阅读说明：本技术 三维纳米结构氚伏电池 (Three-dimensional nano-structure tritium photovoltaic battery ) 是由 伞海生 陈长松 于 2019-01-25 设计创作，主要内容包括：三维纳米结构氚伏电池,涉及一种同位素电池。呈三明治结构,从上到下依次为：顶部电极、三维纳米结构半导体和底部电极；所述三维纳米结构半导体是由半导体材料构成的三维网格框架结构,网格框架之间设有孔道间隙,三维纳米结构半导体设于底部电极与顶部电极之间,三维纳米结构半导体为氚基同位素源集成的三维纳米结构半导体,所述氚基同位素源贮存于半导体网格框架之间孔道间隙中的氚化金属,或为氚与三维纳米结构半导体材料复合形成的氚化半导体,或为氚化金属与氚化半导体的共存结构；所述氚化金属与三维纳米结构半导体形成肖特基接触或欧姆接触,同时还与顶部电极或底部电极连接。(A three-dimensional nano-structure tritium photovoltaic battery relates to an isotope battery. Is of a sandwich structure and sequentially comprises the following components from top to bottom: a top electrode, a three-dimensional nanostructured semiconductor, and a bottom electrode; the three-dimensional nanostructured semiconductor is a three-dimensional grid framework structure formed by semiconductor materials, pore gaps are arranged between the grid frameworks, the three-dimensional nanostructured semiconductor is arranged between the bottom electrode and the top electrode, the three-dimensional nanostructured semiconductor is a three-dimensional nanostructured semiconductor integrated by a tritium-based isotope source, and the tritiated metal stored in the pore gaps between the semiconductor grid frameworks, or a tritiated semiconductor formed by compounding tritium and the three-dimensional nanostructured semiconductor material, or a coexisting structure of the tritiated metal and the tritiated semiconductor; the tritiated metal and the three-dimensional nanostructure semiconductor form Schottky contact or ohmic contact, and are connected with the top electrode or the bottom electrode.)

1. Three-dimensional nanostructured tritium photovoltaic battery, its characterized in that is sandwich structure, from the top down is in proper order: a top electrode, a three-dimensional nanostructured semiconductor, and a bottom electrode; the three-dimensional nanostructured semiconductor is a three-dimensional grid framework structure formed by semiconductor materials, pore gaps are arranged between the grid frameworks, the three-dimensional nanostructured semiconductor is arranged between the bottom electrode and the top electrode, the three-dimensional nanostructured semiconductor is a three-dimensional nanostructured semiconductor integrated by a tritium-based isotope source, and the tritiated metal stored in the pore gaps between the semiconductor grid frameworks, or a tritiated semiconductor formed by compounding tritium and the three-dimensional nanostructured semiconductor material, or a coexisting structure of the tritiated metal and the tritiated semiconductor; the tritiated metal and the three-dimensional nanostructure semiconductor form Schottky contact or ohmic contact, and are connected with the top electrode or the bottom electrode.

2. A three-dimensional nanostructured tritium photovoltaic cell according to claim 1 characterized in that the three-dimensional nanostructured semiconductor is a monocrystalline or polycrystalline semiconductor.

3. A three-dimensional nanostructured tritium photovoltaic cell according to claim 1, characterized in that the semiconducting material comprises both elemental semiconductors comprising germanium and silicon and compound semiconductors comprising group iii and group v compounds, group ii and group vi compounds, oxide semiconductors, and solid solutions consisting of group iii-v compounds and group ii-vi compounds.

4. A three-dimensional nanostructured tritium photovoltaic cell according to claim 3, characterized in that the group iii and v compounds are selected from gallium arsenide, gallium phosphide, gallium nitride; the II and VI compounds are selected from cadmium sulfide and zinc sulfide; the oxide semiconductor is selected from zinc oxide, tin oxide, titanium oxide and gallium oxide; the solid solution formed by the III-V group compound and the II-VI group compound is selected from gallium aluminum arsenic and gallium arsenic phosphorus.

