A Graphene-Based Isotope Battery with Improved Performance Using Perfluorosulfonic Acid Polymer and Its Preparation Method

Abstract

The present invention belongs to the field of micro-energy and nuclear technology applications, and discloses a graphene-based isotope battery that uses a perfluorosulfonic acid polymer to improve performance, and its preparation method. The graphene-based isotope battery comprises a radioactive source, a perfluorosulfonic acid polymer layer, a graphene layer, an intrinsic semiconductor material layer, an N-type semiconductor material layer, and a back electrode, stacked in order from top to bottom. The perfluorosulfonic acid polymer layer serves as an intermediate dielectric layer for graphene transfer and a high-efficiency P-type dopant for graphene, and together with the graphene layer, forms a perfluorosulfonic acid composite graphene layer. The preparation method of the present invention can effectively address the current problems of unsatisfactory output performance of graphene-based isotope batteries caused by low graphene work function and intrinsic carrier concentration, as well as wrinkles and damage during graphene transfer. Furthermore, the addition of the intrinsic semiconductor material layer can effectively increase the barrier width of the graphene-based isotope battery device, further improving the overall output performance of the device.

Description

Technical Field

[0001] The present invention relates to the fields of micro-energy and nuclear technology applications, and in particular to a graphene-based isotope battery using a perfluorosulfonic acid polymer to improve performance and a preparation method thereof. Background Art

[0002] Microelectronic devices used in extreme environments like deep space and the deep ocean require a compatible miniature independent power supply to ensure long-term stable operation even in the event of a main power failure. Isotope batteries are an excellent choice for this purpose due to their long lifespan, stable operation, and ease of direct integration with microelectronic devices.

[0003] In 2020, the Hefei Institutes of Physical Science, Chinese Academy of Sciences, published a patent titled "A Graphene-Based Heterojunction Isotope Battery" (Patent No.: 202010868066.8). Graphene and semiconductor materials form a heterojunction to reduce the absorption and blocking effect of traditional electrode materials on radioactive sources, thereby improving the energy conversion efficiency of isotope batteries. In 2021, researchers used graphene and N-type silicon semiconductors to prepare a graphene / silicon Schottky (heterojunction) isotope battery with an activity of 5mCi / cm 2 of 63 Under Ni radiation source irradiation, an open circuit voltage of 48mV and a current of 30.3nA / cm 2 The short-circuit current and output power are about 0.5nW / cm 2 (Micro-Nano Electronics Technology, 2021, 58: 10-16).

[0004] However, since the heterojunction isotope battery uses graphene produced by chemical vapor deposition (CVD), not only is the work function and intrinsic carrier concentration low, but problems such as wrinkles and damage, unremoved impurities and etching solution residues generated during the transfer process have a great impact on the barrier height and carrier mobility of the graphene-based isotope battery, resulting in low output performance of the graphene-based isotope battery device, which is difficult to match the power requirements of microelectronic devices.

[0005] Therefore, there is an urgent need to explore new graphene doping and transfer methods suitable for isotope batteries, which is of great significance to improving the output performance of graphene-based isotope batteries. Summary of the Invention

[0006] The present invention aims to solve the problems existing in the work function and transfer process of graphene prepared by chemical vapor deposition, and provides a graphene-based isotope battery with improved performance by using perfluorosulfonic acid polymer and a preparation method thereof.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] The first aspect of the present invention is to provide a graphene-based isotope battery using a perfluorosulfonic acid polymer to improve performance, comprising a radioactive source (1), a perfluorosulfonic acid polymer layer (2), a graphene layer (3), an intrinsic semiconductor material layer (4), an N-type semiconductor material layer (5), and a back electrode (6) stacked in sequence from top to bottom; wherein the perfluorosulfonic acid polymer layer (2) serves as an intermediate dielectric layer for graphene transfer and a high-efficiency P-type dopant for graphene, and forms a perfluorosulfonic acid composite graphene layer (7) with the graphene layer (3).

