Nanowire gap structure-based micro-nano battery, preparation method and application

Abstract

The invention discloses a micro-nano battery based on a nanowire gap structure, which comprises a substrate, a positive electrode and a negative electrode are grown on the surface of the substrate in situ, liquid or solid electrolyte is arranged at the opposite end parts of the positive electrode and the negative electrode and in the gap, and metal current collectors are respectively deposited at the outer end parts of the positive electrode and the negative electrode. The nanowire electrode is positioned through the in-situ growth technology, precise electrode spacing control from the nanometer scale to the micrometer scale is achieved, the battery size is remarkably reduced, and the method is suitable for integrated application of micro-nano electronic device functions and large-scale high-density micro batteries.

Description

Technical Field

[0001] The present invention relates to the technical field of micro-nano batteries based on nanowire gap structures, and more specifically, to a micro-nano electrode micro-battery based on nanowire gap structures and a preparation method, as well as the integration of micro-battery arrays. The invention can be widely used in semiconductor micro-nano electronic devices, especially in the energy supply of micro-nano electronic devices and wearable electronics. Background Art

[0002] As a key component for energy conversion and storage, batteries play a vital role in the stable operation of portable electronic devices, electric vehicles, and renewable energy systems. As the global demand for sustainable energy solutions grows, the development of high-performance, low-cost, and environmentally friendly battery technology has become a top priority. However, traditional battery systems face many challenges in terms of energy density, charging rate, and cycle life, which limits their widespread use in demanding application scenarios.

[0003] Recently, microbattery technology has gradually become a research hotspot in the battery field due to its compact design and high performance, providing new ideas for solving the above challenges. The main advantages of microbatteries are reflected in the following aspects: by adopting advanced nanomaterials and manufacturing processes, microbatteries can provide high energy density while maintaining a small volume, which is conducive to the miniaturization and lightweight of equipment; microbatteries have a compact structure and are easy to integrate with other components, making it easy to build a multifunctional integrated intelligent system; compared with block batteries, microbatteries are more suitable for miniaturized and flexible application scenarios.

[0004] At present, there is a lot of research on microbatteries. The construction of nanowire electrodes is a key research direction in this field. Nanowires, with their unique structure of high aspect ratio, not only optimize the interface contact between electrodes and electrolytes in microbatteries, but also promote the transmission path of electrons and ions. (Chem. Rev. 114, 11828–11862 (2014); Adv.Funct. Mater. 2412548 (2024); J. Power Sources 205, 433-438 (2012)) The high crystallinity of this structure helps to alleviate the problem of volume expansion and give the material better mechanical stability, thereby effectively avoiding the powdering phenomenon that may occur during the lithiation and delithiation process, and significantly improving the stability of the interface. (Nat. Nanotechnol. 3, 31-35 (2008); J. Am. Chem. Soc. 133, 20914-20921 (2011); Chem. Rev. 119, 11042–11109 (2019)).

[0005] However, according to the inventors, the main challenges faced by current nanowire electrode technology in microbattery applications are: 1) The distance between nanowire electrodes is usually on the order of tens of microns, which is still large compared to the scale of the nanowires themselves, resulting in a larger overall battery size and insufficient integration density.

[0006] Traditional chemical synthesis methods make it difficult to precisely control the length and radius of nanowires when used to prepare them, which requires additional steps for the selection and transfer of nanowires, increasing preparation costs and reducing efficiency, which is not conducive to large-scale industrial production.

[0007] Traditional preparation techniques cannot achieve customized design of nanowire morphology, which limits the design flexibility of nanowire electrodes and their potential for wide application in microbatteries.

[0008] Therefore, there is an urgent need to develop a nanowire electrode microbattery with small electrode spacing and precise positioning to facilitate high-density large-scale integration. Summary of the invention

[0009] Purpose of the invention: In view of the problems and shortcomings in the prior art, the present invention proposes a nanowire electrode with small spacing and precise positioning growth, and a nanowire electrode microbattery that can be integrated on a large scale with high density, aiming to provide an efficient energy supply solution for micro-nano electronic devices and wireless wearable electronic devices.