5. The three-dimensional nanostructure tritium photovoltaic cell as claimed in claim 1, characterized in that the three-dimensional nanostructure is an ordered or disordered thin film material composed of at least one basic structural unit of zero dimension, one dimension and two dimensions, and the thickness of the thin film material can be 1-500 μm; the basic structural unit can comprise nanodots, nanoparticles, nanowires, nanorods, nanopillars, nanotubes, nanoflowers, nanosheets, nanobelts, nanosprings, nanorings, nanocombs, nanoscalds, nanoneedles, nanocages, nanotopods, tower-like nanostructures, disk-like nanostructures, star-like nanostructures, branch-like nanostructures, hollow nanospheres, and nanoarrays.

6. A three-dimensional nanostructured tritium photovoltaic cell according to claim 1, characterized in that the three-dimensional nanostructured semiconductor enhances the generation and transport efficiency of carriers by a material modification process comprising high temperature reduction annealing, ion implantation doping of metallic or non-metallic elements, high temperature diffusion doping, chemical reaction doping in an inert gas or hydrogen atmosphere.

7. A three-dimensional nanostructured tritium photovoltaic cell according to claim 1, characterized in that the tritium-based isotope source comprises tritiated metal and tritiated semiconductor, the tritiated metal being transition metal, alkali metal, alkaline earth metal, rare earth metal and alloys thereof tritiated at high temperature and tritiated to form stable metal-tritium bond with metal; the tritiated semiconductor is formed by compounding tritium and a semiconductor material due to the fact that metal and nonmetal elements in the semiconductor and tritium form stable chemical bonds after the semiconductor material is tritiated at high temperature.

8. A three-dimensional nanostructured tritium photovoltaic cell according to claim 7, characterized in that the transition metals comprise titanium, zirconium, scandium, palladium, cobalt, the alkali metals comprise lithium, the alkaline earth metals comprise beryllium and magnesium, the rare earth metals comprise lanthanum, uranium, erbium, the alloys comprise zirconium cobalt, zirconium vanadium, lanthanum nickel; the metal-tritium bond includes a titanium-tritium bond, a lithium-tritium bond, and a magnesium-tritium bond, and the metal and nonmetal elements in the semiconductor form stable chemical bonds with tritium including a titanium-tritium bond, a silicon-tritium bond, an oxygen-tritium bond, and a sulfur-tritium bond.

9. A three-dimensional nanostructured tritium photovoltaic cell according to claim 1, characterized in that the integration method of the tritiated metal in the three-dimensional nanostructure is as follows: firstly, pre-depositing a metal thin layer of 5-1000 nm on the surface of a three-dimensional nanostructure semiconductor through atomic layer deposition, chemical vapor deposition, metal sputtering, metal electroplating or metal evaporation technology, and then tritiating the metal thin layer in a tritium atmosphere, wherein the temperature range is 100-800 ℃, and the pressure range is 100-1000 kPa;

the tritiated semiconductor is obtained by directly carrying out high-temperature high-pressure tritiation on a three-dimensional nanostructure semiconductor in a tritium atmosphere, wherein the temperature range is 100-800 ℃, and the pressure range is 100-1000 kPa.

10. A three-dimensional nanostructured tritium photovoltaic cell according to claim 1, characterized in that the top and bottom electrodes are selected from metal electrodes, semiconductor electrodes, graphite electrodes, graphene electrodes, conductive polymer electrodes or conductive paste electrodes.

Technical Field

The invention relates to an isotope battery, in particular to a three-dimensional nanostructure tritium photovoltaic battery which directly converts beta radiant energy of isotope tritium into electric energy by using a three-dimensional nanostructure semiconductor.