[0009] Preferably, the radiation source (1) comprises 3 H. 14 C. 32 P. 63 Ni, 90 Sr. 137 Cs, 147 One or more beta-radiating sources of Pm.

[0010] Preferably, the graphene layer (3) is a single layer, a few layers or a multilayer graphene prepared by chemical vapor deposition, and has a thickness of 0.3 nm to 10 nm.

[0011] Preferably, the graphene layer (3) is copper-based or nickel-based surface graphene prepared by chemical vapor deposition.

[0012] Preferably, the graphene layer (3) has 1 single layer, 3 to 5 layers, and 10 to 20 layers.

[0013] Preferably, the N-type semiconductor material layer (5) is one of Si, GaAs, GaN, SiC, wide bandgap semiconductors, and ultra-wide bandgap semiconductors.

[0014] Preferably, the metal back electrode (6) is a composite electrode of one or a combination of several of Au, Ag, Ni, Al, Ti, Cu, Ge, In, and Ga.

[0015] Preferably, the perfluorosulfonic acid composite graphene layer (7) has a thickness of 10 nm to 5 μm and can be directly used as an upper electrode of an isotope battery.

[0016] The second aspect of the present invention is to provide a method for preparing a graphene-based isotope battery using a perfluorosulfonic acid polymer to improve performance, comprising the following steps:

[0017] S1. epitaxially growing an intrinsic semiconductor material layer (4) on an N-type semiconductor material layer (5) by using a molecular beam or plasma chemical vapor deposition method;

[0018] S2. Based on the sample prepared in step S1, a metal back electrode (6) is formed on the back side of the N-type semiconductor material layer (5) by scraping or magnetron sputtering;

[0019] S3, directly coating the perfluorosulfonic acid polymer layer (2) on the surface of the copper-based or nickel-based graphene prepared by chemical vapor deposition, wet-etching the copper-based or nickel-based material to obtain a perfluorosulfonic acid composite graphene layer (7), transferring the layer to the upper surface of the sample prepared in step S2 and leading out as an upper electrode;

[0020] S4. Loading a radioactive source (1) on the surface of the device prepared in step S3 completes the preparation of a graphene-based isotope battery with improved performance using a perfluorosulfonic acid polymer.

[0021] Preferably, in step S1, the thickness of the N-type semiconductor material layer (5) is 50 μm to 500 μm; and the thickness of the epitaxial intrinsic semiconductor material layer (4) is 100 nm to 200 μm.

[0022] More preferably, in step S1, the thickness of the N-type semiconductor material layer (5) is 100 μm to 300 μm; and the thickness of the epitaxial intrinsic semiconductor material layer (4) is 500 nm to 50 μm.

[0023] Preferably, in step S3, the perfluorosulfonic acid polymer layer (2) is directly coated on the surface of the graphene layer (3) by drop casting or spin coating.

[0024] More preferably, in step S3, a Nafion solution with a mass fraction of 0.5% to 5% is directly dropped on the surface of the copper-based or nickel-based graphene or spin-coated on the surface of the copper-based or nickel-based graphene at a low speed of 200 to 600 rpm.

[0025] Preferably, in step S4, loading the radioactive source (1) on the surface of the device includes loading a solid radioactive source and a gaseous radioactive source.

[0026] Preferably, if a solid-state radioactive source is loaded, it can be loaded directly on the device surface by electrodeposition or chemical deposition.

[0027] If a gaseous radioactive source is loaded, the corresponding metal or metal compound material storing the gaseous radioactive source is first deposited on the surface of the device, and then the gaseous radioactive source is adsorbed and loaded.

