200-SCS type semiconductor characteristic tester. The electrical output data of the cells were collected using a photovoltaic test module (Keithley Klckstart test software) of a semiconductor property tester model 4200-SCS, and the test results were as follows:
example 1 preparation based on blending147The open circuit voltage of the Pm barium titanate beta radiation volt-effect battery is 90mV, and the short circuit current is 7.2 nA; example 2 preparation based on blending147The open-circuit voltage of the Pm lanthanum-doped lead zirconate titanate beta radiation volt-effect battery is 100mV, and the short-circuit current is 6.5 nA; example 3 preparation based on blending147The open-circuit voltage of the beta radiation volt-effect battery with Pm bismuth ferrite is 80mV, and the short-circuit current is 5.52 nA.
FIG. 3 is a graph of induced current versus radiation source switching for the material of example 3. As shown by the I-t curve, the energy conversion device has obvious radiation volt effect.
FIG. 4 is a constant voltage test plot of the material of example 3. As shown by a V-t curve, under the irradiation of a radiation source, the energy conversion device has the capability of outputting voltage stably for a long time.
FIG. 5 is a plot of resistivity versus material of example 3147And (3) a change graph of the doping amount of the Pm. As can be seen from the figure: rare earth elements147The incorporation of Pm can effectively reduce the resistivity of the bismuth ferrite.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A beta-radiation volt effect cell, characterized in that it comprises an upper electrode layer,147A Pm doped ferroelectric ceramic layer and a lower electrode layer; the upper electrode layer, the ferroelectric ceramic layer and the lower electrode layer are sequentially connected.
2. The battery of claim 1, wherein the upper electrode layer has a thickness of 150 to 400 nm.
Preferably, the147The thickness of the Pm doped ferroelectric ceramic layer is 0.8-1.2 mm.
Preferably, the thickness of the lower electrode layer is 150-400 nm.
Preferably, the147Pm doped ferroelectric ceramic layer147The doping amount of Pm is 0.5-10%.
3. The battery according to claim 1 or 2, wherein an electrode material forming the upper electrode layer and an electrode material forming the lower electrode layer are the same or different and are independently selected from at least one of metals such as silver, aluminum, copper, magnesium, and the like.
Preferably, the ferroelectric material forming the ferroelectric ceramic layer includes lead zirconate titanate (Pb (Zr)1-yTiy)O3Wherein 1 is>y>0) Lanthanum-doped lead zirconate titanate (Pb)1-xLax(Zr1-yTiy)O3Wherein 1 is>x>0、1>y>0) Barium titanate (BaTiO)3) Lanthanum-doped barium titanate (Ba)1- xLaxTiO3Wherein 1 is>x>0) Bismuth ferrite (BiFeO)3) Lanthanum-doped bismuth ferrite (Bi)1-xLaxFeO3Wherein 1 is>x>0) At least one of (a).
4. The battery of any of claims 1-3, further comprising an electrode lead and a battery packaging structure.
Preferably, the open-circuit voltage of the battery is 80-110 mV.
Preferably, the short-circuit current of the battery is 5-8 nA.
5. The method of manufacturing a beta-radiation volt effect battery according to any one of the claims 1-4 characterized in that the method comprises the steps of:
(1) preparation of147Pm doped ferroelectric ceramic;
(2) prepared in step (1) by using a vacuum thermal evaporation method147Depositing metal electrodes on the upper surface and the lower surface of the Pm-doped ferroelectric ceramic to form an upper electrode layer and a lower electrode layer;
(3) performing direct current saturation polarization treatment on the product prepared in the step (2) by using a ferroelectric tester;
(4) and (4) carrying out electrode lead wire connection and battery packaging on the product prepared in the step (3) to prepare the beta radiation volt effect battery.
6. The method according to claim 5, wherein in the step (1), the ferroelectric ceramic is a ferroelectric ceramic of a lamellar structure.
