A micro-nano battery based on nanowire gap structure, preparation method and application

Abstract

The application discloses a micro-nano battery based on a nanowire gap structure, which comprises a substrate, positive and negative electrodes in-situ grown on the surface of the substrate, liquid or solid electrolyte arranged between the opposite ends of the positive and negative electrodes and the gap, and metal current collectors respectively deposited on the outer ends of the positive and negative electrodes. The nanowire electrodes are positioned by the in-situ growth technology, the accurate electrode gap control in the nanometer to micrometer scale is realized, the battery size is significantly reduced, and the micro-nano battery is suitable for micro-nano electronic device function and large-scale high-density micro-battery integrated application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of micro-nano battery based on nanowire gap structure, more particularly, to a micro-nano electrode micro battery based on nanowire gap structure and a preparation method thereof, and integration of micro battery array. It can be widely applied to semiconductor micro-nano electronic devices, especially for the energy supply of micro-nano electronic devices and wearable electronics. BACKGROUND

[0002] Batteries, as key components of energy conversion and storage, play a crucial role in the stable operation of portable electronic devices, electric vehicles, and renewable energy systems. With the growing global demand for sustainable energy solutions, developing high-performance, low-cost, and environmentally friendly battery technologies has become a top priority. However, traditional battery systems face numerous challenges in terms of energy density, charging rate, and cycle life, limiting their widespread application in demanding scenarios.

[0003] Recently, micro-battery 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 micro-batteries are as follows: by adopting advanced nanomaterials and manufacturing processes, micro-batteries can provide higher energy density while maintaining small size, which is beneficial for the miniaturization and lightweight of devices; micro-batteries have compact structures, which are easy to integrate with other components, facilitating the construction of multifunctional integrated intelligent systems; compared with bulk batteries, micro-batteries are more suitable for miniaturized and flexible application scenarios.

[0004] Currently, there are many studies on micro-batteries. The construction of nanowire electrodes is a key research direction in this field. Nanowires, with their unique high aspect ratio structure, not only optimize the interface contact between electrodes and electrolytes in micro-batteries, 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 characteristics of this structure help to alleviate the problem of volume expansion and give the material better mechanical stability, effectively avoiding the possibility of pulverization during lithiation and delithiation, 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 of the current nanowire electrode technology in microbattery applications are mainly:

[0006] 1) The distance between nanowire electrodes is usually in the order of tens of microns, which is still large compared to the size of the nanowire itself, resulting in a large overall size of the battery and insufficient integration density.

[0007] Traditional chemical synthesis methods are difficult to accurately control the length and radius of nanowires when used to prepare nanowires, which requires additional steps for nanowire selection and transfer, increasing the preparation cost and reducing the efficiency, which is not conducive to large-scale industrial production.

[0008] Traditional preparation techniques cannot achieve customized design of nanowire morphology, limiting the design flexibility of nanowire electrodes and their potential for wide application in microbatteries.

[0009] Therefore, it is urgent to develop a nanowire electrode microbattery with small electrode spacing and precise positioning for high-density large-scale integration. SUMMARY

[0010] The present application provides a nanowire electrode with small spacing and precise positioning, and a nanowire electrode microbattery with high-density large-scale integration, aiming to provide an efficient energy supply solution for micro / nano electronic devices and wireless wearable electronic devices.

[0011] The present application provides a micro / nano battery based on a nanowire gap structure, comprising a substrate, characterized in that: the substrate surface is in-situ grown with positive and negative electrodes with gaps, the opposite ends and gaps of the positive and negative electrodes are provided with liquid or solid electrolyte, and the outer ends of the positive and negative electrodes are respectively deposited with metal current collectors.

[0012] The present application also provides an integrated micro / nano battery based on a nanowire gap structure, comprising a substrate, characterized in that: the substrate surface is in-situ grown with an array of positive and negative electrodes with gaps, the opposite ends and gaps of each pair of positive and negative electrodes are provided with liquid or solid electrolyte, and the outer ends of each pair of positive and negative electrodes are respectively deposited with metal current collectors.

[0013] As a preferred embodiment, the positive and negative electrodes are both in-situ grown micro / nanowires, or one electrode is in-situ grown micro / nanowire and the other electrode is in-situ deposited lithium-containing metal electrode.

[0014] As a preferred embodiment, the micro or nanowire positive and negative electrode materials are heavily doped semiconductor materials.

[0015] As a preferred embodiment, 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.

[0016] The application provides a preparation method of a micro-nano battery based on a nanowire gap structure.

[0017] A. Defining a guide step on a substrate by using a photolithography technology, and etching the step structure on the substrate by using an inductively coupled plasma etching method;

[0018] B. Preparing a metal or metal alloy catalytic layer at the end of the step by using a photolithography technology and an evaporation sputtering metal deposition technology, so as to serve as a growth starting point position of the nanowire; then, under the plasma action of a reducing gas H2, processing is performed at a temperature higher than the melting point of the metal, so that the metal or metal alloy catalytic layer covering the guide channel is changed into separated nanometer particles;

[0019] C. Covering a precursor on the sample surface by using a plasma enhanced chemical vapor deposition technology, and absorbing the precursor by the metal or metal alloy nanometer particles to generate positive and negative electrode nanowires with a gap or to generate an independent nanowire electrode, and the residual precursor layer is removed by a reactive ion etching technology;

[0020] D. Selectively depositing a gold electrode as a metal current collector at the two ends of the positive and negative electrode nanowires by using a photolithography and electron beam evaporation technology,

[0021] 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 a gold electrode as a metal current collector at the two ends of the independent nanowire electrode and the lithium-containing metal electrode;

[0022] E. Depositing a layer of solid electrolyte interface at the end where the positive and negative electrodes are close to each other and in the gap by using an atomic layer deposition technology, or performing drop dispensing of a liquid electrolyte by using an inkjet printing technology, so as to complete the preparation of the micro-nano battery.