[0028] The present invention adopts the above technical solution, which has the following technical effects compared with the prior art:

[0029] (1) Using perfluorosulfonic acid polymer as the intermediate dielectric layer for graphene transfer and as an efficient P-type dopant for graphene, the problems existing in the graphene work function and transfer process are solved, and the integrity of graphene transfer is ensured while improving the graphene work function and intrinsic carrier concentration;

[0030] (2) On the N-type semiconductor material layer, the graphene-based isotope battery is prepared by epitaxially growing the intrinsic semiconductor material layer using molecular beam or plasma chemical vapor deposition method, which can effectively increase the barrier width of the graphene-based isotope battery device and further improve the overall output performance of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a schematic diagram of the structure of a graphene-based isotope battery that uses perfluorosulfonic acid polymer to improve performance;

[0032] The reference numerals in the figures are: 1-radiation source, 2-perfluorosulfonic acid polymer layer, 3-graphene layer, 4-intrinsic semiconductor material layer, 5-N-type semiconductor material layer, 6-back electrode, 7-perfluorosulfonic acid composite graphene layer. DETAILED DESCRIPTION

[0033] The main technical solution of this invention is to use a perfluorosulfonic acid polymer layer as an intermediate dielectric layer for graphene transfer and a high-efficiency P-type dopant for graphene, effectively resolving the problems with graphene work function and transfer processes encountered in existing methods for preparing isotope batteries. Furthermore, by adding an intrinsic semiconductor material layer between the perfluorosulfonic acid composite graphene layer and the N-type semiconductor material layer, the barrier width of the graphene-based isotope battery device is effectively increased, thereby improving the carrier collection efficiency and, consequently, the overall output performance of the battery.

[0034] Specifically, if Figure 1 As shown, the graphene-based isotope battery is a stacked structure consisting of a radiation source 1, a perfluorosulfonic acid polymer layer 2, a graphene layer 3, an intrinsic semiconductor material layer 4, an N-type semiconductor material layer 5, and a back electrode 6 from top to bottom; the perfluorosulfonic acid polymer layer serves as an intermediate dielectric layer for graphene transfer and an efficient P-type dopant for graphene, and together with the graphene layer forms a perfluorosulfonic acid composite graphene layer 7.

[0035] The present invention will be described in detail and specifically below through specific examples to provide a better understanding of the present invention, but the following examples do not limit the scope of the present invention.

[0036] Example 1

[0037] This embodiment is based on 63 Ni radioactive source, providing a graphene / silicon isotope battery using perfluorosulfonic acid polymer to improve performance, the preparation method of which is as follows:

[0038] A 30μm-thick, low-doped intrinsic epitaxial layer was grown on a 4-inch, 300μm-thick N-type monocrystalline silicon wafer using molecular beam epitaxy. A metal aluminum electrode was deposited on the back of the N-type silicon wafer using magnetron sputtering. The 4-inch wafer was then cut into 1cm×1cm silicon units using a dicing machine and stored in a moisture-proof cabinet for later use.

[0039] A single-layer copper-based graphene grown by chemical vapor deposition was selected, and a 5% mass fraction of Nafion solution was spin-coated at a low speed of 300 rpm on the surface of a single-layer copper-based graphene with an area of 5mm×5mm. The surface was placed in a FeCl3 solution and the copper substrate was etched. The obtained 2μm perfluorosulfonic acid composite graphene layer was washed several times in deionized water and transferred to the surface of the cut silicon basic unit and led out as the upper electrode to obtain a perfluorosulfonic acid composite graphene / silicon transducer device. The constant current electrodeposition mode was used to 63 A Ni radioactive source is loaded onto the surface of a perfluorosulfonic acid composite graphene / silicon transducer device to complete the preparation of a graphene / silicon isotope battery using a perfluorosulfonic acid polymer.

[0040] Different from the above, as a comparative example, PMMA was spin-coated on a 5mm×5mm single-layer copper-based graphene surface by spin coating, and the surface was placed in a FeCl3 solution until the copper substrate was etched. The PMMA / graphene was washed several times in deionized water and then transferred to the surface of the cut silicon basic unit. The surface was then immersed in a hot acetone solution to remove the PMMA covering the surface, thereby obtaining a graphene / silicon transducer device. The constant current electrodeposition mode was used to deposit the PMMA. 63 The Ni radioactive source is loaded onto the surface of the graphene / silicon transducer device, thereby completing the preparation of the graphene / silicon isotope battery without using perfluorosulfonic acid polymer.