Background

Extreme regions such as deep sea and polar regions have problems of severe environment, difficulty in reaching, and the like. Where human activity tends to be less in the past. In recent years, due to the fact that the regions are rich in resources, important in geographical positions, and have no affiliated division, related research work is vigorously carried out in all countries in the world. For example, by establishing a deep sea observation network, environmental parameters such as the temperature, the landform and the ocean current of deep sea can be recorded, and a deep sea map can be drawn, wherein the deep sea geographic data parameters have great scientific, economic and military values. These areas all have the characteristics of unattended operation, inconvenient maintenance, harsh environment and the like. Therefore, long-term maintenance-free requirements are placed on the sensing and monitoring equipment and the wireless communication equipment established in the region. Among these, energy systems are the most typical of these installations for life and maintenance free requirements. The conventional power supply modes such as solar energy, chemical fuel energy, ocean energy, wind energy, temperature difference energy and the like cannot meet the power supply requirements of sensor monitoring and communication equipment due to the problems of environmental influence, regular maintenance, large volume and weight and the like, and become a bottleneck problem restricting the deployment of monitoring equipment. In order to solve the problem of maintenance-free energy systems in equipment, scientific researchers thought of nuclear energy in recent years. The nuclear fusion and nuclear fission energy can generate huge energy, but the device is huge and complicated, and the operation and maintenance requirements are high. However, batteries manufactured by utilizing the radiant energy generated by isotope decay have the characteristics of long service life, no environmental influence, no maintenance and the like, and are the most rational candidate energy sources of the environmental monitoring system.

The isotope battery has several conversion mechanisms of temperature difference, thermion, direct charging, heat engine and radiation volt effect, etc., considering miniaturization and energy conversion efficiency, the radiation volt effect conversion mode is an ideal candidate, the radiation volt effect battery directly generates electric energy by utilizing the kinetic energy of radiation particles and the action of a semiconductor structure, the energy density is ten thousand times of that of a lithium battery, the theoretical efficiency of the battery can reach 30%, from the use of an isotope radiation source, three factors are mainly considered, namely 1) the average energy of β particles, 2) the half-life period of an isotope source, 3) the isotope source and the manufacturing cost, and the radiation damage threshold of a semiconductor is 250-300 KeV, so that the β source with high radiation kinetic energy, such as krypton-85, ruthenium-106, strontium-90, etc., can cause the attenuation of the performance of the battery, considering the service life and the average energy of the battery, the half-life period of the isotope source must exceed 5 years, so the more suitable isotope source is tritium (the average energy5.7KeV, half-life 12.3 years) and⁶³ni (average energy 17.4KeV, half life 100 years). Due to the fact that⁶³The source of Ni is limited, the price is very expensive, and the resource of tritium is very abundant and widely exists in nuclear reactor waste and ocean. Thus, tritium is the most ideal isotope for the preparation of an industrialized beta-voltaic cell. Since commercial tritium feedstocks are typically present in the form of tritium gas, how to integrate tritium into semiconductor energy conversion substrates is a problem that is currently urgently addressed.

The traditional beta-volt battery mainly utilizes single crystal semiconductors (such as silicon, diamond, silicon carbide, gallium nitride and the like) to manufacture a planar device, and realizes a battery structure by integrating a radiation source on the surface of the device. The main disadvantage of this configuration is the inefficient use of the radiation source and the limited number of active radiation sources integrated per unit area. For example, Russian Moscow physical and technical research has led to the use of nickel-63 (C)⁶³Ni) as a radiation source, the output power of the cell can reach the μ W level, and the endurance can reach 100 years, but the efficiency is only 1.25% (documents: diamond&Related Materials, vol.84, pp.41-47,2018) the company of City L abs in the united states has currently realized the commercialization of tritium-based beta-volt batteries, gallium arsenide (GaAs) crystals are used as conversion Materials, 100 curie tritium is integrated on the surface of a device and multi-sheet battery cascade is realized, the output power of the battery can reach about 100 muw, but the actual efficiency is less than 3% (https:// citylibs.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a three-dimensional nano-structure tritium photovoltaic battery.