[0010] The present application provides a micro-nano battery based on a nanowire gap structure, comprising a substrate, characterized in that: positive and negative electrodes with a gap are in-situ grown on the surface of the substrate, liquid or solid electrolytes are provided at the opposite ends and the gaps of the positive and negative electrodes, and metal current collectors are respectively deposited at the outer ends of the positive and negative electrodes.

[0011] The present invention also provides an integrated micro-nano battery based on a nanowire gap structure, comprising a substrate, characterized in that an array of positive and negative electrodes with gaps are in-situ grown on the surface of the substrate, liquid or solid electrolytes are provided at the opposite ends and gaps of each pair of positive and negative electrodes, and metal current collectors are deposited at the outer ends of each pair of positive and negative electrodes, respectively.

[0012] Preferably, the positive and negative electrodes are both micro / nanowires grown in situ, or one electrode is a micro / nanowire grown in situ and the other electrode is a lithium-containing metal electrode formed by in situ deposition.

[0013] Preferably, the micron or nanowire positive and negative electrode materials are heavily doped semiconductor materials.

[0014] Preferably, the heavily doped semiconductor material is a semiconductor material or a heavily doped silicon micro / nanowire, such as a silicon micro / nanowire or a germanium silicon micro / nanowire.

[0015] The present invention provides a method for preparing a micro-nano battery based on a nanowire gap structure, characterized in that it comprises the following steps: A. Use photolithography to define a guide step on the substrate, and then use inductively coupled plasma etching to etch a step structure on the substrate; B. Using photolithography and evaporation sputtering metal deposition processes, a metal or metal alloy catalyst layer is prepared at the end of the step as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the metal or metal alloy catalyst layer covering the guide channel is treated at a temperature higher than the melting point of the metal to transform it into separate nanoparticles; C. Covering the surface of the sample with a precursor by plasma enhanced chemical vapor deposition technology, the metal or metal alloy nanoparticles absorb the precursor to generate positive and negative electrode nanowires with gaps, or generate an independent nanowire electrode, and the residual precursor layer is removed by reactive ion etching process; D. selectively depositing gold electrodes as metal current collectors at both ends of the positive and negative electrode nanowires by photolithography and electron beam evaporation processes. Or, depositing a lithium-containing metal layer as a metal electrode at a position 10 nm to 10 μm away from the independent nanowire electrode, and then depositing gold electrodes as metal current collectors at both ends of the independent nanoelectrode wire and the lithium-containing metal electrode; E. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited at the end where the positive and negative electrodes are close and in the gap, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the micro-nano battery.

[0016] The present invention also discloses a method for preparing a micro-nano battery based on a nanowire gap structure, which is characterized in that the steps include: A. Using photolithography technology to define a curved step on a flexible substrate; then using an inductively coupled plasma etching method to etch a step structure on the flexible substrate; B. Using photolithography and evaporation sputtering metal deposition processes, an InGa alloy catalytic metal layer is prepared at one end of the step, and this end point is used as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the InGa alloy catalytic metal layer is treated at a temperature higher than the melting point of the metal, so that the InGa alloy catalytic metal layer covering the guide channel is transformed into separated InGa alloy metal nanoparticles; C. Covering the surface of the sample with a precursor by plasma enhanced chemical vapor deposition technology, and the metal or metal alloy nanoparticles absorb the precursor to generate a curved nanowire electrode; D. selectively depositing a lithium-containing metal layer as a microbattery metal electrode at a distance of 10 nm to 10 μm from the nanowire electrode by photolithography and electron beam evaporation process; E. Selectively depositing gold electrodes as metal current collectors at both ends of the nanowire electrode and the lithium-containing metal electrode by photolithography and electron beam evaporation processes; F. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited at the opposite ends and gaps of the positive and negative electrodes, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the micro-nano battery.

