Radiation-lithium battery integrated cell

Abstract

The application discloses an integrated battery of isotope and lithium battery, which comprises a current collector, a negative electrode and a diaphragm arranged in sequence from top to bottom, and lithium battery electrolyte filled in the battery; and further comprises conductive material, semiconductor nanorod array film, active material layer, isotope radiation source and bottom electrode; the semiconductor nanorod array film is vertically arranged on the bottom electrode; the active material layer is attached to the surface of the semiconductor nanorod array film or filled in the gap or above the semiconductor nanorod array film or mixed with the conductive material and then filled in the gap or above the semiconductor nanorod array film; and the isotope radiation source is arranged in the gap of the semiconductor nanorod array film. The application integrates the isotope power generation and the lithium battery energy storage structure, has the function of converting the radiation energy of the isotope into electric energy and storing the energy by using the lithium battery structure, and improves the energy utilization efficiency and output power of the isotope battery.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of isotope batteries, in particular to an integrated beta-voltaic and lithium battery. BACKGROUND

[0002] With the rapid development of wireless sensor networks, the demand for micro power supply in harsh environments (such as deep sea, deep earth, deep space, polar regions and desert areas) has increased significantly. Compared with traditional batteries (such as chemical batteries, fuel cells, solar cells, etc.), isotope batteries have longer life, stronger environmental adaptability and higher energy density, and have broad application prospects and great market potential.

[0003] There are four main energy conversion methods for isotope batteries: thermoelectric conversion, direct energy conversion, direct charging and indirect energy conversion. Among them, direct conversion isotope batteries are based on the radiation volt effect, which is a device that directly converts isotope radiation energy into electrical energy. This type of isotope battery collects charged ions ionized by radiation particles in a specific environment, or electron-hole pairs excited in a semiconductor transducer material, to achieve current multiplication and energy conversion. The transducer structure of direct conversion isotope batteries mainly includes p-n junction and Schottky junction structures. Compared with thermoelectric conversion nuclear batteries, direct energy conversion isotope batteries have high safety and controllability; compared with direct charging and indirect energy conversion isotope batteries, they have greater advantages in energy conversion efficiency and output performance.

[0004] Beta-voltaic battery is a direct conversion isotope battery, but the collection and utilization of beta-voltaic battery energy is a challenge. In practical applications, beta-voltaic batteries are usually connected together with rechargeable energy storage devices (batteries, lithium batteries, supercapacitors, etc.). Due to the low open-circuit voltage of beta-voltaic batteries, they cannot meet the charging voltage requirements of batteries or lithium batteries or the high charge requirements of capacitors, and often need to connect multiple beta-voltaic batteries in series and parallel and use additional energy management circuits to ensure that the output voltage of the isotope battery matches the input voltage requirements of the energy storage unit. The connection between multiple device units through the line also introduces Ohmic transmission loss, which leads to increased cost and reduced energy utilization of this integrated approach. SUMMARY

[0005] The present application aims to solve the above-mentioned problems in the prior art and provide an integrated battery that converts isotope radiation beta particle energy into electrical energy and stores it using lithium ion redox reactions, i.e. an integrated beta-voltaic and lithium battery.

[0006] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] The integrated battery comprises a current collector, a negative electrode and a diaphragm arranged in sequence from top to bottom, and a lithium battery electrolyte filled in the battery; further comprises a conductive material, a semiconductor nanorod array film, an active material layer, an isotope radiation source and a bottom electrode; the semiconductor nanorod array film is vertically arranged on the bottom electrode; the active material layer is attached to the surface of the semiconductor nanorod array film or filled in the gap or above the semiconductor nanorod array film or mixed with the conductive material and then filled in the gap or above the semiconductor nanorod array film; the isotope radiation source is arranged in the gap of the semiconductor nanorod array film.