[0041] The Keithley4200-SCS parameter analyzer produced by Keithley was used to analyze the 63 The output performance of graphene / silicon isotope batteries using perfluorosulfonic acid polymer and not using perfluorosulfonic acid polymer as Ni source was tested. The results showed that the open circuit voltage of graphene / silicon isotope battery using perfluorosulfonic acid polymer was 0.15V and the short circuit current was 54nA / cm 2 ; The graphene / silicon isotope battery without perfluorosulfonic acid polymer has an open circuit voltage of 0.07V and a short circuit current of 30nA / cm 2 This shows that the use of perfluorosulfonic acid polymer layer can effectively improve the output performance of graphene-based isotope batteries.

[0042] Example 2

[0043] This embodiment is based on 3H radioactive source, providing a graphene / silicon isotope battery using perfluorosulfonic acid polymer to improve performance, the preparation method of which is as follows:

[0044] A 10μm-thick, low-doped intrinsic epitaxial layer was grown on a 4-inch, 150μm-thick N-type monocrystalline silicon wafer using molecular beam epitaxy. After applying a scraped indium gallium electrode to the back of the N-type silicon wafer, the 4-inch wafer was cut into 1cm×1cm silicon units using a dicing machine and stored in a moisture-proof cabinet for later use.

[0045] A single-layer copper-based graphene grown by chemical vapor deposition was selected, and a 5% mass fraction of Nafion solution was spin-coated at a low speed of 300 rpm on the surface of a single-layer copper-based graphene with an area of 5mm×5mm. The surface was placed in a FeCl3 solution and the copper substrate was etched. The obtained 2μm perfluorosulfonic acid composite graphene layer was washed several times in deionized water and transferred to the surface of the cut silicon basic unit and led out as the upper electrode to obtain a perfluorosulfonic acid composite graphene / silicon transducer device. Titanium metal was deposited on the surface of the perfluorosulfonic acid composite graphene / silicon transducer device using a constant current electrodeposition mode, and the titanium film was used to absorb the titanium metal. 3 H, completed the preparation of graphene / silicon isotope battery using perfluorosulfonic acid polymer.

[0046] Different from the above, as a comparative example, PMMA was spin-coated on a 5mm×5mm single-layer copper-based graphene surface by spin coating, and the copper substrate was placed in a FeCl3 solution. After the copper substrate was etched, the PMMA / graphene was washed several times in deionized water and transferred to the surface of the cut silicon basic unit. It was then soaked in a hot acetone solution to remove the PMMA covering the surface, thereby obtaining a graphene / silicon transducer device. Titanium metal was deposited on the surface of the perfluorosulfonic acid composite graphene / silicon transducer device by sputtering, and the titanium film was used to absorb the titanium metal. 3 H, that is, the preparation of graphene / silicon isotope battery without using perfluorosulfonic acid polymer is completed.

[0047] The Keithley4200-SCS parameter analyzer produced by Keithley was used to analyze the 3 The output performance of the graphene / silicon isotope battery using perfluorosulfonic acid polymer and not using perfluorosulfonic acid polymer as H source was tested. The results showed that the graphene / silicon isotope battery using perfluorosulfonic acid polymer had an open circuit voltage of 0.32V and a short circuit current of 92nA / cm 2 ; The graphene / silicon isotope battery without perfluorosulfonic acid polymer has an open circuit voltage of 0.12V and a short circuit current of 48nA / cm 2 This shows that the use of perfluorosulfonic acid polymer layer can effectively improve the output performance of graphene-based isotope batteries.