[0017] The present invention also discloses a method for preparing an integrated micro-nano battery based on a nanowire gap structure, characterized in that: A. Use photolithography to define and guide a number of orthogonal steps on the substrate, and then use inductively coupled plasma etching to etch the step structure on the substrate; the etching channel depth is 50~200 nm; B. Using photolithography and evaporation sputtering metal deposition processes, a metal or metal alloy catalyst layer is prepared at one end or both ends of each orthogonal step as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the metal or metal alloy catalyst layer covering the guide channel is treated at a temperature higher than the melting point of the metal to transform it into separate nanoparticles; C. Covering the sample surface with a precursor by plasma enhanced chemical vapor deposition technology, the metal or metal alloy nanoparticles absorb the precursor to generate a plurality of pairs of nanowire arrays with gaps, that is, the preparation of positive and negative nanowire electrodes with precise positioning is achieved, and the gap control range is 10 nm to 10 um. The residual precursor layer is removed by reactive ion etching process; D. Selectively deposit gold electrodes as metal current collectors at both ends of each pair of positive and negative nanowire electrodes by photolithography and electron beam evaporation process, with a thickness of 30~100 nm; E. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited between the adjacent ends and gaps of each pair of positive and negative electrodes, or liquid electrolyte is dispensed through inkjet printing technology to complete the preparation of the integrated micro-nano battery array; the thickness of the electrolyte is controlled at 100~500 nm to ensure ion conduction and isolate the electron path.

[0018] Preferably, the present invention also provides a method for preparing an integrated micro-nano battery based on a nanowire gap structure, characterized in that the steps include: A. Use photolithography to define and guide several steps on the substrate, and then use inductively coupled plasma etching to etch the step structure on the substrate; the etching channel depth is 50~200 nm; B. Using photolithography and evaporation sputtering metal deposition processes, a metal or metal alloy catalyst layer is prepared at each step end as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the metal or metal alloy catalyst layer covering the guide channel is treated at a temperature higher than the melting point of the metal to transform it into separate nanoparticles; C. Covering the sample surface with a precursor by plasma enhanced chemical vapor deposition technology, the metal or metal alloy nanoparticles absorb the precursor to generate a plurality of pairs of nanowire arrays with gaps, that is, the preparation of positive and negative nanowire electrodes with precise positioning is achieved, and the gap control range is 10 nm~10 um, or a plurality of independent nanowire arrays are generated, and the residual precursor layer is removed by reactive ion etching process; D. Selectively deposit gold electrodes as metal current collectors at both ends of each pair of positive and negative nanowire electrodes by photolithography and electron beam evaporation process, with a thickness of 30~100 nm; Alternatively, a lithium-containing metal layer is deposited at a distance of 10 nm to 10 μm from the independent nanowire electrode as a metal electrode, and then gold electrodes are deposited at both ends of each independent nanoelectrode wire and the lithium-containing metal electrode as metal current collectors; E. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited at the end close to each pair of positive and negative electrodes and in the gap, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the integrated micro-nano battery array; the thickness of the electrolyte is controlled at 100~500 nm to ensure ion conduction and isolate the electron path.

[0019] Preferably, the precursor is an amorphous silicon precursor or an amorphous silicon (a-Si) / amorphous germanium (a-Ge) stacked film precursor.

[0020] Preferably, the electrolyte material is a carbonate electrolyte, a fluorine-containing electrolyte, an aqueous electrolyte, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a polymer solid electrolyte or a glass ceramic electrolyte.

[0021] Preferably, the substrate material is silicon nitride or silicon dioxide or a flexible material, such as polydimethylsiloxane (PDMS).

[0022] The present invention also discloses the application of the above-mentioned micro-nano battery, which is characterized in that: the micro-nano battery is applied to semiconductor micro-nano electronic devices, or is used for energy supply of micro-nano electronic devices and wearable electronics.

[0023] One or more technical solutions provided by this application have at least the following technical effects or advantages: 1. Based on the existing preparation process of nanowire electrode microbatteries, the present invention combines nanowires with high theoretical energy density, etc., and proposes a new nanowire electrode microbattery that can be precisely positioned and a preparation method thereof.

[0024] 2. The present invention positions nanowire electrodes through in-situ growth technology, achieves precise control of electrode spacing from nanometer to micrometer scale, significantly reduces battery size, and is suitable for the integrated application of micro-nano electronic device functions and large-scale high-density micro-batteries.