[0008] The current collector is a copper foil, an aluminum foil, a composite copper foil or a composite aluminum foil; the negative electrode is a lithium foil or a lithium alloy foil; the diaphragm is a polyethylene, a polypropylene or other polyolefin microporous membrane or a glass fiber diaphragm; the lithium battery electrolyte is an electrolyte formed by dissolving at least one of LiClO4, LiPF6, LiBF6 or LiAsF6 in an organic matter; the organic matter is at least one of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or methyl ethyl carbonate (EMC).

[0009] The conductive material comprises a large specific surface carbon-based material such as a carbon nanotube, graphene, carbon fiber, conductive graphite particles and the like, which improves the interface charge transport performance and increases the electrochemical reaction site. The carbon-based material is preferably a carbon-based material prepared by carbon-14, which meets the conductive performance and is used as a radiation source.

[0010] The semiconductor nanorod array film is a crystalline wide-bandgap semiconductor film with a band gap greater than 2.3eV, which is formed by a plurality of parallel nanorods arranged side by side; the rod diameter of the semiconductor nanorod array film is 10-1000nm, and the rod length is 200nm-100μm.

[0011] The semiconductor material of the semiconductor nanorod array film can be at least one of a semiconductor metal oxide, a semiconductor compound and a semiconductor element, including titanium dioxide, zinc oxide, zirconium dioxide, cadmium oxide, niobium pentoxide, cerium oxide, gallium trioxide, tin dioxide, tungsten trioxide, silicon carbide, gallium nitride, indium gallium nitride, gallium phosphide, indium nitride, aluminum nitride, aluminum phosphide, arsenic aluminum, etc., molybdenum disulfide, cadmium sulfide, zinc sulfide, magnesium sulfide, zinc selenide, magnesium selenide, diamond, etc.

[0012] The active material layer is a layered structured compound with a band gap of 1-5eV.

[0013] The active material layer is selected from at least one of vanadium pentoxide, molybdenum disulfide, molybdenum oxide and cadmium sulfide, and achieves the performance of charging and discharging by deintercalating lithium ions, simultaneously forms a heterojunction with the semiconductor nanorod array film as a hole transport layer material, enhances the transport and separation of carriers, reduces the probability of carrier recombination, and improves the energy conversion efficiency of the beta-volt battery. The preparation method of the active material includes a hydrothermal synthesis method, a chemical bath deposition (CBD) method and a successive ionic layer absorption and reaction (SILAR) method.

[0014] The isotope radiation source is a radiation source capable of radiating beta particles during decay, and has a half-life of not less than 10 years. In order to prevent radiation damage to the semiconductor material, the average energy of the beta particles is not higher than 250KeV. The material of the isotope radiation source can be a single element material or a compound material. Preferably, the isotope radiation source can use isotopes such as tritium, carbon-14, nickel-63 and promethium-147. Specifically, tritium exists in the form of titanium tritide; carbon-14 exists in the form of carbon cloth, graphite, graphene and carbon nanotubes; nickel-63 and promethium-147 exist in the form of single element metals.

[0015] The bottom electrode is metal, semiconductor, graphite, graphene, carbon cloth, etc., and is preferably prepared from a radioactive isotope material having a conductive property, including at least one of nickel-63, promethium-147 and carbon-14.

[0016] Compared with the prior art, the technical scheme of the present application has the following beneficial effects:

[0017] The beta-volt-lithium battery integrates the power generation unit and the energy storage unit in one device, saves the line connection and does not need an additional energy management circuit. When the radioactive isotope material integrated in the battery radiates high-energy beta particles, the isotope radiation energy can be continuously converted into chemical energy by the energy conversion structure in the battery and directly stored in the battery. According to the demand of the external load, the battery can control and release energy at any time, realizes the functions of trickle charging and energy storage, and high-power long-time discharging. These greatly improve the energy utilization rate of the beta-volt battery and reduce the ohmic transmission loss and cost. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 FIG. 1 is a structural schematic diagram of the beta-volt-lithium battery of embodiment 1 of the present application;

[0019] Figure 2This is a schematic diagram of the structure of the integrated volt-lithium battery of Embodiment 2 of the present invention.