[0048] Example 3

[0049] This embodiment is based on 63 Ni radioactive source, providing a graphene / silicon carbide isotope battery that uses perfluorosulfonic acid polymer to improve performance, and its preparation method is as follows:

[0050] A 30μm-thick, low-doped intrinsic epitaxial layer was grown on a 4-inch, 300μm-thick N-type single-crystal silicon carbide wafer using molecular beam epitaxy. A nickel / titanium / gold composite electrode was magnetron sputtered onto the back of the N-type single-crystal silicon carbide. A laser scriber then cut the 4-inch wafer into 1cm×1cm silicon carbide units, which were then stored in a moisture-proof cabinet for later use.

[0051] A few-layer (3-5 layers) copper-based graphene grown by chemical vapor deposition was selected, and a 2.5% mass fraction of Nafion solution was spin-coated at a low speed of 300 rpm on the surface of a few-layer copper-based graphene with an area of 5mm×5mm. The graphene was placed in a FeCl3 solution and the copper substrate was etched. The obtained 1μm perfluorosulfonic acid composite graphene layer was washed several times in deionized water and transferred to the surface of the cut silicon carbide basic unit and led out as the upper electrode to obtain a perfluorosulfonic acid composite graphene / silicon carbide transducer device. The constant current electrodeposition mode was used to 63 A Ni radioactive source is loaded onto the surface of a perfluorosulfonic acid composite graphene / silicon carbide transducer device to complete the preparation of a graphene / silicon carbide isotope battery using a perfluorosulfonic acid polymer.

[0052] Different from the above, as a comparative example, PMMA was spin-coated on a 5mm×5mm surface of a few-layer copper-based graphene, placed in a FeCl3 solution until the copper substrate was etched, and the PMMA / graphene was washed several times in deionized water and transferred to the surface of the cut silicon carbide basic unit. It was then immersed in a hot acetone solution to remove the PMMA covering the surface, thereby obtaining a graphene / silicon carbide transducer device. 63 The Ni radioactive source is loaded onto the surface of the graphene / silicon carbide transducer device, thereby completing the preparation of the graphene / silicon carbide isotope battery without using perfluorosulfonic acid polymer.

[0053] The Keithley4200-SCS parameter analyzer produced by Keithley was used to analyze the 63 The output performance of graphene / silicon carbide isotope batteries using perfluorosulfonic acid polymer and not using perfluorosulfonic acid polymer as Ni source was tested. The results showed that the open circuit voltage of graphene / silicon carbide isotope battery using perfluorosulfonic acid polymer was 0.8V and the short circuit current was 38nA / cm 2; The graphene / silicon isotope battery without perfluorosulfonic acid polymer has an open circuit voltage of 0.35V and a short circuit current of 16nA / cm 2 This shows that the use of perfluorosulfonic acid polymer layer can effectively improve the output performance of graphene-based isotope batteries.

[0054] Example 4

[0055] This embodiment is based on 3 H radioactive source, providing a graphene / silicon carbide isotope battery using perfluorosulfonic acid polymer to improve performance, the preparation method of which is as follows:

[0056] A 15μm-thick, low-doped intrinsic epitaxial layer was grown on a 4-inch, 300μm-thick N-type single-crystal silicon carbide wafer using molecular beam epitaxy. The backside of the N-type single-crystal silicon carbide was magnetron sputtered with nickel / titanium / aluminum / nickel. The 4-inch wafer was then cut into 1cm×1cm silicon carbide units using a laser scriber and stored in a moisture-proof cabinet for later use.

[0057] Multilayer (10 layers) copper-based graphene grown by chemical vapor deposition was selected, and a 2.5% mass fraction of Nafion solution was spin-coated at a low speed of 300 rpm on the surface of the multilayer copper-based graphene with an area of 5mm×5mm. The graphene was placed in a FeCl3 solution and the copper substrate was etched. The obtained 1μm perfluorosulfonic acid composite graphene layer was washed several times in deionized water and transferred to the surface of the cut silicon carbide basic unit and led out as the upper electrode to obtain a perfluorosulfonic acid composite graphene / silicon carbide transducer device. The constant current electrodeposition mode was used to 63 A Ni radioactive source is loaded onto the surface of a perfluorosulfonic acid composite graphene / silicon transducer device to complete the preparation of a graphene / silicon carbide isotope battery using a perfluorosulfonic acid polymer.