[0025] 3. Compared with traditional microbatteries, the nanowire electrode microbattery prepared by the present invention achieves a smaller electrolyte area and significantly improves the energy density of the microbattery, making it suitable for applications in long-range wireless scenarios.

[0026] 4. The microbattery prepared by the present invention does not require additional steps for the selection and transfer of nanowires, which reduces the preparation cost and improves the processing efficiency, and is suitable for large-scale industrial production.

[0027] 5. The preparation method of the present invention realizes customized design of nanowire morphology, making the design of nanowire electrodes more flexible and improving their application potential in microbatteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a flow chart for preparing a silicon nanowire electrode microbattery in Example 1 of the present invention.

[0029] Figure 2 This is a front view of the silicon nanowire electrode microbattery device structure in Example 1 of the present invention.

[0030] Figure 3 This is a schematic cross-sectional view of a silicon nanowire electrode microbattery device in Example 1 of the present invention.

[0031] Figure 4 This is a flow chart for preparing a silicon nanowire electrode microbattery in Example 2 of the present invention.

[0032] Figure 5 This is a flow chart of the preparation of the microbattery array in Example 3 of the present invention.

[0033] Figure 6 This is a flow chart for preparing a silicon nanowire electrode microbattery in Example 4 of the present invention.

[0034] Figure 7 This is a flow chart for preparing a silicon nanowire electrode microbattery in Example 5 of the present invention. DETAILED DESCRIPTION

[0035] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods. Example

[0036] This embodiment provides a micro-nano battery based on a nanowire gap structure, such as Figure 2-Figure 3 As shown, it includes a silicon dioxide substrate 1, on which nanowire-like materials with gaps are in-situ grown as a microbattery anode 2 and a microbattery cathode 3, and a microbattery anode metal collector 4 and a microbattery cathode metal collector 5 are deposited at both ends of the microbattery anode 2 and the microbattery cathode 3, respectively, for connecting an external test circuit; a microbattery electrolyte 6 is provided on the microbattery anode 2 and the microbattery cathode 3 and in the gap therebetween.

[0037] This embodiment also provides a method for preparing a silicon nanowire electrode microbattery. Figure 1 As shown, the following steps are included: A. Use photolithography to define the guide step on the silicon dioxide substrate; then use the inductively coupled plasma (ICP) etching method to etch the step structure on the substrate; O2 gas can be used for etching during the etching process, and the ICP power and gas flow rate can be adjusted during the process. The etching channel depth is 50 nm. Figure 1 (a) as shown; B. Using photolithography and evaporation sputtering metal deposition processes, an InGa alloy catalytic metal layer is prepared at one end of two orthogonal steps, and this end point is used as the starting point for the growth of the nanowires; then, under the action of the plasma of reducing gas H2, the InGa alloy catalytic metal layer is treated at a temperature higher than the melting point of the metal, so that the InGa alloy catalytic metal layer covering the guide channel is transformed into separated InGa alloy metal nanoparticles, such as Figure 1 (b) as shown; C. Amorphous silicon is covered on the sample surface by plasma enhanced chemical vapor deposition (PECVD) technology, and two silicon nanowires with a gap are directly grown at 280°C with high theoretical energy density to achieve precise positioning of nanowire electrodes with a gap control range of 10 nm. The residual amorphous silicon layer is removed by reactive ion etching (RIE) process, such as Figure 1 (c) as shown; D. Through photolithography and electron beam evaporation (EBE) process, gold electrodes are selectively deposited at both ends of the positive and negative electrodes as metal current collectors with a thickness of 30 nm; the electrodes have good contact with the silicon nanowires, such as Figure 1 (d) as shown; E. Through atomic layer deposition (ALD) technology, a dense solid electrolyte interface, such as LiPON (lithium phosphorus nitride), is deposited between the positive and negative electrodes and the gap. The thickness is controlled at 100 nm to ensure ion conduction and isolate the electronic path, such as Figure 1 (e) shown.

