Betavoltaic device

Abstract

The present invention relates to an apparatus for generating electrical energy, a method for generating electrical energy, a product for use in an apparatus for generating electrical energy, and a method for manufacturing an apparatus for generating electrical energy. In a predetermined embodiment, the present invention provides an electrical energy generating apparatus, wherein the apparatus comprises at least one cell comprising a first electrode and a second electrode spaced apart—the first electrode comprises a low work function material and the second electrode comprises a high work function material—and a beta particle emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode—the semiconductor material may generate electron-hole pairs in response to beta particle emission from the radionuclide.

Description

Technology Field

[0001] Claim of priority

[0002] This application claims priority to Australian provisional application 2019901722 filed on May 21, 2019 and Australian provisional application 2019901723 filed on May 21, 2019, the contents of all of which are incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to a device for generating electrical energy, a method for generating electrical energy, a product for use in a device for generating electrical energy, and a method for manufacturing a device for generating electrical energy. Background Technology

[0005] The use of electrochemical devices to generate electrical energy is widespread. While these devices rely on conventional chemical reactions to supply power, their service life is limited unless they are recharged or refueled. Rechargeable electrochemical devices can extend the service life of electrochemical energy devices, but they also have many inherent limitations, particularly as the devices lose their ability to be recharged over time.

[0006] In addition, devices that convert ionizing radiation into electrical energy have been developed. For example, devices utilizing beta radiation to generate electricity have been developed and are generally referred to as "betavoltaic" devices. Such devices are attracting significant interest in fields requiring long-term power output or where changing or servicing power sources is impractical.

[0007] Considering the large quantities of waste radionuclides generated by various processes historically and in the future, it would be advantageous to power such devices by utilizing the unique energy particle emissions of these waste radionuclides. This would provide economic and / or environmental benefits associated with utilizing waste radionuclides.

[0008] However, during the development of betavolta devices, there have typically been many limitations, such as low conversion efficiency, low power output, and / or reduced lifespan due to radiation damage.

[0009] The present invention relates to a betavoltaic device capable of using various different beta particle-emitting radionuclides to generate electricity, and improving one or more of the disadvantages of the prior art as discussed herein and / or providing one or more advantages.

[0010] The present invention relates to a device for generating electrical energy, a method for generating electrical energy, a product for use in a device for generating electrical energy, and a method for manufacturing a device for generating electrical energy.

[0011] A predetermined embodiment of the present invention provides an electric energy generating device, said device

[0012] A first electrode and a second electrode spaced apart—the first electrode comprises a low work function material, and the second electrode comprises a high work function material—; and

[0013] A beta particle-emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode—the semiconductor material may generate electron-hole pairs in response to beta particle emission from the radionuclide—

[0014] It includes at least one battery containing

[0015] A predetermined embodiment of the present invention provides a method for generating electricity, the method comprising the step of using an electricity generating device as described herein to generate electrical energy.

[0016] A predetermined embodiment of the present invention provides a method for generating electrical energy, said method

[0017] A step of generating a potential difference between a first electrode and a second electrode that are closely spaced apart—the first electrode comprises a low work function material, and the second electrode comprises a high work function material—;

[0018] A step of generating electron-hole pairs from energy beta particles emitted from a radionuclide located in very close proximity to a semiconductor material disposed between the first electrode and the second electrode—the electron-hole pairs move under the influence of an electric field—; and

[0019] A step of capturing the electron-hole pair into an external circuit using the electric field existing between the electrodes.

[0020] A method comprising; and thereby generating electrical energy.

[0021] A predetermined embodiment of the present invention provides a method for generating electrical energy, said method

[0022] A step of generating an electric field between a spaced-apart first electrode and a second electrode—the first electrode comprises a low work function material and the second electrode comprises a high work function material, and the electric field is generated due to different Schottky junctions at the two different electrodes—;

[0023] A step of generating electron-hole pairs from energy beta particles emitted from a radionuclide located in very close proximity to a semiconductor material disposed between the first electrode and the second electrode—the electron-hole pairs move under the influence of an electric field—; and

[0024] A step of capturing the electron-hole pair into an external circuit using the electric field existing between the electrodes.

[0025] A method comprising; and thereby generating electrical energy.

[0026] A predetermined embodiment of the present invention provides an apparatus for generating electrical energy using the method described herein.

[0027] A predetermined embodiment of the present invention provides a product comprising a first material having a low work function, a second material having a high work function, a beta particle emitting radionuclide disposed between the first material and the second material, and a semiconductor material capable of generating electron-hole pairs in response to the emission of beta particles from the radionuclide.

[0028] A predetermined embodiment of the present invention provides an electric energy generating device comprising a product as described in this specification.

[0029] A predetermined embodiment of the present invention provides a method for generating electrical energy, the method comprising the step of using a product as described herein.

[0030] A predetermined embodiment of the present invention provides a method for manufacturing an electric energy generating device, the method comprising the step of integrating one or more electric cells into the electric energy generating device, wherein the one or more electric cells comprise a spaced-apart first electrode and a second electrode—the first electrode comprises a low work function material and the second electrode comprises a high work function material—and a beta particle emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode—the semiconductor material may generate electron-hole pairs in response to beta particle emission from the radionuclide.

[0031] A predetermined embodiment of the present invention provides an electric energy generating device manufactured by a method as described in this specification.

[0032] Other embodiments are disclosed in this specification. Brief explanation of the drawing

[0033] For a better understanding of the present invention and to clearly show how the present invention can be practiced according to one or more embodiments of the present invention, reference will be made to the accompanying drawings by way of example. FIG. 1 shows that a semiconductor material for a betavolta device can occupy any position within a space surrounded by three terminal members, namely, (i) a pure semiconductor polymer having suitable electronic properties; (ii) a semiconductor single-phase complex comprising an inorganic compound chemically combined with the polymer (generally containing nitrogen and / or sulfur heteroatoms); and (iii) a crystalline semiconductor having a defined chemical composition and stoichiometry. This semiconductor material may include a mixture or blend between any two terminal members or between all three terminal members (on a nanometer scale). Specific details for implementing the invention

[0034] The present invention relates to a device for generating electrical energy, a method for generating electrical energy, a product for use in a device for generating electrical energy, and a method for manufacturing a device for generating electrical energy.

[0035] The present invention is based on the recognition that electrical energy can be generated by using a device that uses a semiconductor material placed between electrodes having different work functions and exposes said semiconductor material to a beta particle-emitting radionuclide. Electrical energy is generated when electron-hole pairs are generated in said semiconductor material in response to the emission of beta particles from said radionuclide, along with the potential difference between said electrodes.

[0036] Without being bound by theory, the present invention is based on the potential difference generated between a spaced-apart first electrode and a second electrode by forming different Schottky junctions at two different electrodes. Electron-hole pairs are generated in a semiconductor material when excited by electric beta particles emitted from a radionuclide integrated within the semiconductor material. The electron-hole pairs generated within this material move under the influence of an electric field. The electron-hole pairs are swept into an external circuit using the potential difference existing between the two different electrodes, thereby generating electrical energy.