Preferably, in the step (1), the material forming the ferroelectric ceramic of the lamellar structure includes lead zirconate titanate (Pb (Zr)1-yTiy)O3Wherein 1 is>y>0) Lanthanum-doped lead zirconate titanate (Pb)1-xLax(Zr1-yTiy)O3Wherein 1 is>x>0、1>y>0) Barium titanate (Ba)TiO3) Lanthanum-doped barium titanate (Ba)1-xLaxTiO3Wherein 1 is>x>0) Bismuth ferrite (BiFeO)3) Lanthanum-doped bismuth ferrite (Bi)1-xLaxFeO3Wherein 1 is>x>0) At least one of (1).
7. The production method according to claim 5 or 6, wherein in the step (1), the material for forming the ferroelectric ceramic layer is147Pm doped barium titanate or147When the lanthanum-doped barium titanate is doped with Pm,147the preparation method of the Pm doped ferroelectric ceramic comprises the following steps:
a1) barium hydroxide, titanium dioxide and optionally lanthanum oxide are used as precursors and are dropwise added147Pm(NO3)3Incorporation of147Pm, carrying out hydrothermal reaction for 6 hours at 180 ℃ to obtain the doped147Pm barium titanate or147Pm doped lanthanum-doped barium titanate powder;
b1) mixing the mixture obtained in step a1)147Pm barium titanate or147Mixing Pm-doped lanthanum-doped barium titanate powder with a binder polyvinyl alcohol, drying for 1-2 hours at the temperature of 60-80 ℃, pressing into a sheet with the thickness of 0.8-1.2 mm by using a tablet press under the pressure of 10-25 MPa, and sintering for 8-12 hours at the temperature of 600-700 ℃; then sintering for 3-8 hours at the temperature of 1150-1250 ℃ to prepare the doped material147Pm barium titanate or147Pm doped lanthanum-doped barium titanate ceramic.
8. The production method according to any one of claims 5 to 7, wherein in the step (1), the material for forming the ferroelectric ceramic layer is147Pm-doped lead zirconate titanate or147When the lead zirconate titanate is doped with lanthanum and mixed with Pm,147the preparation method of the Pm doped ferroelectric ceramic comprises the following steps:
mixing PbO and ZrO2、TiO2、147Pm2O3And optionally La2O3Mixing the nano powder, adding the resin balls, ball-milling and uniformly mixing, drying for 1-2 hours at the temperature of 60-80 ℃, and then using a tablet press to perform mixing at the pressure of 10-25 MPaPressing the mixture into a sheet with the thickness of 0.8-1.2 mm under pressure, and continuously heating the sheet for 1-2 hours at the temperature of 100-180 ℃ by using a resistance furnace to combust the resin so as to form holes in the sheet; cooling and sintering at 1000-1200 ℃ for 3-8 hours to obtain147Pm-doped lead zirconate titanate or147Pm doped lanthanum-doped lead zirconate titanate ceramic.
9. The production method according to any one of claims 5 to 8, wherein in the step (1), the material for forming the ferroelectric ceramic layer is147Pm doped bismuth ferrite or147When the lanthanum-doped bismuth ferrite is doped with Pm,147the preparation method of the Pm doped ferroelectric ceramic comprises the following steps:
adding Bi2O3、Fe2O3、147Pm2O3And optionally La2O3Mixing and adding NaCl and KCl, mixing uniformly, sintering the uniformly mixed powder at 600-800 ℃ for 1-5 h, adding water into the cooled mixture to remove NaCl and KCl, washing, drying, and preparing to obtain the product147Pm-doped bismuth ferrite or lanthanum-doped bismuth ferrite ceramic.
10. The production method according to any one of claims 5 to 9, wherein in the step (2), metal electrodes are deposited on the upper and lower surfaces of the ferroelectric ceramic at an evaporation rate of 5 to 20mg/s using a vacuum thermal evaporation apparatus.
Preferably, in the step (3), the ferroelectric ceramic is subjected to direct current saturation polarization treatment by using a ferroelectric tester, and the polarization voltage is 100-.
Preferably, in the step (3), the pressurizing rate of the direct current saturation polarization treatment of the ferroelectric ceramic by using the ferroelectric tester is 0.3-0.5 KV/mm/min.
CN202111376529.XA 2021-11-19 2021-11-19 Based on147Pm doped ferroelectric ceramic battery with beta radiation volt effect and preparation method thereof Pending CN114743712A (en)

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