[0038] The microbattery prepared with nanowire electrodes having morphology programming capability and precise positioning characteristics proposed in the embodiments of the present invention can be integrated on a large scale and has a wide range of applications, providing efficient energy supply for micro-nano electronic devices and flexible electronic devices. Example

[0039] This embodiment provides a method for preparing a silicon nanowire electrode microbattery. Figure 4 As shown, there are the following steps: A. Use photolithography to define two orthogonal steps on a silicon dioxide substrate; then use inductively coupled plasma (ICP) etching to etch a step structure on the substrate; O2 gas can be used for etching during the etching process, and ICP power and gas flow rate can be adjusted during the process. The etching channel depth is 80 nm. Figure 4 (a) as shown; B. Using photolithography and evaporation sputtering metal deposition processes, indium gallium alloy catalytic metal layers are prepared at both ends of two mutually perpendicular steps, and these ends serve as the starting point for the growth of nanowires; then, under the action of reducing gas H2 plasma, the indium gallium alloy catalytic metal layer is treated at a temperature higher than the melting point of the metal, so that the indium gallium alloy catalytic metal layer covering the guide channel is transformed into separated indium gallium alloy metal nanoparticles, such as Figure 4 (b) as shown; C. Amorphous silicon is covered on the sample surface by plasma enhanced chemical vapor deposition (PECVD) technology, and silicon nanowires with gaps and high theoretical energy density are directly grown at 280°C to achieve the preparation of positive and negative electrodes of the nanowires with precise positioning. The gap control range is 30nm, and the residual amorphous silicon layer is removed by reactive ion etching (RIE) process, such as Figure 4 (c) as shown; D. Through photolithography and electron beam evaporation (EBE) process, gold electrodes are selectively deposited at both ends of the positive and negative electrode nanowires as metal current collectors with a thickness of 50 nm; the electrodes have good contact with the silicon nanowires, such as Figure 4 (d) as shown; E. Through atomic layer deposition (ALD) technology, a dense solid electrolyte interface, such as LiPON (lithium phosphorus nitride), is deposited between the opposite ends of the positive and negative electrodes and the gap. The thickness is controlled at 230 nm to ensure ion conduction and isolate the electronic path, such as Figure 4 (e) shown. Example

[0040] This embodiment provides a method for preparing a germanium-silicon nanowire electrode microbattery array, such as Figure 5 As shown, the following steps are included: A. Use photolithography to define and guide a number of orthogonal steps on a silicon dioxide substrate; then use inductively coupled plasma (ICP) etching to etch a step structure on the substrate; O2 gas can be used for etching during the etching process, and ICP power and gas flow rate can be adjusted during the process. The etching channel depth is 110 nm. Figure 5 (a) as shown; B. Using photolithography and evaporation sputtering metal deposition processes, an InGa alloy catalytic metal layer is prepared at one end of a number of orthogonal steps, and this end point is used as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the InGa alloy catalytic metal layer is treated at a temperature higher than the melting point of the metal, so that the InGa alloy catalytic metal layer covering the guide channel is transformed into separated InGa alloy metal nanoparticles, such as Figure 5 (b) as shown; C. The surface of the sample is covered with germanium-doped amorphous silicon by plasma-enhanced chemical vapor deposition (PECVD) technology, and germanium-silicon nanowires with gaps and high theoretical energy density are directly grown at 280°C to achieve the preparation of the positive and negative electrodes of the nanowires with precise positioning. The gap control range is 8nm, and the residual germanium-doped amorphous silicon layer is removed by reactive ion etching (RIE) process, such as Figure 5 (c) as shown; D. Through photolithography and electron beam evaporation (EBE) process, gold electrodes are selectively deposited at both ends of the positive and negative electrode nanowires as metal current collectors with a thickness of 80 nm; the electrodes have good contact with the silicon nanowires, such as Figure 5 (d) as shown; E. Through inkjet printing technology, liquid electrolyte, such as LiClO4 (lithium perchlorate), is dripped between the opposite ends of the positive and negative electrodes and the gap to ensure ion conduction and isolate the electronic path, such as Figure 5 (e) shown. Example