[0037] Some embodiments of the present invention relate to products and methods having a combination of one or more advantages. For example, some of the advantages of some of the embodiments disclosed herein include one or more of the following: a novel and / or improved device for generating electrical energy; a novel method for converting beta emission from a radionuclide into electrical energy; using radioactive materials previously considered waste to generate electrical energy; manufacturing a device capable of providing power for specific remote power requirements; manufacturing a betavolta electrical energy generator having improved resistance to radiation-induced damage; a betavolta device that allows for achieving varying full lifespans required for specific applications by selecting radioisotopes with different half-lives to power the device; the suitability of materials used to manufacture electric batteries to allow for scalable and automated manufacturing methods; solving one or more problems and / or providing one or more advantages, or providing commercial alternatives. Other advantages of some embodiments of the present invention are also disclosed herein.

[0038] A predetermined embodiment of the present invention provides an electric energy generating device.

[0039] A predetermined embodiment of the present invention provides an electric energy generating device, said device

[0040] A first electrode and a second electrode spaced apart—the first electrode comprises a low work function material, and the second electrode comprises a high work function material—; and

[0041] A beta particle-emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode—the semiconductor material may generate electron-hole pairs in response to beta particle emission from the radionuclide—

[0042] It includes at least one battery containing

[0043] The term "cell" as used in this specification refers to a functional unit for generating electrical energy.

[0044] In a specific embodiment, the device includes more than one battery. In a specific embodiment, the device includes a plurality of batteries. A suitable number of batteries can be selected based on the desired characteristics of the required device. Methods of electrically connecting individual batteries to achieve current flow are known in the art.

[0045] The dimensions of the first electrode and the second electrode can be selected based on the characteristics of the material used for the electrodes and the desired characteristics of the electric energy generating device.

[0046] In a predetermined embodiment, the first electrode and the second electrode are spaced apart by a distance ranging from 0.3 to 100 micrometers. In a predetermined embodiment, the first electrode and the second electrode are spaced apart by a distance ranging from 0.5 to 30 micrometers. Other distances are considered.

[0047] In this embodiment, an inter-electrode electric field is generated between a first electrode and a second electrode that are closely separated by different Schottky junctions at each electrode. The Schottky junction formed between the first electrode, comprising a semiconductor and a low work function material, will have a barrier height, depletion width, and energy profile different from that formed at the second electrode, comprising a high work function material. Taken together, the electric fields associated with the two different Schottky junctions can reinforce each other to provide a macroscopic field of significant size for collecting charge carriers into an external circuit.

[0048] Methods for determining the work function of a material are known in the art and include methods utilizing electron emission from a sample induced by an electric field (field electron emission), photon absorption (photoelectron emission), high temperature (thermal ion emission), or the use of Kelvin probe measurements. The relative method uses the difference in work function between the sample and a reference metal.

[0049] In a predetermined embodiment, the first electrode and / or the second electrode comprises a metal. In a predetermined embodiment, the first electrode and / or the second electrode comprises a non-metal. In a predetermined embodiment, the first electrode and / or the second electrode comprises a composite material (e.g., cermet). In a predetermined embodiment, the first electrode and / or the second electrode comprises a material that has been treated (e.g., coated) to change the work function of the electrode.

[0050] Low work function materials and high work function materials are available for purchase and / or can be manufactured by methods known in the art.

[0051] In a given embodiment, the low work function material includes a material having a work function of less than 3.0 eV.

[0052] In a predetermined embodiment, the low work function material comprises a material having a work function of 2.5 eV or less. In a predetermined embodiment, the low work function material comprises a material having a work function in the range of 2.7 to 3.5 eV.

[0053] In a given embodiment, the low work function material comprises a metal and / or an intermetallic compound.

[0054] The term "metal" as used herein refers to one or more metals, or a material containing a significant proportion of metals.

[0055] In a predetermined embodiment, the low work function material is a substantially pure elemental metal. In a predetermined embodiment, the low work function material comprises two or more metals. In a predetermined embodiment, the low work function material comprises one or more metals and other materials. In a predetermined embodiment, the low work function material is an alloy.

[0056] The term "intermetallic compound" as used herein refers to a material composed of two or more elemental metals of a defined stoichiometry, which also includes other nonmetallic elements, e.g., Mg2Ca, Al2Ca, Mg 17 Al 12 It may contain materials such as.

[0057] In a given embodiment, the low work function material comprises a metal and / or a metal containing a compound comprising one or more of europium, strontium, barium, samarium, calcium, magnesium, cerium, sodium, lithium, potassium, rubidium, cesium, dysprosium, neodymium, gadolinium, terbium, holmium, erbium, thulium, lanthanum, scandium, thorium, yttrium, and ytterbium. Such low work function materials are commercially available and / or can be manufactured by methods known in the art.

[0058] In a given embodiment, the low work function material comprises samarium metal. Samarium metal is available for purchase.

[0059] Examples of other low work function materials include Ag-O-Cs, WO-Ba, Sc2O3, and LaB6, all of which are available for purchase or can be manufactured by methods known in the art.

[0060] In a predetermined embodiment, the low work function material comprises a metal. In a predetermined embodiment, the low work function material comprises a mixture of metals. In a predetermined embodiment, the low work function material comprises a metal treated (e.g., coated) with another material to change the work function of the electrode.

[0061] In a given embodiment, the low work function material includes a nonmetal.

[0062] In a predetermined embodiment, the material having a low work function includes a composite material. In a predetermined embodiment, the material having a low work function includes a material processed to change the work function of the material.

[0063] In a predetermined embodiment, the high work function material comprises a material having a work function greater than 4.0 eV. In a predetermined embodiment, the high work function material comprises a chemical element having a work function greater than 4.0 eV.

[0064] In a given embodiment, the high work function material comprises a metal and / or an intermetallic compound.

[0065] In a predetermined embodiment, the high work function material is a substantially pure elemental metal. In a predetermined embodiment, the high work function material comprises two or more metals. In a predetermined embodiment, the high work function material comprises one or more metals and other materials. In a predetermined embodiment, the high work function material is an alloy.

[0066] In a given embodiment, the high work function material comprises a metal selected from one or more of nickel, platinum, silver, gold, aluminum, cadmium, cobalt, chromium, copper, beryllium, bismuth, cadmium, iron, gallium, mercury, indium, iridium, manganese, molybdenum, niobium, osmium, lead, palladium, rhenium, rhodium, ruthenium, antimony, silicon, tin, tantalum, technetium, titanium, vanadium, tungsten, zinc, and zirconium. Such high work function materials are commercially available and / or can be manufactured by methods known in the art.

[0067] In a given embodiment, the high work function material includes nickel metal.

[0068] In a predetermined embodiment, the material having a high work function comprises a metal. In a predetermined embodiment, the material having a high work function comprises a mixture of metals. In a predetermined embodiment, the material having a high work function comprises a metal treated with another material to change the work function of the electrode.

[0069] In a given embodiment, the material having a high work function includes a nonmetal.

[0070] In a given embodiment, the second electrode comprises a ceramic metal composite (i.e., a cermet material).

[0071] In a predetermined embodiment, the material having a high work function includes a composite material. In a predetermined embodiment, the material having a high work function includes a material that has been treated (e.g., coated) to change the work function of the material.

[0072] Beta particle-emitting radionuclides known in the art are available for purchase and can additionally be obtained from sources derived from radionuclide waste, byproducts of fission reactors, and radionuclides specifically produced and left over for industrial, medical, or research purposes.

[0073] In a given embodiment, the beta particle-emitting radionuclide originates from waste radionuclide material.