[0058] Different from the above, as a comparative example, PMMA was spin-coated on a multilayer copper-based graphene surface with an area of 5mm×5mm by spin coating, and the surface was placed in a FeCl3 solution. After the copper substrate was etched, the PMMA / graphene was washed several times in deionized water and transferred to the surface of the cut silicon carbide basic unit. The surface was then soaked in a hot acetone solution to remove the PMMA covering the surface, thereby obtaining a graphene / silicon carbide transducer device. After palladium metal was deposited on the surface of the perfluorosulfonic acid composite graphene / silicon carbide transducer device by electrodeposition, the palladium film was used to absorb the palladium. 3 H, that is, the preparation of graphene / silicon carbide isotope battery without using perfluorosulfonic acid polymer is completed.

[0059] The Keithley4200-SCS parameter analyzer produced by Keithley was used to analyze the 3The output performance of the graphene / silicon carbide isotope battery using perfluorosulfonic acid polymer and not using perfluorosulfonic acid polymer as the H source was tested. The results showed that the graphene / silicon carbide isotope battery using perfluorosulfonic acid polymer had an open circuit voltage of 1.05V and a short circuit current of 75nA / cm 2 ; The graphene / silicon carbide isotope battery without perfluorosulfonic acid polymer has an open circuit voltage of 0.6V and a short circuit current of 30nA / cm 2 This shows that the use of perfluorosulfonic acid polymer layer can effectively improve the output performance of graphene-based isotope batteries.

[0060] Example 5

[0061] This embodiment is based on 90 Sr radioactive source, providing a graphene / diamond isotope battery using perfluorosulfonic acid polymer to improve performance, the preparation method of which is as follows:

[0062] A 4-inch, 300μm-thick, single-polished N-type diamond wafer was used as the substrate. A 5μm-thick, low-doped intrinsic epitaxial layer was grown on the N-type diamond substrate using molecular beam epitaxy. Titanium / gold electrodes were deposited on the back of the N-type diamond using magnetron sputtering. A laser scriber then cut the 4-inch wafer into diamond units with an active area of 1cm x 1cm. These units were then stored in a moisture-proof cabinet for later use.

[0063] A few-layer (3-5 layers) copper-based graphene grown by chemical vapor deposition was selected, and a Nafion solution with a mass fraction of 2.5% was spin-coated at a low speed of 300 rpm on the surface of a few-layer copper-based graphene with an area of 5 mm × 5 mm. The graphene was placed in a FeCl3 solution and the copper substrate was etched. The obtained 1 μm perfluorosulfonic acid composite graphene layer was washed several times in deionized water and transferred to the surface of a cut diamond basic unit and led out as an upper electrode to obtain a perfluorosulfonic acid composite graphene / diamond transducer device. 90 Sr radioactive source 90 SrTiO3 is loaded onto the surface of the perfluorosulfonic acid composite graphene / diamond transducer device to complete the preparation of the graphene / diamond isotope battery using perfluorosulfonic acid polymer.

[0064] Different from the above, as a comparative example, PMMA was spin-coated on a 5mm×5mm surface of a few-layer copper-based graphene, which was then placed in a FeCl3 solution and etched to completion. The PMMA / graphene was then washed several times in deionized water and transferred to the surface of a cut diamond unit. The unit was then immersed in a hot acetone solution to remove the PMMA covering the surface, thereby obtaining a graphene / diamond transducer device. 90 Sr radioactive source 90SrTiO3 is loaded onto the surface of the perfluorosulfonic acid composite graphene / diamond transducer device, thereby completing the preparation of the graphene / diamond isotope battery without using perfluorosulfonic acid polymer.