[0041] This embodiment provides a method for preparing a silicon nanowire electrode microbattery. Figure 6 As shown, there are the following steps: A. Use photolithography to define two orthogonal steps on a silicon dioxide substrate; then use inductively coupled plasma (ICP) etching to etch a step structure on the substrate; O2 gas can be used for etching during the etching process, and ICP power and gas flow rate can be adjusted during the process. The etching channel depth is 110 nm. Figure 6 (a) as shown; B. Using photolithography and evaporation sputtering metal deposition processes, indium gallium alloy catalytic metal layers are prepared at one end of two mutually perpendicular steps, and this end point is used as the starting point of the growth of the nanowire; then, under the action of reducing gas H2 plasma, the indium gallium alloy catalytic metal layer is treated at a temperature higher than the melting point of the metal to transform the indium gallium alloy catalytic metal layer covering the guide channel into separated indium gallium alloy metal nanoparticles, such as Figure 6 (b) as shown; C. Amorphous silicon is covered on the sample surface by plasma enhanced chemical vapor deposition (PECVD) technology, and silicon nanowires with gaps and high theoretical energy density are directly grown at 280°C to achieve the preparation of positive and negative electrodes of nanowires with precise positioning. The gap control range is 5um, and the residual amorphous silicon layer is removed by reactive ion etching (RIE) process, such as Figure 6 (c) as shown; D. Through photolithography and electron beam evaporation (EBE) process, gold electrodes are selectively deposited at both ends of the positive and negative electrode nanowires as metal current collectors with a thickness of 100 nm; the electrodes have good contact with the silicon nanowires, such as Figure 6 (d) as shown; E. Through atomic layer deposition (ALD) technology, a dense solid electrolyte interface, such as LiPON (lithium phosphorus nitride), is deposited between the opposite ends of the positive and negative electrodes and the gap. The thickness is controlled at 500 nm to ensure ion conduction and isolate the electronic path, such as Figure 6 (e) shown. Example

[0042] The present embodiment provides a micro-nano battery based on a nanowire gap structure, including a polydimethylsiloxane (PDMS) substrate, on which a serpentine silicon nanowire material is in-situ grown as a micro-battery electrode, a lithium-containing metal layer electrode is deposited at a position 30 nm away from the serpentine silicon nanowire electrode, a solid electrolyte interface is deposited at the opposite ends and gaps of the serpentine silicon nanowire electrode and the lithium-containing metal electrode, and metal current collectors are respectively deposited at the outer ends for connecting an external test circuit.

[0043] This embodiment also provides a method for preparing a flexible silicon nanowire electrode microbattery. Figure 7 As shown, there are the following steps: A. Use photolithography to define a serpentine-shaped step on a polydimethylsiloxane (PDMS) substrate; then use inductively coupled plasma (ICP) etching to etch the step structure on the substrate; O2 gas can be used for etching during the etching process, and ICP power and gas flow rate can be adjusted during the process. The etching channel depth is 110 nm. Figure 7 (a) as shown; B. Using photolithography and evaporation sputtering metal deposition processes, an InGa alloy catalytic metal layer is prepared at one end of the step, and this end point is used as the starting point for the growth of the nanowire; then, under the action of the plasma of reducing gas H2, the InGa alloy catalytic metal layer covering the guide channel is treated at a temperature higher than the melting point of the metal, so that the InGa alloy catalytic metal layer is transformed into separated InGa alloy metal nanoparticles, such as Figure 7 (b) as shown; C. Amorphous silicon is covered on the sample surface by plasma enhanced chemical vapor deposition (PECVD) technology, and silicon nanowires with high theoretical energy density are directly grown at 280°C to achieve the preparation of precisely positioned nanowire electrodes. The residual amorphous silicon layer is removed by reactive ion etching (RIE) process, such as Figure 7 (c) as shown; D. Through photolithography and electron beam evaporation (EBE) process, a lithium metal layer is selectively deposited 3 μm away from the silicon nanowire as the metal electrode of the microbattery with a thickness of 30 nm. Figure 7 (d) as shown; E. Gold electrodes were selectively deposited on the silicon nanowire electrodes and lithium metal electrodes as metal current collectors by photolithography and electron beam evaporation (EBE) process, with a thickness of 50 nm. The electrodes had good contact with the silicon nanowires, such as Figure 7 (e) as shown; F. Through atomic layer deposition (ALD) technology, a dense solid electrolyte interface, such as LiPON (lithium phosphorus nitride), is deposited at the opposite ends and gaps of the silicon nanowire electrode and the lithium metal electrode. The thickness of the solid electrolyte interface is controlled at 400 nm to ensure ion conduction and isolate the electronic path, such as Figure 7 (f) shown.