[0020] Figure labels: 1-Current collector; 2-Battery negative electrode; 3-Separator; 4-Conductive nanomaterial; 5-Lithium-ion battery electrolyte; 6-Semiconductor nanorod array thin film; 7-Active material layer; 8-Isotope radiation source; 9-Bottom electrode. Detailed Implementation

[0021] To make the technical problems, technical solutions and beneficial effects of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0022] Example 1

[0023] like Figure 1 As shown, the integrated volt-lithium battery structure described in this embodiment includes a current collector 1, a battery negative electrode 2, a separator 3, conductive nanomaterials 4, a lithium electrolyte 5, a semiconductor nanorod array thin film 6, an active material layer 7, an isotope radiation source 8, and a bottom electrode 9.

[0024] In this embodiment, the current collector 1 is made of aluminum foil; the battery negative electrode 2 is a lithium sheet; the separator 3 is glass fiber; the conductive nanomaterial 4 is carbon nanotubes prepared from carbon-14; the semiconductor nanorod array film 6 is a wide bandgap semiconductor zinc oxide, which is formed by vertically stacking multiple semiconductor nanorods on the bottom electrode 9; the active material layer 7 is attached to the outer surface of the semiconductor nanorods; the isotopic radiation source 8 is nickel-63, which is deposited in the gaps between the semiconductor nanorod array film 6; and the bottom electrode 9 is a nickel-63 sheet.

[0025] The method for preparing the integrated volt-lithium battery described in this embodiment includes the following steps:

[0026] (1) Preparation of semiconductor nanorod array thin film: A layer of zinc acetate was coated on the bottom electrode nickel-63 substrate and annealed as a seed layer. The growth solution was composed of 0.05M zinc nitrate hexahydrate, 0.05M hexamethyltetramine, 0.02M polyetherimide and deionized water. Zinc oxide nanorod array thin film was prepared on nickel-63 substrate by hydrothermal synthesis process. Then the sample was placed in an inert atmosphere or hydrogen atmosphere for high-temperature annealing. The diameter of the semiconductor nanorods was 10-1000 nm and the length was 200 nm-100 μm.

[0027] (2) Active material layer modified semiconductor nanorod array film: with the nickel-63 sheet with semiconductor nanorod array film as the substrate, with ammonium vanadate, oxalic acid and deionized water to form the growth solution, using hydrothermal synthesis process to deposit vanadium pentoxide on the semiconductor nanorod array film, and then the sample is annealed at high temperature in air, finally the semiconductor nanorod array film with deposited vanadium pentoxide is obtained.

[0028] (3) Isotope radiation source 8 deposited in the gap of semiconductor nanorod array film: with the solution containing nickel-63 ions as the electrolyte, using electrochemical plating technology, nickel-63 metal is plated in the gap of semiconductor nanorod;

[0029] (4) Preparation of conductive nanomaterial 4: V2O5 nanorod powder (VNRs), conductive agent single-walled carbon nanotubes (SWCNTs) and binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8:1:1, then N-methyl pyrrolidone (NMP) is added to form a slurry with uniform color and good flowability, which is uniformly coated on the top of the semiconductor nanorod array film with deposited vanadium pentoxide by a coater. Then it is moved to a vacuum drying oven with a temperature setting of 120°C for drying for more than 12h, and finally the sample is transferred to a vacuum drying oven at 80°C for drying.

[0030] (5) Assemble the battery in an argon-filled glove box (H2O, O2 are less than 1ppm), the above prepared electrode sheet is used as the positive electrode of the battery, the positive electrode is put into the customized acrylic groove, the electrode is led out at the bottom through the aluminum foil, then the electrolyte is added, the electrolyte is 1M LiPF6 dissolved in ethylene carbonate (EC) / dimethyl carbonate (DMC), then the glass fiber separator, lithium sheet, current collector and copper foil leading electrode are covered in turn, and finally the screw is fixed and the gap is sealed with epoxy resin glue.