[0074] Examples of beta particle-emitting radionuclides include 90 Sr, 99 Tc, 3 H, 14 C, 63 Ni, 137 Cs, 147 Pm, 151 Sm, 121m Sn, 155 Eu, 93 Zr, 126 Sn, 60 Co, 210 Pb, 90 Y, 129 I, 188 W, 35 S, 121m Sn, 123 Sn, 45 Ca, 106 Ru, 170 Tm, 171 Tm, 134 Cs, 32 Si, 113 Cd, and 79 One or more of Se are included. The radionuclides may be provided in a suitable chemical form for use in various embodiments of the present invention.

[0075] In a given embodiment, the radionuclide is 90 Sr, 99 Tc, 3 H, 14 C, 63 Ni, 137 Cs, 147 Pm, 151 Sm, 121m Sn, 155 Eu, 93 Zr, 126 Sn, 60 Co, and 210 It includes one or more of Pb.

[0076] In a predetermined embodiment, the radionuclide comprises a single type of radionuclide. In a predetermined embodiment, the radionuclide comprises two or more individual types of radionuclides.

[0077] In a given embodiment, the radionuclide is ultimately 90 Sr and126 It includes isotopes that produce multiple β-particle emissions through a chain of daughter radionuclides that decay as they decay into stable isotopes / nuclei such as Sn.

[0078] In addition, you will understand that a single radionuclide beta decay event triggers a cascade of secondary electrons extending from the original decaying atom to tens of micrometers (μm), and that each secondary electron itself can potentially induce multiple excited electronic states within the semiconductor. You will also understand that radionuclides can undergo multimode emission.

[0079] In a given embodiment, the radionuclide has one or more of the following preferred characteristics: (i) the radionuclide emits β-particles having an energy in the range of 1 to 100 kiloelectron volts (keV); (ii) the radionuclide emits β-particles at a controlled rate with a half-life in the range of 1 to 40 years, e.g., about 5 years (to minimize the replacement period); (iii) the radionuclide is an isotope of an element with easy-to-handle chemical properties; and (iv) the radionuclide emits β-particles with little or no association with gamma (γ) radiation emission.

[0080] In a given embodiment, the radionuclides are dispersed in the semiconductor material.

[0081] In a given embodiment, the radionuclide is incorporated into the chemical structure and / or structural framework of the semiconductor material.

[0082] In a given embodiment, the radionuclide is 10 -1 GBq / mm 3 to 10 4 GBq / mm 3 It is integrated into semiconductor materials with a range of specific activity. The suitable specific activity can be selected based on the desired characteristics of the electric energy generating device.

[0083] In a given embodiment, the semiconductor material includes a composite semiconductor material.

[0084] In a given embodiment, a binder material is used to deposit, coat, or fuse a semiconductor material to at least one of the electrodes. Methods for depositing, coating, or fusing the material are known in the art.

[0085] In a given embodiment, the semiconductor material includes a single-phase composite semiconductor material.

[0086] In a given embodiment, the single-phase composite semiconductor material comprises an inorganic semiconductor chemically composited with a polymer.

[0087] In a given embodiment, the inorganic semiconductor has a band gap of at least 1.1 eV.

[0088] Examples of inorganic semiconductors include one or more of halides and chalcogenides, which are available for purchase or can be manufactured by methods known in the art.

[0089] In a given embodiment, the inorganic semiconductor comprises one or more of cesium halide, rubidium halide, potassium halide, lead halide, bismuth halide, antimony halide, arsenic halide, tellurium halide, tin halide; tellurides of Zn, Cd, Hg, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se; selenides of Zn, Cd, Hg, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Te; and sulfides of Zn, Cd, Hg, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se.

[0090] In a given embodiment, the single-phase composite semiconductor material comprises a halide chemically composited with a polymer. For example, the halide may be supramolecularly composited with nitrogen or sulfur atoms in the polymer.

[0091] In a given embodiment, the inorganic semiconductor comprises one or more of BiI3, PbI2, CsPbBr3, CsPbI3, CsPbCl3, CsSnI3, CsSnBr3, and CsSnCl3.

[0092] Other inorganic semiconductors include, for example, ZnS and / or CdSe, all of which are available for purchase and / or can be manufactured by methods known in the art.

[0093] In a given embodiment, the polymer comprises nylon, polyimide, polythiophene, polypyrrole, polyacrylonitrile, polyurethane, polycarbazole, polyaniline, polysulfide, polysulfoxide, polythioester, polythiocarbonate, polysulfate, polythiourethane, polysulfoxymine, and polysulfonium salt, or a mixture of one or more of the aforementioned polymers.

[0094] In a given embodiment, the single-phase composite semiconductor material comprises a polymer and a high concentration of inorganic semiconductor. For example, the single-phase composite semiconductor material may have an inorganic semiconductor concentration of at least 50% (w / w), or in the range of 50% to 95% (w / w).

[0095] In a given embodiment, the inorganic semiconductor and the radionuclide are separate species.

[0096] In a given embodiment, the inorganic semiconductor includes a radionuclide. For example, the inorganic semiconductor is 210 PbI2 and / or Bi 129 It may be I3. Such compounds can be purchased or manufactured by methods known in the art.

[0097] In a predetermined embodiment, the radionuclide is mixed with the polymer. In a predetermined embodiment, the radionuclide is dispersed in the polymer. In a predetermined embodiment, the radionuclide is located adjacent to the polymer. In a predetermined embodiment, both the polymer and the semiconductor exist in the form of fine particles, and the particles exist as a mixture with the semiconductor.

[0098] In a given embodiment, the radionuclide is incorporated into the chemical structure of the polymer. Methods for incorporating the radionuclide into the polymer are known in the art, for example, suitable radionuclides (e.g. 3 H or 14 It includes the use of monomers labeled as C), or the use of gaseous radionuclides (e.g., tritium gas) that incorporate radionuclides into the polymer by exchange.

[0099] In a predetermined embodiment, the radionuclide is mixed with the polymer. In a predetermined embodiment, the radionuclide is dispersed in the polymer. In a predetermined embodiment, the radionuclide is located adjacent to the polymer. In a predetermined embodiment, both the polymer and the radionuclide exist in the form of fine particles, and the particles exist as a mixture with a semiconductor.

[0100] In a given embodiment, a radionuclide is incorporated into the chemical structure of the polymer, and an inorganic semiconductor is mixed with the polymer.

[0101] In a given embodiment, a radionuclide forms part of an inorganic semiconductor, and the inorganic semiconductor is mixed with a polymer.

[0102] In a given embodiment, the radionuclide, the inorganic semiconductor, and the polymer are each in the form of microparticles, and the particles exist as a mixture.

[0103] In a given embodiment, the radionuclide is incorporated into a higher-order structure present in a material containing an inorganic semiconductor, such as by incorporating it into a void in an irregular structure present in the inorganic semiconductor.

[0104] In a given embodiment, the semiconductor material comprises a semiconductor polymer. The semiconductor polymer (and / or its monomer components) may be commercially available or manufactured by methods known in the art.

[0105] In a given embodiment, the semiconductor polymer comprises one or more of polythiophene, polyacetylene, polyphenylene vinylene, polypyrrole polyphenylene sulfide, polyaniline, polyvinylacetylene, polypyrrole, polyindole, polyvinylene, polyazulene, and organo-boron polymers. Examples include P3HT and PEDOT polymers. Other types of polymers are considered.