[0065] The Keithley4200-SCS parameter analyzer produced by Keithley was used to analyze the 90 The output performance of graphene / diamond isotope batteries using perfluorosulfonic acid polymer and graphene / diamond isotope batteries without perfluorosulfonic acid polymer as Sr source was tested. The results showed that the open circuit voltage of graphene / diamond isotope battery using perfluorosulfonic acid polymer was 1.8V and the short circuit current was 1.5μA / cm 2 ; The graphene / diamond isotope battery without perfluorosulfonic acid polymer has an open circuit voltage of 0.8V and a short circuit current of 0.78μA / cm 2 This shows that the use of perfluorosulfonic acid polymer layer can effectively improve the output performance of graphene-based isotope batteries.

[0066] Example 6

[0067] This embodiment is based on 147 A Pm radioactive source is provided, providing a graphene / silicon isotope battery that uses perfluorosulfonic acid polymer to improve performance, and the specific preparation method thereof is as follows:

[0068] A 30μm-thick, low-doped intrinsic epitaxial layer was grown on a 4-inch, 300μm-thick N-type monocrystalline silicon wafer using molecular beam epitaxy. A metal aluminum electrode was deposited on the back of the N-type silicon wafer using magnetron sputtering. The 4-inch wafer was then cut into 1cm×1cm silicon units using a dicing machine and stored in a moisture-proof cabinet for later use.

[0069] A few-layer (3-5 layers) copper-based graphene grown by chemical vapor deposition was selected, and a 2.5% mass fraction of Nafion solution was spin-coated at a low speed of 300 rpm on the surface of a few-layer copper-based graphene with an area of 5 mm × 5 mm. The graphene was placed in a FeCl3 solution and the copper substrate was etched. The obtained 1 μm perfluorosulfonic acid composite graphene layer was washed several times in deionized water and transferred to the surface of the cut silicon basic unit and led out as the upper electrode to obtain a perfluorosulfonic acid composite graphene / silicon transducer device. 147 Pm radioactive source 147 The PmCl3 is loaded onto the surface of the perfluorosulfonic acid composite graphene / silicon transducer device to complete the preparation of the graphene / silicon isotope battery using perfluorosulfonic acid polymer.

[0070] Different from the above, as a comparative example, PMMA was spin-coated on a 5mm×5mm surface of a few-layer copper-based graphene, placed in a FeCl3 solution until the copper substrate was etched, and the PMMA / graphene was washed several times in deionized water and transferred to the surface of the cut silicon basic unit, and then soaked in a hot acetone solution to remove the PMMA covering the surface, thereby obtaining a graphene / silicon transducer device. 147 Pm radioactive source 147 The PmCl3 is loaded onto the surface of the perfluorosulfonic acid composite graphene / silicon transducer device, thereby completing the preparation of the graphene / silicon isotope battery without using perfluorosulfonic acid polymer.

[0071] The Keithley4200-SCS parameter analyzer produced by Keithley was used to analyze the 147 The output performance of graphene / silicon isotope batteries using perfluorosulfonic acid polymer and graphene / silicon isotope batteries without perfluorosulfonic acid polymer was tested. The results showed that the open circuit voltage of the graphene / silicon isotope battery using perfluorosulfonic acid polymer was 0.35V and the short circuit current was 0.8μA / cm 2 ; The graphene / silicon isotope battery without perfluorosulfonic acid polymer has an open circuit voltage of 0.15V and a short circuit current of 0.3μA / cm 2 This shows that the use of perfluorosulfonic acid polymer layer can effectively improve the output performance of graphene-based isotope batteries.

[0072] While the specific embodiments of the present invention have been described in detail above, these are merely exemplary and the present invention is not limited thereto. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, any equivalent changes and modifications made without departing from the spirit and scope of the present invention are intended to be encompassed within the scope of the present invention.