[0031] Example 2

[0032] As shown in Figure 2 , the structure of the integrated radioisotope-lithium battery of the present embodiment includes a current collector 1, a battery negative electrode 2, a separator 3, a conductive nanomaterial 4, a lithium battery electrolyte 5, a semiconductor nanorod array film 6, an active material layer 7, an isotope radiation source 8, and a bottom electrode 9.

[0033] In this embodiment, the material of the current collector 1 is aluminum foil; the negative electrode 2 of the battery is lithium sheet; the separator 3 is glass fiber; the conductive nanomaterial 4 is carbon-14 prepared carbon nanotube; the semiconductor nanorod array film 6 is a wide band gap semiconductor zinc oxide, which is vertically stacked by a plurality of semiconductor nanorods on the bottom electrode 9; the active material layer 7 is a molybdenum disulfide film coated on the surface of the semiconductor nanorod; the isotope radiation source 8 is carbon-14 nanotube deposited in the gap of the semiconductor nanorod array film 6; and the bottom electrode 9 is carbon-14 prepared carbon cloth.

[0034] The preparation method of the embodiment of the radio-voltaic-lithium battery integrated battery comprises the following steps:

[0035] (1) Preparation of semiconductor nanorod array film: a layer of zinc acetate is coated on the carbon-14 prepared carbon cloth, and after annealing, it is used as a seed layer. A growth solution composed of 0.05M zinc nitrate hexahydrate, 0.05M hexamethyltetramine, 0.02M polyetherimide and deionized water is used to prepare a zinc oxide nanorod array film on the carbon-14 prepared carbon cloth by hydrothermal synthesis process, and then the sample is placed in an inert atmosphere or hydrogen atmosphere for high temperature annealing; the rod diameter of the semiconductor nanorod is 10-1000nm, and the rod length is 200nm-100μm.

[0036] (2) Modification of the active material layer of the semiconductor nanorod array film: the carbon-14 cloth with the semiconductor nanorod array film is used as the substrate, a growth solution composed of ammonium molybdate, thiourea and deionized water is used to deposit molybdenum disulfide on the zinc oxide nanorod array film by hydrothermal synthesis process, and then the sample is annealed at high temperature under argon atmosphere, and finally the semiconductor nanorod array film with deposited molybdenum disulfide is obtained.

[0037] (3) Deposition of isotope radiation source 8 in the gap of the semiconductor array film: carbon nanotubes are soaked in a growth solution composed of radioactive isotope citric acid, deionized water, ethanol and ammonia solution. After the carbon nanotubes are dried at 80℃, the sample is calcined in a box furnace at 200℃ for 3h to form the isotope radiation source carbon-14 nanotube, which is coated in the gap of the semiconductor nanorod array film with deposited molybdenum disulfide.

[0038] (4) Preparation of conductive nanomaterial: carbon-14 nanotubes and adhesive polyvinylidene fluoride (PVDF) are mixed in a mass ratio of 1:1, N-methyl pyrrolidone (NMP) is added to form a slurry with uniform color and good fluidity, which is uniformly coated on the top of the semiconductor nanorod array film with deposited molybdenum disulfide by a coater. Then it is moved to a vacuum drying oven with a temperature setting of 120℃ for drying for more than 12h, and finally the sample is transferred to a vacuum drying oven at 80℃ for drying.

[0039] (5) In the glove box filled with argon (H2O, O2 are less than 1 ppm), the battery is assembled, the electrode piece prepared above is used as the positive electrode of the battery, the positive electrode of the battery is put into the customized acrylic groove, the electrode is led out through the aluminum foil at the bottom, then the electrolyte is added dropwise, the electrolyte is 1M LiPF6 dissolved in ethylene carbonate (EC) / dimethyl carbonate (DMC), the glass fiber separator, lithium sheet, current collector and copper foil leading electrode are covered in turn, and the top acrylic plate is finally fixed with screws and sealed with epoxy resin glue to seal the gap.