[0106] In a specific embodiment, the radionuclide is mixed with the semiconductor polymer. In a specific embodiment, the radionuclide is dispersed within the semiconductor polymer. In a specific embodiment, the radionuclide is located adjacent to the semiconductor polymer. In a specific embodiment, both the semiconductor polymer and the radionuclide exist in the form of fine particles, and the particles exist as a mixture with the semiconductor.

[0107] In a given embodiment, the radionuclide is incorporated into the chemical structure of the semiconductor polymer. Methods for incorporating the radionuclide into the polymer are known in the art, for example, suitable radionuclides (e.g. 3 H or 14 It includes the use of monomers labeled as C), or the use of gaseous radionuclides (e.g., tritium gas) that incorporate radionuclides into the semiconductor polymer by means of exchange.

[0108] In a given embodiment, the semiconductor material comprises a semiconductor polymer and an additional semiconductor.

[0109] Examples of additional semiconductors include one or more of halides, chalcogenides, oxides, nitrides, carbides, perovskites, borides, tellurides, selenides, antimonides, germanides, arsenides, sulfides, silicides, phosphides, aluminides, carbon allotropes, and intermetallic compounds, all of which are available for purchase or can be manufactured by methods known in the art.

[0110] In a given embodiment, the additional semiconductor comprises one or more of BiI3, PbI2, CsPbBr3, CsPbI3, CsPbCl3, CsSnI3, CsSnBr3, and CsSnCl3. Other inorganic semiconductors comprise one or more of, for example, PbZrO3, PbTiO3, SrTiO3, SrZnO3, and (K,Cs)TaO3, all of which are available for purchase.

[0111] In a given embodiment, the semiconductor material comprises a semiconductor polymer and a low concentration of additional semiconductor. For example, the semiconductor material may have an additional semiconductor concentration in the range of at least 5% (w / w) or 5% to 50% (w / w) of the semiconductor polymer.

[0112] In a given embodiment, the semiconductor material comprises a semiconductor polymer and an additional semiconductor, and a radionuclide forms part of the additional semiconductor.

[0113] In a given embodiment, the semiconductor material comprises a semiconductor polymer and an additional semiconductor, wherein the radionuclide, the additional semiconductor, and the semiconductor polymer are each in the form of microparticles, and the particles exist as a mixture.

[0114] In a given embodiment, the semiconductor material comprises a semiconductor polymer and an additional semiconductor, and the radionuclides and / or the additional semiconductor are dispersed in the matrix of the semiconductor polymer.

[0115] In a given embodiment, the semiconductor material includes a crystalline semiconductor.

[0116] In a predetermined embodiment, the crystalline semiconductor comprises one or more of nitrides, carbides, halides, mixed chalcogenides, tellurides, selenides, antimonides, germanides, arsenides, silicides, phosphides, aluminides, carbon allotropes, perovskites or other complex oxo-anionic crystal phase materials, simple oxides, doped oxides, sulfides, fluorides, and intermetallic compounds, all of which may be commercially available or manufactured by methods known in the art. In a predetermined embodiment, the crystalline semiconductor comprises one or more of titanates, zirconates, molybdates, vanadates, technetates, pertechnetates, tungstates, niobates, tantalates, doped tin oxide, doped zinc oxide, hafnates, germanium oxide, cobaltates, ironates, and manganates, all of which may be commercially available or manufactured by methods known in the art. Other crystalline semiconductors are considered.

[0117] In a given embodiment, the crystalline semiconductor comprises titanate and / or zirconate.

[0118] In a given embodiment, the crystalline semiconductor comprises one or more of strontium zirconate (SrZrO3), strontium titanate (SrTiO3), and titanium oxide.

[0119] In a given embodiment, the crystalline semiconductor has one or more of the following desirable properties: a low electron-hole-pair recombination rate; high mobility for electrons and holes under the influence of an electric field; a melting point of at least 250°C; oxidation resistance; hardness; strength, resistance to impact fracture, erosion and / or wear. Methods for evaluating the above-mentioned properties are known in the art.

[0120] In a predetermined embodiment, the crystalline semiconductor comprises a band gap of at least 2.0 eV. In a predetermined embodiment, the crystalline semiconductor has a band gap of at least 2.6 eV. In a predetermined embodiment, the crystalline semiconductor has a band gap of at least 3.1 eV. In a predetermined embodiment, the crystalline semiconductor has a band gap of at least 3.2 eV. In a predetermined embodiment, the crystalline semiconductor has a band gap of at least 3.4 eV. In a predetermined embodiment, the crystalline semiconductor has a band gap in the range of 2.6 to 5.4 eV, 3.1 to 5.4 eV, 3.2 to 5.4 eV, or 3.4 to 5.4 eV. Methods for determining the band gap of a semiconductor are known in the art and are typically expressed for a standard hydrogen electrode.

[0121] In a given embodiment, the crystalline semiconductor has the characteristic of high charge carrier mobility.

[0122] In a given embodiment, the semiconductor material comprises a crystalline semiconductor, and the radionuclide is 90 Sr, 99 Tc, 3 H, 14 C, 63 Ni, 137 Cs, 147 Pm, 151 Sm, 121m Sn, 155 Eu, 93 Zr, 210 Pb, 60 Co and 126 It includes one or more of Sn. Other beta particle-emitting radionuclides are considered.

[0123] In a given embodiment, a radionuclide is incorporated into the chemical or structural framework of a crystalline semiconductor.

[0124] In this regard, radionuclides substitute a portion of some Sr in the lattice for strontium titanate (SrTiO3), for example. 90It may be an atom capable of substituting into the lattice of a crystalline semiconductor, such as Sr. In other embodiments, the radionuclide may be an atom or an inorganic compound capable of occupying a void or other structural defect in the lattice.

[0125] In a given embodiment, the radionuclide is 10 -1 GBq / mm 3 to 10 4 GBq / mm 3 It is integrated into crystalline semiconductors within a range of inerts. A suitable inert can be selected based on the desired characteristics of the electric energy generating device.

[0126] Methods for incorporating radionuclides into crystalline semiconductors are known in the industry.

[0127] In a given embodiment, a radionuclide is incorporated into a chemical or structural framework of a crystalline semiconductor. Methods for incorporating a beta-particle emitting radionuclide into a crystalline chemical or structural framework are known in the art and include, for example, isotope exchange using an isotope concentration gradient.

[0128] In a given embodiment, a radionuclide is incorporated into the chemical or structural framework of a crystalline semiconductor by one or more of replacing a suitable atom in the lattice of the crystalline semiconductor with the radionuclide (substitution integration), by inserting the radionuclide into the framework of the crystalline semiconductor, or by incorporating the radionuclide into a gap or void of the structural framework.

[0129] In a given embodiment, the radionuclide is incorporated into a less ordered structure present in a crystalline semiconductor, such as by incorporating it into a void in an irregular structure present in the semiconductor.

[0130] In a predetermined embodiment, the semiconductor material comprises a crystalline semiconductor and a binder. In a predetermined embodiment, the semiconductor material comprises a crystalline semiconductor and a polymer binder.

[0131] In a given embodiment, a binder material is used to deposit, coat, or fuse a semiconductor material to at least one of the electrodes. Methods for depositing, coating, or fusing the material are known in the art.

[0132] In a predetermined embodiment, a semiconductor material is deposited, coated, or fused onto a first electrode and / or a second electrode. In a predetermined embodiment, the material is deposited, coated, or fused onto the first electrode. In a predetermined embodiment, the material is deposited onto the second electrode. In a predetermined embodiment, the material is deposited onto both electrodes.