Claims

1. A graphene-based isotope battery using perfluorosulfonic acid polymer to improve performance, characterized in that: The invention comprises a radioactive source (1), a perfluorosulfonic acid polymer layer (2), a graphene layer (3), an intrinsic semiconductor material layer (4), an N-type semiconductor material layer (5), and a back electrode (6) stacked in sequence from top to bottom; wherein the perfluorosulfonic acid polymer layer (2) serves as an intermediate dielectric layer for graphene transfer and a high-efficiency P-type dopant for graphene, and together with the graphene layer (3) forms a perfluorosulfonic acid composite graphene layer (7).

2. The graphene-based isotope battery with improved performance using perfluorosulfonic acid polymer according to claim 1, characterized in that: The radioactive source (1) is 3 H. 14 C. 32 P. 63 Ni, 90 Sr. 137 Cs, 147 One or more beta-radiating sources of Pm.

3. The graphene-based isotope battery with improved performance using perfluorosulfonic acid polymer according to claim 1, characterized in that: The graphene layer (3) is a single layer or multilayer graphene prepared by chemical vapor deposition, and has a thickness of 0.3 nm to 10 nm.

4. The graphene-based isotope battery with improved performance using perfluorosulfonic acid polymer according to claim 1, characterized in that: The N-type semiconductor material layer (5) is one of Si, GaAs, GaN, and SiC.

5. The graphene-based isotope battery with improved performance using perfluorosulfonic acid polymer according to claim 1, characterized in that: The back electrode (6) is an electrode made of one or a combination of Au, Ag, Ni, Al, Ti, Cu, Ge, In, and Ga.

6. The graphene-based isotope battery with improved performance using perfluorosulfonic acid polymer according to claim 1, characterized in that: The perfluorosulfonic acid composite graphene layer (7) has a thickness of 10 nm to 5 μm and can be directly used as an upper electrode of a graphene-based isotope battery.

7. A method for preparing a graphene-based isotope battery using a perfluorosulfonic acid polymer to improve performance as claimed in any one of claims 1 to 6, characterized in that: The steps include: S1. epitaxially growing an intrinsic semiconductor material layer (4) on the N-type semiconductor material layer (5) by using a molecular beam or plasma chemical vapor deposition method; S2. Based on the sample prepared in step S1, a back electrode (6) is formed on the back side of the N-type semiconductor material layer (5) by scraping or magnetron sputtering; S3, directly coating the perfluorosulfonic acid polymer layer (2) on the surface of the copper-based or nickel-based graphene prepared by chemical vapor deposition, and wet-etching the copper-based or nickel-based material to obtain the perfluorosulfonic acid composite graphene layer (7), which is transferred to the upper surface of the sample prepared in step S2 and led out as the upper electrode; S4. Loading a radioactive source (1) on the surface of the device prepared in step S3 completes the preparation of a graphene-based isotope battery with improved performance using a perfluorosulfonic acid polymer.

8. The method for preparing a graphene-based isotope battery using perfluorosulfonic acid polymer to improve performance according to claim 7, characterized in that: In step S1, the thickness of the N-type semiconductor material layer (5) is 50 μm to 500 μm; The thickness of the epitaxial intrinsic semiconductor material layer (4) is 100 nm to 200 μm.

9. The method for preparing a graphene-based isotope battery using perfluorosulfonic acid polymer to improve performance according to claim 7, characterized in that: In step S3, the perfluorosulfonic acid polymer layer (2) is directly coated on the surface of the copper-based or nickel-based graphene prepared by chemical vapor deposition by drop casting or spin coating.

10. The method for preparing a graphene-based isotope battery using perfluorosulfonic acid polymer to improve performance according to claim 7, characterized in that: In step S4, the radioactive source (1) is loaded onto the surface of the device, including loading of a solid radioactive source and a gaseous radioactive source.

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