[0044] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements can be made without departing from the principles of the present invention, such as different shape designs of nanowires, heavily doped materials, selection of hard or flexible substrate materials, and selection of materials for metal electrode deposition, etc. These improvements should also be regarded as the scope of protection of the present invention.

Claims

1. A micro-nano battery based on a nanowire gap structure, comprising a substrate, characterized in that: Positive and negative electrodes with gaps are in-situ grown on the surface of the substrate, liquid or solid electrolytes are provided at the opposite ends and gaps of the positive and negative electrodes, and metal current collectors are deposited at the outer ends of the positive and negative electrodes respectively.

2. An integrated micro-nano battery based on a nanowire gap structure, comprising a substrate, characterized in that: A positive and negative electrode array with gaps is in-situ grown on the substrate surface, liquid or solid electrolytes are provided at the opposite ends and gaps of each pair of positive and negative electrodes, and metal current collectors are deposited at the outer ends of each pair of positive and negative electrodes.

3. The micro-nano battery based on nanowire gap structure according to claim 1, characterized in that: The positive and negative electrodes are both micro / nano wires grown in situ, or one electrode is a micro / nano wire grown in situ and the other electrode is a lithium-containing metal electrode generated by in situ deposition.

4. The micro-nano battery based on the nanowire gap structure according to claim 3, characterized in that: The material of the micro / nano wire is a heavily doped silicon micro / nano wire material or a semiconductor material.

5. A method for preparing a micro-nano battery based on a nanowire gap structure, characterized in that: The steps include: A. Use photolithography to define a guide step on the substrate, and then use inductively coupled plasma etching to etch a step structure on the substrate; B. Using photolithography and evaporation sputtering metal deposition processes, a metal or metal alloy catalyst layer is prepared at the end of the step as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the metal or metal alloy catalyst layer covering the guide channel is treated at a temperature higher than the melting point of the metal to transform it into separate nanoparticles; C. Covering the sample surface with a precursor by plasma enhanced chemical vapor deposition technology. At 200-300°C, metal or metal alloy nanoparticles absorb the precursor to generate positive and negative electrode nanowires with gaps, or generate an independent nanowire electrode. The residual precursor layer is removed by reactive ion etching process. D. selectively depositing gold electrodes as metal current collectors at both ends of the positive and negative electrode nanowires by photolithography and electron beam evaporation processes. Or, depositing a lithium-containing metal layer as a metal electrode at a position 10 nm to 10 μm away from the independent nanowire electrode, and then depositing gold electrodes as metal current collectors at both ends of the independent nanoelectrode wire and the lithium-containing metal electrode; E. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited at the end where the positive and negative electrodes are close and in the gap, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the micro-nano battery.

6. The method for preparing a micro-nano battery based on a nanowire gap structure according to claim 5, characterized in that: The following steps are involved: A. Use photolithography to define two orthogonal steps on the substrate, and then use inductively coupled plasma etching to etch the step structure on the substrate, with the etching channel depth of 50~200nm; B. Using photolithography and evaporation sputtering metal deposition processes, a metal or metal alloy catalyst layer is prepared at one end or both vertical ends of the step as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the metal or metal alloy catalyst layer covering the guide channel is treated at a temperature higher than the melting point of the metal to transform it into separate nanoparticles; C. The surface of the sample is covered with a precursor by plasma enhanced chemical vapor deposition technology. At 200-300°C, the metal or metal alloy nanoparticles absorb the precursor to generate two nanowires with a gap, thereby achieving precise positioning of the positive and negative nanowire electrodes. The gap control range is 10 nm-10 um. The residual precursor layer is removed by reactive ion etching process. D. Selectively deposit gold electrodes as metal current collectors at both ends of the positive and negative nanowire electrodes by photolithography and electron beam evaporation process, with a thickness of 30~100 nm; E. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited at the end where the positive and negative electrodes are close and in the gap, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the micro-nano battery; the thickness of the electrolyte is controlled at 100~500nm to ensure ion conduction and isolate the electron path.