[0040] The application integrates the radiation power generation and the lithium battery energy storage structure, has the function of converting the radiation energy of isotopes into electric energy and storing energy by using the lithium battery structure, and the battery improves the energy utilization efficiency and output power of the isotope battery.

Claims

1. A battery integrating radiative and lithium cells, comprising a current collector, a negative electrode and a separator arranged in order from top to bottom, and a lithium cell electrolyte filled in the battery; characterized in that: The device further comprises a conductive material, a semiconductor nanorod array film, an active material layer, an isotope radiation source and a bottom electrode; the semiconductor nanorod array film is vertically arranged on the bottom electrode; the active material layer is attached to the surface of the semiconductor nanorod array film or filled in the gaps or above the semiconductor nanorod array film or mixed with the conductive material and then filled in the gaps or above the semiconductor nanorod array film; the isotope radiation source is arranged in the gaps of the semiconductor nanorod array film. The negative electrode is a lithium foil or a lithium alloy foil; the lithium battery electrolyte is an electrolyte formed by dissolving conductive salts of LiClO4, LiPF6, LiBF6 or LiAsF6 in an organic substance; the semiconductor material of the semiconductor nanorod array film comprises at least one of titanium dioxide, zinc oxide, zirconium dioxide, cadmium oxide, niobium pentoxide, cerium oxide, gallium sesquioxide, tin dioxide, tungsten trioxide, silicon carbide, gallium nitride, indium gallium nitride, gallium phosphide, indium nitride, aluminum nitride, aluminum phosphide, aluminum arsenide, etc., molybdenum disulfide, cadmium sulfide, zinc sulfide, magnesium sulfide, zinc selenide, magnesium selenide, diamond; the active material layer is selected from at least one of vanadium pentoxide, molybdenum disulfide, molybdenum oxide and cadmium sulfide; the bottom electrode is prepared by using a radioactive isotope material with conductive properties, including at least one of nickel-63, promethium-147 and carbon-14.

2. The vanadium-lithium integrated battery of claim 1, wherein: The current collector is a copper foil, an aluminum foil, a composite copper foil or a composite aluminum foil; the separator is a polyolefin microporous membrane or a glass fiber separator; the organic substance is at least one of ethylene carbonate, diethyl carbonate, dimethyl carbonate or methyl ethyl carbonate.

3. The radio-lithium cell integrated battery according to claim 1, wherein: the lithium cell is a lithium-ion cell. The conductive material comprises at least one of carbon nanotubes, graphene, carbon fibers and conductive graphite particles.

4. The radio-lithium cell integrated battery of claim 1, wherein: the lithium cell is a lithium-ion cell. The conductive material comprises a carbon-based material prepared by carbon-14.

5. The vanadium-lithium integrated battery of claim 1, wherein: the lithium battery is a lithium-ion battery. The semiconductor nanorod array film is a crystalline wide-bandgap semiconductor film with a band gap greater than 2.3eV, which is formed by a plurality of parallel nanorods arranged side by side; the rod diameter of the semiconductor nanorod array film is 10-1000nm, and the rod length is 200nm-100μm.

6. The vanadium-lithium integrated battery of claim 1, wherein: the lithium battery is a lithium-ion battery. The active material layer is a layered structured compound with a band gap of 1-5eV.

7. The radio-lithium cell integrated battery of claim 1, wherein: the lithium cell is a lithium-ion cell. The isotope radiation source is a radiation source capable of emitting beta particles during decay, and has a half-life of not less than 10 years.

8. The radio-lithium cell integrated battery according to claim 7, wherein: The isotope radiation source uses at least one of tritium, carbon-14, nickel-63 and promethium-147 isotopes.

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