[0133] In a given embodiment, a material is deposited, coated, and / or fused onto one of the electrodes. Methods of depositing, coating, or fusing the material are known in the art.

[0134] In a given embodiment, the semiconductor material is in a form suitable for coating onto an electrode by a wet coating process.

[0135] In a predetermined embodiment, the device comprises a plurality of cells including an insulating layer between the cells. Insulating materials are known in the art. In a predetermined embodiment, the insulating layer is a thin film.

[0136] In a specific embodiment, the batteries are electrically connected in series. In a specific embodiment, the batteries are electrically connected in parallel. Methods for connecting batteries are known in the art.

[0137] A method for manufacturing an electric generating device as described in this specification is known in the art.

[0138] In a given embodiment, an electric energy generating device as described herein may be used in applications requiring a power source for an extended period, such as military applications, communications applications, mining applications, space applications, and medical applications. Other applications are considered.

[0139] The electric energy generating device described herein is also referred to herein as a "betavolta device" that generates an electric current using energy from a radionuclide source emitting beta particles (electrons).

[0140] A predetermined embodiment of the present invention provides a betavolta device.

[0141] In a predetermined embodiment, the present invention provides a betavolta device, said device

[0142] A first electrode and a second electrode spaced apart—the first electrode comprises a low work function material, and the second electrode comprises a high work function material—; and

[0143] A beta particle-emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode—the semiconductor material may generate electron-hole pairs in response to beta particle emission from the radionuclide—

[0144] It includes at least one battery containing

[0145] A betavolta device and a method for manufacturing the same are described in this specification.

[0146] A predetermined embodiment of the present invention provides a method for generating electrical energy.

[0147] The method of generating electrical energy is as described in this specification.

[0148] In a predetermined embodiment, the present invention provides a method for generating electrical energy, said method

[0149] A step of generating a potential difference between a first electrode and a second electrode that are closely spaced apart—the first electrode comprises a low work function material, and the second electrode comprises a high work function material—;

[0150] A step of generating electron-hole pairs from energy beta particles emitted from a radionuclide located in very close proximity to a semiconductor material disposed between the first electrode and the second electrode—the electron-hole pairs move under the influence of an electric field—; and

[0151] A step of capturing the electron-hole pair into an external circuit using the electric field existing between the electrodes.

[0152] It includes; thereby generates electrical energy.

[0153] In a predetermined embodiment, the present invention provides a method for generating electrical energy, said method

[0154] A step of generating an electric field between a spaced-apart first electrode and a second electrode—the first electrode comprises a low work function material and the second electrode comprises a high work function material, and the electric field is generated due to different Schottky junctions at the two different electrodes—;

[0155] A step of generating electron-hole pairs from energy beta particles emitted from a radionuclide located in very close proximity to a semiconductor material disposed between the first electrode and the second electrode—the electron-hole pairs move under the influence of an electric field—; and

[0156] A step of capturing the electron-hole pair into an external circuit using the electric field existing between the electrodes.

[0157] It includes; thereby generates electrical energy.

[0158] In a predetermined embodiment, the generation of a potential difference involves the use of materials having different work functions. In a predetermined embodiment, the first electrode comprises a low work function material, and the second electrode comprises a high work function material.

[0159] Suitable first electrodes and second electrodes, and low work function materials and high work function materials are described in this specification.

[0160] Radionuclides and semiconductor materials are described herein. Examples of semiconductor materials are described herein.

[0161] A predetermined embodiment of the present invention provides an apparatus for generating electrical energy using the method described herein. A method for manufacturing the apparatus using the method is as described herein.

[0162] A predetermined embodiment of the present invention provides a product.

[0163] In a given embodiment, the product is suitable for use in a betavolta device.

[0164] In a given embodiment, the present invention provides a product comprising a first material having a low work function, a second material having a high work function, a beta particle emitting radionuclide disposed between the first material and the second material, and a semiconductor material capable of generating electron-hole pairs in response to the emission of beta particles from said radionuclide.

[0165] The method for manufacturing the product is as described herein. Low work function materials and high work function materials are described herein. Radionuclides and semiconductor materials are described herein.

[0166] In a specific embodiment, the product is used to manufacture an electric battery. In a specific embodiment, the product is used in an electric generating device. Other uses are considered.

[0167] A predetermined embodiment of the present invention provides an electric energy generating device comprising a product as described in this specification.

[0168] The method of utilizing the product in an electric generating device is as described in this specification.

[0169] A predetermined embodiment of the present invention provides a method for generating electrical energy, the method comprising the step of using a product as described herein in a device for generating electrical energy.

[0170] A predetermined embodiment of the present invention provides a method for manufacturing an electric energy generating device.

[0171] In a given embodiment, the present invention provides a method for manufacturing an electric energy generating device, the method comprising the step of integrating one or more electric cells into the electric energy generating device, wherein the one or more electric cells comprise a spaced-apart first electrode and a second electrode—the first electrode comprises a low work function material and the second electrode comprises a high work function material—and a beta particle emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode—the semiconductor material may generate electron-hole pairs in response to beta particle emission from the radionuclide.

[0172] Suitable first electrodes and second electrodes, and low work function materials and high work function materials are described in this specification.

[0173] Radionuclides and semiconductor materials are described herein. Examples of semiconductor materials are described herein.

[0174] A predetermined embodiment of the present invention provides an electric energy generating device manufactured by a method as described in this specification.

[0175] A predetermined embodiment of the present invention provides a method for manufacturing an electric battery for use in an electric generating device as described herein.

[0176] The present invention is further explained by the following examples. It should be understood that the following description is merely for illustrating specific embodiments and is not intended to limit the description.

[0177] Example 1 - Manufacture of a Betavolta Device Using Single-Phase Composite Semiconductor Material

[0178] A non-radioactive, layered, asymmetric metal-semiconductor-metal structure was created and provided as a prototype betavolta device for testing under ultraviolet (UV) photon flux. To avoid the use of radioactive materials, UV photons were used to simulate the electron excitation effect provided by beta radiation. The UV source provides photons with energies of 4–5 eV.

[0179] The first metal layer used was a thin strip of lightly polished pure nickel metal about 150 μm thick, which serves as two electrodes and as a substrate for the semiconductor composite layer. The pure nickel was obtained from Mid-North Coast Components, located in Port Macquarie, NSW, Australia.

[0180] Two different semiconductor composite materials were fabricated as distinct exemplary examples for semiconductor components of a novel beta-volta AMSM structure. The semiconductor layer is where charge carriers are generated in response to radiative excitation, and the layer thickness was performed to be 2 to 5 μm.

[0181] The first semiconductor composite material is a cesium-modified polyaniline-nylon composite and was prepared by: (a) dissolving Nylon-6 (0.24 grams; Duromer Products, Australia) with 0.009 grams of cesium bromide (Sigma Aldrich, 99.999%; Product #203017) in 95% formic acid (2 mL) in a glass vial and stirring the mixture at 50°C until completely transparent (about 30 minutes); (b) preparing a dispersion of finely ground polyaniline (0.053 grams - Emeraldine of Aldrich; Product #428329) in formic acid (1.5 mL) by stirring the components together at 50°C for about 20 minutes; (c) mixing the cesium-treated nylon solution and the polyaniline dispersion together and stirring the resulting blend for at least 20 minutes, and increasing the viscosity by lightly heating to remove some formic acid; (d) transferring the blended formic acid dispersion / solution of the cesium-treated polyaniline-nylon into a small syringe equipped with a 0.45 µm syringe filter; (e) drop-casting a few drops of the cesium-treated polyaniline-nylon onto a nickel metal substrate by pushing the dispersion / solution through the syringe filter; (f) allowing the deposited fluid to spread slowly over the substrate by gently rotating a slide until almost all the formic acid evaporates; (g) drying the film on a hot plate at about 110°C once it has solidified. The concentration of CsBr in the film was approximately 3 wt%.