The invention is of a sandwich structure, which comprises the following components in sequence from top to bottom: a top electrode, a three-dimensional nanostructured semiconductor, and a bottom electrode; the three-dimensional nanostructured semiconductor is a three-dimensional grid framework structure formed by semiconductor materials, pore gaps are arranged between the grid frameworks, the three-dimensional nanostructured semiconductor is arranged between the bottom electrode and the top electrode, the three-dimensional nanostructured semiconductor is a three-dimensional nanostructured semiconductor integrated by a tritium-based isotope source, and the tritiated metal stored in the pore gaps between the semiconductor grid frameworks, or a tritiated semiconductor formed by compounding tritium and the three-dimensional nanostructured semiconductor material, or a coexisting structure of the tritiated metal and the tritiated semiconductor; the tritiated metal and the three-dimensional nanostructure semiconductor form Schottky contact or ohmic contact, and are connected with the top electrode or the bottom electrode.

The three-dimensional nanostructured semiconductor may be a monocrystalline or polycrystalline semiconductor. The semiconductor material comprises two main classes of element semiconductors and compound semiconductors, wherein the element semiconductors comprise germanium and silicon, the compound semiconductors comprise III and V group compounds, II and VI group compounds, oxide semiconductors and solid solutions composed of III-V group compounds and II-VI group compounds; the group III and V compounds may be selected from gallium arsenide, gallium phosphide, gallium nitride, and the like; the II and VI compounds can be selected from cadmium sulfide, zinc sulfide and the like; the oxide semiconductor may be selected from zinc oxide, tin oxide, titanium oxide, gallium oxide, and the like; the solid solution composed of the III-V group compound and the II-VI group compound can be selected from gallium aluminum arsenic, gallium arsenic phosphorus and the like.

The three-dimensional nanostructure is an ordered or disordered film material consisting of at least one basic structural unit of zero dimension, one dimension and two dimensions, and the thickness of the film material can be 1-500 mu m. The basic structural units comprise nanodots, nanoparticles, nanowires, nanorods, nanopillars, nanotubes, nanoflowers, nanosheets, nanobelts, nanofprings, nanorings, nanocombs, nanoscalds, nanoneedles, nanocages, nanotopods, tower-shaped nanostructures, disk-shaped nanostructures, star-shaped nanostructures, branch-shaped nanostructures, hollow nanospheres, nanoarrays and the like.

In order to improve the energy conversion efficiency of the tritium-photovoltaic battery, the three-dimensional nanostructure semiconductor improves the generation and transportation efficiency of carriers through a material modification process. The material modification process may include high temperature reduction annealing, ion implantation doping of metallic or non-metallic elements, high temperature diffusion doping, chemical reaction doping, etc. in an inert gas or hydrogen atmosphere.

The tritium-based isotope source comprises tritiated metal and a tritiated semiconductor, wherein the tritiated metal is transition metal, alkali metal, alkaline earth metal, rare earth metal and alloy thereof, tritium and metal form stable metal-tritium bonds after high-temperature tritiation, so that the metal layer absorbs a large amount of tritium to form the tritiated metal; the tritiated semiconductor is formed by compounding tritium and a semiconductor material due to the fact that metal and nonmetal elements in the semiconductor and tritium form stable chemical bonds after the semiconductor material is tritiated at high temperature. The transition metal includes titanium, zirconium, scandium, palladium, cobalt, etc., the alkali metal includes lithium, etc., the alkaline earth metal includes beryllium, magnesium, etc., the rare earth metal includes lanthanum, uranium, erbium, etc., and the alloy includes zirconium cobalt, zirconium vanadium, lanthanum nickel, etc. The metal-tritium bond includes a titanium-tritium bond, a lithium-tritium bond, a magnesium-tritium bond, and the like, and the metal and nonmetal elements in the semiconductor form stable chemical bonds with tritium, including a titanium-tritium bond, a silicon-tritium bond, an oxygen-tritium bond, a sulfur-tritium bond, and the like.