7. The method for preparing a micro-nano battery based on a nanowire gap structure according to claim 5, characterized in that: The following steps are involved: A. Using photolithography technology to define a curved step on a flexible substrate; then using an inductively coupled plasma etching method to etch a step structure on the flexible substrate; B. Using photolithography and evaporation sputtering metal deposition processes, an InGa alloy catalytic metal layer is prepared at one end of the step, and this end point is used as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the InGa alloy catalytic metal layer is treated at a temperature higher than the melting point of the metal, so that the InGa alloy catalytic metal layer covering the guide channel is transformed into separated InGa alloy metal nanoparticles; C. Covering the surface of the sample with a precursor by plasma enhanced chemical vapor deposition technology, at 200-300°C, the metal or metal alloy nanoparticles absorb the precursor to generate a curved nanowire electrode; D. selectively depositing a lithium-containing metal layer as a microbattery metal electrode at a distance of 10 nm to 10 μm from the nanowire electrode by photolithography and electron beam evaporation process; E. Selectively depositing gold electrodes as metal current collectors at both ends of the nanowire electrode and the lithium-containing metal electrode by photolithography and electron beam evaporation processes; F. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited on the opposite ends and gaps of the nanowire electrode and the lithium metal electrode, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the micro-nano battery.

8. A method for preparing an integrated micro-nano battery based on a nanowire gap structure, characterized in that: A. Use photolithography to define and guide several steps on the substrate, and then use inductively coupled plasma etching to etch the step structure on the substrate; the etching channel depth is 50~200 nm; B. Using photolithography and evaporation sputtering metal deposition processes, a metal or metal alloy catalyst layer is prepared at each step end as the starting point for the growth of the nanowire; then, under the action of a plasma of reducing gas H2, the metal or metal alloy catalyst layer covering the guide channel is treated at a temperature higher than the melting point of the metal to transform it into separate nanoparticles; C. Covering the surface of the sample with a precursor by plasma enhanced chemical vapor deposition technology. At 200-300°C, metal or metal alloy nanoparticles absorb the precursor to generate a plurality of pairs of nanowire arrays with gaps, that is, the preparation of positive and negative nanowire electrodes with precise positioning is achieved. The gap control range is 10 nm-10 um, or a plurality of independent nanowire arrays are generated. The residual precursor layer is removed by reactive ion etching process. D. Selectively deposit gold electrodes as metal current collectors at both ends of each pair of positive and negative nanowire electrodes by photolithography and electron beam evaporation process, with a thickness of 30~100 nm; Or, depositing a lithium-containing metal layer electrode at a position 10 nm to 10 μm away from the independent nanowire electrode, and then depositing gold electrodes as metal current collectors at both ends of each independent nanowire electrode and lithium-containing metal electrode; E. Through atomic layer deposition technology, a layer of solid electrolyte interface is deposited at the end close to each pair of positive and negative electrodes and in the gap, or liquid electrolyte is dripped through inkjet printing technology to complete the preparation of the integrated micro-nano battery array; the thickness of the electrolyte is controlled at 100~500 nm to ensure ion conduction and isolate the electron path.

9. The method for preparing a micro-nano battery based on a nanowire gap structure according to any one of claims 5 to 7, characterized in that: The precursor is an amorphous silicon precursor or an amorphous silicon / amorphous germanium stacked film precursor.

10. An application of a micro-nano battery, using the micro-nano battery according to any one of claims 1, 3-8, characterized in that: The micro-nano battery is applied to semiconductor micro-nano electronic devices, or used for energy supply of micro-nano electronic devices and wearable electronics.

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