[0182] The second semiconductor material prepared was a single-phase, fully complexed bismuth triiodide (BiI3)-nylon composite containing a high mass loading of BiI3. This was prepared by the following steps: (a) closely mixing fine Nylon-12 powder (0.5 g; Duromer Products, Australia) with fine BiI3 powder (0.5 g; > 98%, Tokyo Chemical Industry (TCI) Product # B5787); (b) placing the powder mixture into a vial and heating the mixture to about 150°C to allow the BiI3 to be absorbed into the nylon; (c) placing the nylon-BiI3 powder onto a nickel metal substrate and heating the nickel from below at about 250°C until the material completely solidified (about 5 minutes)—as evidenced by the transparent dark orange color of the resulting blended polymer melt, which also demonstrates the complexation of the amide groups of nylon with the iodide. (d) A step of spreading the molten material over the entire substrate by maintaining the heating and forming it to a desired thickness.

[0183] The third semiconductor composite material produced was a composite of a single-phase, fully composite bismuth triiodide (BiI3)-nylon mixture containing polyaniline and a high mass loading of BiI3. This was prepared by the following steps: (a) closely mixing fine Nylon-12 powder (0.5 grams) with fine BiI3 powder (0.5 grams); (b) placing the powder mixture into a vial and heating the mixture to approximately 150°C so that BiI3 is absorbed into the nylon; (c) mixing the nylon-BiI3 powder with finely ground polyaniline (0.053 grams - in the form of emeraldine salt); (d) placing nylon-BiI3-polyaniline powder on a nickel metal substrate and heating the nickel from below at about 250°C until the material is completely solidified (about 5 minutes)—as is evident from the transparent dark orange-green color of the resulting blended polymer melt; (e) spreading the melt over the entire substrate and pressing a polished samarium metal electrode into the melt while it is melting.

[0184] Each exemplary example of a semiconductor composite occupies a different position in a three-axis configuration diagram illustrating the various types of semiconductor materials described herein (see FIG. 1). This diagram illustrates a space enclosed by three terminal members, namely: (i) a pure semiconductor polymer having suitable electronic properties; (ii) a semiconductor single-phase composite comprising an inorganic compound chemically combined with the polymer (generally containing nitrogen and / or sulfur heteroatoms); and (iii) a crystalline semiconductor having a defined chemical composition and stoichiometry. This semiconductor material may include a mixture or blend between any two terminal members or between all three terminal members (on a nanometer scale).

[0185] In the case of the first and second semiconductor composite materials described above, the second (low work function) metal layer is 10 -6It consisted of a thin layer of vacuum-deposited samarium metal approximately 150 nm thick applied within a standard vacuum deposition chamber operating at mbar—where a crucible filled with samarium metal (Treibacher Industrie AG; Austria) was bombarded by an electron beam focused toward the center of the crucible. Subsequently, a continuous flux of samarium metal atoms was deposited onto a substrate located approximately 20 cm directly above the crucible. At the end of the samarium metal deposition, a copper metal layer (approx. 150 nm) was applied over the samarium as a protective coating. The conditions for batch electron beam physical deposition in a vacuum chamber equipped with an ion gun were as follows:

[0186]

[0187] Before evaluating the sample, a small area on the copper-face samarium electrode was lightly polished using 3000 grit emery paper until the moment the dark color of the central semiconductor was immediately visible, so that a reasonable fluence of UV photons could penetrate into the semiconductor layer.

[0188] Simulated betavoltaic current measurements were performed by connecting the completed device in series to a Keysight 6½-digit multimeter (model 34465A) operating in DC ammeter mode in the 1 μA range with a resolution of 500 picoamperes. Flat connection clips ensured excellent electrical contact with both the high work function electrode and the low work function electrode. Reference thermal currents were detectable in most samples, indicating that they were not short-circuited and were suitable for further experiments. A UV photon beam (500 mW power) was directed at the worn area of ​​the electrode surface. The ammeter current readings jumped immediately and continued to rise. The recorded value was taken immediately after the UV beam encountered the sample (approximately 1 second). The results are shown in Table 1.

[0189]

[0190] As can be seen from Table 1, significant instantaneous UV-stimulated currents were measured from each prototype Volta-Beta structure tested in the experiment. The induced current immediately after the start of UV irradiation is related to the beta-volta response because it is attributed entirely to charge carriers generated by electron excitons, but later current levels may contain a heat-induced current component as heat gradually accumulates in the sample. Although heat current generation could not be measured in this experiment, the currents recorded in the second column of Table 1 may have underestimated the amount of charge carrier generation and collection arising from the type of electron excitons similar to those generated by beta-radiation, as most of the electron current component of the total current may still be present even after 1 second has passed since the start of UV irradiation.

[0191] The key inference that can be drawn from these experiments is that the electric field collecting charge carriers must be detectable enough to sweep into the external circuit before recombination. This ultimately implies sufficient strength, polarity, and spatial range for different metal-semiconductor junctions to occur at samarium (low work function) and nickel / copper (high work function) electrodes.

[0192] Example 2 - Preparation of a Beta-Volta Device by Incorporating Radionuclides into a Polymer by Exchange

[0193] A first electrode made of samarium metal (e.g., 99.9%) can be manufactured by using a samarium foil / plate with a suitable thickness, for example, in the range of 0.01 to 0.4 mm, which is available, for example, from Sigma-Aldrich (Catalog # 693731). The metal foil / plate can be used in a suitable size, for example, 20 to 40 mm in length x 20 to 40 mm in height. An example of a manufactured samarium metal electrode is described in Example 1.

[0194] A second electrode made of nickel metal (e.g., 99.6%) can be manufactured by using a foil / plate with a suitable thickness, for example, in the range of 0.01 to 0.4 mm, which is available, for example, from Baoji TST Nonferrous Metal Co., Ltd. The metal foil / plate can be used in a suitable size, for example, 20 to 40 mm in length x 20 to 40 mm in height. An example of a manufactured nickel metal electrode is described in Example 1.

[0195] tritium ( 3 H) is a beta-emitting radioisotope that is produced in large quantities as a byproduct of a certain nuclear power generator and as waste from other nuclear processing operations. Hundreds of gigabecquerels of tritium can be provided in gaseous form (T2) at high pressure at multiple tritification facilities (e.g., Canadian Nuclear Laboratories, located in Chalk River, Ontario, Canada) or in other chemical forms (e.g., T2O).

[0196] Inorganic semiconductors, such as BiI3, can be purchased from, for example, Alfa, Ward Hill, Massachusetts (99.999% purity, recrystallized from tetrahydrofuran under N2).

[0197] Matrix polymers, e.g., nylon-11[NH-CO-(CH2) 10 -] n It can be purchased. When polyamide moiety is present in the polymer, it interacts strongly with iodine atoms, which in some cases may be part of an inorganic semiconductor such as BiI3, and these interactions help to solubilize inorganic components in the polymer, as demonstrated in Example 1.