The integration of the tritiated metal in the three-dimensional nanostructure is achieved by using the following process: firstly, a metal thin layer with the thickness of 5-1000 nm is pre-deposited on the surface of a three-dimensional nano-structure semiconductor through processes of atomic layer deposition, chemical vapor deposition, metal sputtering, metal electroplating or metal evaporation and the like, and then tritiation is carried out on the metal thin layer in a tritium atmosphere, wherein the temperature range is 100-800 ℃, and the pressure range is 100-1000 kPa.

The tritiated semiconductor is obtained by directly carrying out high-temperature high-pressure tritiation on a three-dimensional nanostructure semiconductor in a tritium atmosphere. The temperature range is 100-800 ℃, and the pressure range is 100-1000 kPa.

The top and bottom electrodes may be selected from metal electrodes, semiconductor electrodes, graphite electrodes, graphene electrodes, conductive polymer electrodes, conductive paste electrodes, or the like.

When the output power of a single battery is insufficient, the multi-unit multi-layer stacking integrated packaging can be realized in a parallel connection, series connection or series-parallel mixed connection mode, and the purpose of improving the output voltage and the output power is achieved.

The invention has the beneficial effects that:

the energy conversion material used by the tritium-photovoltaic battery is a three-dimensional nanostructure semiconductor, the application of the three-dimensional nanostructure can increase the action area of the isotope tritium radiation source and the energy conversion material, and the specific gravity of enrichment of isotope tritium in the semiconductor material is greatly improved. In addition, the isotope source three-dimensional structure integration solves the problem of low utilization efficiency of the radiation source caused by low energy self-absorption effect, scattering effect and coupling efficiency of the radiation source, and greatly improves the conversion efficiency and the output power of unit volume of the isotope battery. The tritiated metal and the three-dimensional nanostructure semiconductor form Schottky or ohmic contact, so that electron-hole pairs generated by isotope radiation beta particles can be effectively separated and transmitted, the carrier recombination rate is reduced, and the energy conversion efficiency of the tritium-volt battery is effectively improved. Meanwhile, the tritiated semiconductor is used as a component of the three-dimensional nano-structure semiconductor, and electron-hole pairs generated by beta particles can be effectively separated through a semiconductor heterojunction inside the structure, so that the energy conversion efficiency of the battery reaches about 30%. The three-dimensional nano-structure tritium photovoltaic battery can realize multi-group unit multi-layer stacking integrated packaging in a parallel or series connection mode, can realize high output power per unit volume, and has the characteristics of small volume and high energy density.

Drawings

Fig. 1 is a schematic structural composition diagram of embodiment 1 of the present invention.

FIG. 2 is a schematic view of a manufacturing process according to an embodiment of the present invention. In fig. 2, (a) a metal titanium sheet is used as an anode, a platinum metal sheet is used as a cathode, and a mixed solution of amine fluoride and ethylene glycol is used as an electrolyte; (b) carrying out anodic oxidation on the metal titanium sheet to prepare a titanium dioxide nanotube array film; (c) tritiated titanium dioxide nanotube array films; (d) forming a titanium metal film on the surface of the titanium dioxide nanotube by an atomic layer deposition technology; (e) a titanium metal film on the surface of the tritiated titanium dioxide nanotube; (f) and (3) plating a gold electrode on the upper surface of the titanium dioxide nanotube array film covered with the titanium tritide by evaporation.

Fig. 3 is a schematic diagram of series-parallel stack packaging of multiple sets of three-dimensional nanostructure tritium photovoltaic battery units according to an embodiment of the invention.

In FIGS. 1 to 3, the symbols are: 1-top electrode, 2-tritiated three-dimensional nanostructure semiconductor, 3-tritiated metal, 4-bottom electrode, 5-metal packaging tube shell, 6-insulating substrate, 7-metal lead, 8-pin, 9-conductive connecting wire and 10-external load.

Detailed Description

The following examples will further illustrate the present invention with reference to the accompanying drawings.