[0198] The BiI3-Nylon-11 composite can be prepared, for example, as described in Example 1, to provide a dark orange solution containing approximately 65% ​​to 75% by weight of BiI3, or by using a melt of Nylon-11 (pre-dried under vacuum at 150°C to remove moisture) at 200°C to 240°C under N2 for 5 to 15 minutes.

[0199] 3 The H radionuclide can be incorporated into the polymer by using a special tritiumation chamber operated at elevated temperature and pressure to facilitate hydrogen-tritium exchange in the polymer matrix. Subsequently, the composite can be deposited on a heated first electrode and / or second electrode using a process such as drop-casting to produce a coating of approximately 1 to 30 micrometers after cooling.

[0200] Next, the first electrode and the second electrode are brought close together (e.g., 1 to 30 micrometers) so that the electrodes are generally parallel.

[0201] Next, a betavoltaic electric energy generating device using a single battery is manufactured by completing a circuit (with a low resistance load) between the first electrode and the second electrode. Next, to manufacture a multi-battery electric energy generating device, a multi-battery can be manufactured using the first electrode, the second electrode, and a coating applied to either of the two electrodes. In this case, a thin insulating layer is located between the first electrode and the second electrode of each battery connected in series or parallel with the individual battery.

[0202] The electric energy generating device described above is expected to have many advantages. For example, the device will generate electrical energy over a long period of time, reflecting the available lifespan of the radionuclides used to power the device. The device will also have resistance to radiation damage and heat generated by the decay of radionuclides.

[0203] Example 3 - Preparation of a Beta-Volta Device by Incorporating Radionuclides into a Polymer Using Labeled Monomers

[0204] A first electrode made of samarium metal (e.g., 99.9%) can be manufactured by using a samarium foil / plate with a suitable thickness, for example, in the range of 0.01 to 0.4 mm, which is available, for example, from Sigma-Aldrich (Catalog # 693731). The metal foil / plate can be used in a suitable size, for example, 20 to 40 mm in length x 20 to 40 mm in height. An example of a manufactured samarium metal electrode is described in Example 1.

[0205] A second electrode made of nickel metal (e.g., 99.6%) can be manufactured by using a foil / plate with a suitable thickness, for example, in the range of 0.02 to 0.4 mm, which is available, for example, from Baoji TST Nonferrous Metal Co., Ltd. The metal foil / plate can be used in a suitable size, for example, 20 to 40 mm in length x 20 to 40 mm in height. An example of a manufactured nickel metal electrode is described in Example 1.

[0206] Inorganic semiconductors, such as PbI2, can be purchased from, for example, Sigma-Aldrich (99.999% purity).

[0207] 3 H or 14 Nylon-11[NH-CO-(CH2) labeled with radionuclide C 10 -] n Insulating polymers such as can be obtained. For example, in the case of nylon-11, the polymer is incorporated into the monomer 11-aminoundecanate 3 H and 14 It can be labeled using C, and the polymer can be produced by the polymerization of the labeled monomer using standard synthesis conditions.

[0208] The PbI2-Nylon-11 composite can be prepared, for example, from a melt of labeled Nylon-11 (pre-dried under vacuum at 150°C to remove moisture) at 220°C to 290°C under N2 to provide a deep, clear orange solution containing approximately 65 wt% PbI2. This PbI2- 3 H or 14 A C nylon-11 composite is produced. The solution can then be deposited onto a heated first electrode and / or second electrode using a polymer film coating process, such as sheet extrusion, to produce a coating of approximately 1 to 30 micrometers after cooling.

[0209] Next, the first electrode and the second electrode are brought close together (e.g., 1 to 50 micrometers) so that the electrodes are generally parallel.

[0210] Next, a betavoltaic electric energy generating device using a single battery is manufactured by completing a circuit (with a low resistance load) between the first electrode and the second electrode. Next, to manufacture a multi-battery electric energy generating device, a multi-battery can be manufactured using the first electrode, the second electrode, and a coating applied to either of the two electrodes. In this case, a thin insulating layer is located between the first electrode and the second electrode of each battery connected in series or parallel with the individual battery.

[0211] The electric energy generating device described above is expected to have many advantages. For example, the device will generate electrical energy over a long period of time, reflecting the available lifespan of the radionuclides used to power the device. The material will be resistant to radiation damage and will also provide resistance to the heat generated by the decay of the radionuclides.

[0212] Example 4 - Manufacture of a Beta-Volta Device Using a Crystalline Semiconductor

[0213] A first electrode made of samarium metal (99.9%) can be manufactured by using a samarium foil / plate with a suitable thickness, for example, in the range of 0.02 to 0.4 mm, which is available, for example, from Sigma-Aldrich (Catalog # 693731). The metal foil / plate can be used in a suitable size, for example, 20 to 40 mm in length x 20 to 40 mm in height.

[0214] A second electrode made of nickel metal (99.6%) can be manufactured by using a nickel foil / plate with a suitable thickness, for example, in the range of 0.02 to 0.4 mm, which is available for purchase, for example, from Baoji TST Nonferrous Metal Co., Ltd. The metal foil / plate can be used in a suitable size, for example, 20 to 40 mm in length x 20 to 40 mm in height.

[0215] Semiconductor charge-carrier current collector materials in the form of thin slabs can be used. For example, strontium titanate (SrTiO3) together with powered inert SrCO3 and powdered TiO2 90 Sr(e.g., inactive at 500 GBq / g ( 90 Sr, natIt can be doped with a suitable source of Sr)CO3). The mixture can be ball-milled in an ethanol medium using yttria-stabilized zirconia balls in a plastic container for 24 hours. The slurry can then be dried, ground, sieved (100 mesh), and calcined for 2 hours at a suitable temperature in the range of, for example, 1000°C to 1200°C. The calcined powder can then be ball-milled again, dried, and ground into a fine powder, and then a 3 wt% poly(vinyl alcohol) 1799 (PVA) (alcohol decomposition 99.8100% (mol / mol), Aladdin Industrial Co.) solution can be added dropwise to the dried powder as a binder. The mixture can then be coated onto the first and second electrodes using a wet coating process, such as spin coating, and dried to produce a coating of approximately 1 to 50 micrometers.

[0216] Strontium 90 ( 90 Sr), beta particle-emitting radionuclides are 90 It can be obtained as radioactive waste in the form of SrCO3.

[0217] SrCO3 can be purchased in powder form, for example, from Sinopharm Chemical Reagent Co. Ltd.

[0218] TiO2 can be purchased in powder form, for example, from Sinopharm Chemical Reagent Co. Ltd.

[0219] Next, the first electrode and the second electrode (one of which is coated) are brought close together (e.g., 1 to 50 micrometers) so that the electrodes are generally parallel.

[0220] Next, a betavoltaic electric energy generating cell is manufactured by completing a circuit (with a low resistance load) between the first electrode and the second electrode. Subsequently, to manufacture a multi-cell electric energy generating device, a multi-cell can be manufactured using the first electrode, the second electrode, and a coating applied to either of the two electrodes. In this case, a thin insulating layer is located between the first electrode and the second electrode of each cell connected in series or parallel with the individual cell.

[0221] The electric energy generating device described above is expected to have many advantages. For example, the device will generate electrical energy over a long period of time, reflecting the available lifespan of the radionuclides used to power the device. The materials used in the device will be resistant to radiation damage and will also provide resistance to the heat generated by the decay of the radionuclides.

[0222] Example 5 - Preparation of Tritium Semiconductor Polymer

[0223] Tritium-containing polyaniline polymers with desired semiconductor properties can be prepared by two methods. Methods for preparing polyaniline are known in the art, for example [Boeva ​​and Sergeyev (2014) "Polyaniline: Synthesis, Properties and Application" Polymer Science, Ser. C It is recorded in [56: 144-153].

[0224] In one example, polyaniline is, for instance, described in the literature [J. Stejskal and RG Gilbert, Pure Appl. Chem. It can be prepared by chemical polymerization of aniline using ammonium persulfate as described in 74, 857 (2002). 3 H radionuclides can be incorporated into the polymer by using a special tritiumation chamber operated at elevated temperatures to facilitate hydrogen-tritium exchange in the polymer matrix.

[0225] In another example, polyaniline having desired conductive properties is, 3 H or 14 Aniline labeled with radionuclides C, and, for example, literature [J. Stejskal and RG Gilbert , Pure Appl. Chem It can be prepared by chemical polymerization of ammonium persulfate as described in ].

[0226] Although the present invention has been described with reference to specific examples, those skilled in the art will understand that the invention can be implemented in many different forms.

[0227] It should be understood that various changes, additions, and / or modifications may be made to the parts described above without departing from the scope of the present disclosure, and that, in light of the above teachings, the present invention may be implemented in software, firmware, and / or hardware in various ways that are understandable to those skilled in the art.

[0228] As used in this specification, the singular forms “one” (“a,” “an”) and “the” (“the”) may refer to the plural article unless specifically stated otherwise.

[0229] Throughout this specification, unless the context otherwise requires, it will be understood that the term “comprise,” or variations such as “comprises,” or “comprises,” mean that it includes the mentioned element or integer or group of elements or integers, but does not mean that it excludes any other element or integer or group of elements or integers.

[0230] All methods described herein may be performed in any suitable order unless otherwise indicated herein or clearly contradicted by the context. Any and all examples provided herein, or the use of exemplary language (e.g., “like”), are merely intended to better describe exemplary embodiments and do not limit the scope of the claimed invention unless otherwise claimed. No language in this specification should be interpreted as indicating that any unclaimed element is essential.

[0231] The description provided herein relates to various embodiments that may share common characteristics and features. It should be understood that one or more features of one embodiment may be combined with one or more features of another embodiment. Additionally, a single feature or a combination of features of the embodiments may constitute additional embodiments.

[0232] Subject headings used in this specification are included solely for the reader's reference and should not be used to limit the subject matter found in the invention or the claims as a whole. Subject headings should not be used to interpret the scope of the claims or any limitations thereof.

[0233] Future patent applications may be filed based on this application, for example by claiming priority from this application, by claiming a divisional status, and / or by claiming a continuation status. It should be understood that the following claims are provided merely as examples and are not intended to limit the scope of claims that may be made in such future applications. Furthermore, the claims should not be construed as limiting (or excluding) any other understanding of the invention. Features may be added to or omitted from the exemplary claims later.

Claims

Claim 1 An electric energy generating device comprising: a first electrode and a second electrode spaced apart, wherein the first electrode comprises a low work function material and the second electrode comprises a high work function material; and at least one cell comprising a beta particle emitting radionuclide and a semiconductor material disposed between the first electrode and the second electrode, wherein the semiconductor material comprises a semiconductor polymer or a semiconductor polymer composite, and the semiconductor material is capable of generating electron-hole pairs in response to beta particle emission from the radionuclide. Claim 2 In paragraph 1, the above radionuclide is 90 Sr, 99 Tc, 3 H, 14 C, 63 Ni, 137 Cs, 147 Pm, 151 Sm, 155 Eu, 93 Zr, 126 Sn, 60 Co, 210 Pb, 90 Y, 129 I, 188 W, 35 S, 123 Sn, 45 Ca, 106 Ru, 170 Tm, 171 Tm, 134 Cs, 32 Si, 113 Cd, and 79 An electric energy generating device comprising one or more of Se. Claim 3 An electric energy generating device according to claim 1, wherein the low work function material comprises a metal, an intermetallic compound, or a metal-containing compound. Claim 4 An electric energy generating device according to claim 3, wherein the metal, intermetallic compound, or metal-containing compound comprises one or more of europium, strontium, barium, samarium, dysprosium, neodymium, gadolideum, terbium, holmium, erbium, thulium, lanthanum, scandium, thorium, calcium, magnesium, cerium, yttrium, ytterbium, sodium, lithium, potassium, rubidium, and cesium. Claim 5 An electric energy generating device according to claim 1, wherein the low work function material comprises samarium metal. Claim 6 An electric energy generating device according to claim 1, wherein the high work function material comprises a metal and / or an intermetallic compound. Claim 7 An electric energy generating device according to claim 1, wherein the high work function material comprises a metal selected from one or more of nickel, platinum, silver, gold, aluminum, cobalt, chromium, copper, beryllium, bismuth, cadmium, iron, gallium, germanium, mercury, indium, iridium, manganese, molybdenum, niobium, osmium, lead, palladium, rhenium, rhodium, ruthenium, antimony, silicon, tin, tantalum, technetium, titanium, vanadium, tungsten, zinc, and zirconium. Claim 8 An electric energy generating device according to claim 1, wherein the high work function material comprises nickel metal. Claim 9 An electric energy generating device according to claim 1, wherein the radionuclide is dispersed in the semiconductor material. Claim 10 An electric energy generating device according to claim 1, wherein the radionuclide is integrated into the chemical structure of the semiconductor material. Claim 11 An electric energy generating device according to claim 1, wherein the semiconductor material comprises a single-phase composite semiconductor material. Claim 12 In claim 11, the above single-phase composite semiconductor material comprises an inorganic semiconductor chemically composited with a polymer, an electric energy generating device. Claim 13 An electric energy generating device according to claim 1, wherein the semiconductor material comprises a crystalline semiconductor. Claim 14 An electric energy generating device according to claim 1, wherein the first electrode and the second electrode are spaced apart by a distance ranging from 0.3 to 100 micrometers. Claim 15 In claim 1, the device is an electric energy generating device comprising a plurality of batteries. Claim 16 A method for generating electricity comprising the step of using an electric energy generating device according to any one of claims 1 to 15. Claim 17 A method for generating electrical energy, the method comprising: a step of generating a potential difference between a first electrode and a second electrode that are closely spaced apart, wherein the first electrode comprises a low work function material and the second electrode comprises a high work function material; a step of generating electron-hole pairs from energy beta particles emitted from a radionuclide in proximity to a semiconductor material disposed between the first electrode and the second electrode, wherein the electron-hole pairs move under the influence of an electric field between the electrodes; and a step of capturing the electron-hole pairs into an external circuit using the electric field existing between the electrodes; thereby generating electrical energy. Claim 18 A method for generating electrical energy, the method comprising: generating an electric field between a first electrode and a second electrode separated therefrom, wherein the first electrode comprises a low work function material and the second electrode comprises a high work function material, and the electric field is generated due to different Schottky junctions at the two different electrodes; generating electron-hole pairs from energy beta particles emitted from a radionuclide in proximity to a semiconductor material disposed between the first electrode and the second electrode, wherein the electron-hole pairs move under the influence of the electric field; and capturing the electron-hole pairs into an external circuit using the electric field existing between the electrodes; thereby generating electrical energy. Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete Claim 32 delete Claim 33 delete Claim 34 delete

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