[0023] The application further discloses a preparation method of a micro-nano battery based on a nanowire gap structure.

[0024] A. Defining a curved step on a flexible substrate by using a photolithography technology, and etching the step structure on the flexible substrate by using an inductively coupled plasma etching method;

[0025] B. Preparing an indium-gallium alloy catalytic metal layer at one end of the step by using a photolithography technology and an evaporation sputtering metal deposition technology, so as to serve as a growth starting point position of the nanowire; then, under the plasma action of a reducing gas H2, processing is performed 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 changed into separated indium-gallium alloy metal nanometer particles;

[0026] 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 curved nanowire electrodes;

[0027] D. Depositing a lithium-containing metal layer as a micro-battery metal electrode by photolithography and electron beam evaporation process at a distance of 10 nm to 10 um from the nanowire electrode;

[0028] E. Depositing gold electrodes as metal current collectors by photolithography and electron beam evaporation process at both ends of the nanowire electrode and the lithium-containing metal electrode;

[0029] F. Depositing a layer of solid electrolyte interface at the opposite ends and gaps of the positive and negative electrodes by atomic layer deposition technology or dispensing liquid electrolyte by inkjet printing technology, i.e. completing the preparation of micro-nano battery.

[0030] The application also discloses a preparation method of an integrated micro-nano battery based on a nanowire gap structure, characterized in that,

[0031] A. Defining guide several orthogonal steps on the substrate by photolithography technology, and then etching the step structure on the substrate by inductively coupled plasma etching method; the etching channel depth is 50-200 nm;

[0032] B. Preparing a metal or metal alloy catalytic layer at one end or both ends of each orthogonal step as the growth starting position of nanowires by photolithography process and evaporation and sputtering metal deposition process; then treating at a temperature higher than the melting point of the metal under the plasma action of reducing gas H2, so that the metal or metal alloy catalytic layer covering the guide channel is converted into separate nanoparticles;

[0033] 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 several pairs of nanowire arrays with gaps, i.e. to realize the preparation of precisely positioned positive and negative nanowire electrodes, the gap control range is 10 nm to 10 um, and the residual precursor layer is removed by reactive ion etching process;

[0034] D. Depositing gold electrodes as metal current collectors by photolithography and electron beam evaporation process at both ends of each pair of positive and negative nanowire electrodes, the thickness is 30-100 nm;

[0035] E. Depositing a layer of solid electrolyte interface between the end of each pair of positive and negative electrodes and the gap or dispensing liquid electrolyte by inkjet printing technology, i.e. completing the preparation of the integrated micro-nano battery array; the thickness of the electrolyte is controlled to be 100-500 nm to ensure ion conduction and isolate the electron path.

[0036] As a preferred embodiment, the application further provides a preparation method of an integrated micro-nano battery based on a nanowire gap structure, characterized in that the steps include:

[0037] A. Defining guide grooves on the substrate by using photolithography technology, and etching the grooves on the substrate by using inductively coupled plasma etching method; the etching depth of the grooves is 50-200 nm;

[0038] B. Preparing a metal or metal alloy catalytic layer at the end of each groove by using photolithography process and evaporation sputtering metal deposition process, which serves as the growth starting position of the nanowire; then, under the plasma action of reducing gas H2, the metal or metal alloy catalytic layer covering the guide grooves is converted into separated nanoparticles at a temperature higher than the melting point of the metal;

[0039] C. Covering the sample surface with a precursor by using plasma-enhanced chemical vapor deposition technology, and the metal or metal alloy nanoparticles absorb the precursor to generate a plurality of pairs of nanowire arrays with gaps, i.e. to realize the preparation of precisely positioned positive and negative nanowire electrodes, and the gap is controlled to be 10 nm-10 um, or to generate a plurality of independent nanowire arrays, and the residual precursor layer is removed by reactive ion etching process;

[0040] D. Selectively depositing a gold electrode as a metal current collector at the two ends of each pair of positive and negative nanowire electrodes by using photolithography and electron beam evaporation process, and the thickness is 30-100 nm;

[0041] Or, depositing a lithium-containing metal layer as a metal electrode at a distance of 10 nm-10 um from the independent nanowire electrode, and then depositing a gold electrode as a metal current collector at the two ends of each independent nanowire electrode and the lithium-containing metal electrode;

[0042] E. Depositing a layer of solid electrolyte interface between the end of each pair of positive and negative electrodes and the gap or dispensing liquid electrolyte by inkjet printing technology, i.e. completing the preparation of the integrated micro-nano battery array; the thickness of the electrolyte is controlled to be 100-500 nm to ensure ion conduction and isolate the electron path.

[0043] As a preferred embodiment, the precursor is an amorphous silicon precursor or an amorphous silicon (a-Si) / amorphous germanium (a-Ge) stacked film precursor.

[0044] As preferred, the electrolyte material is a carbonate electrolyte, a fluorine-containing electrolyte, an aqueous electrolyte, a sulfide-based solid-state electrolyte, an oxide-based solid-state electrolyte, a polymer solid-state electrolyte, or a glass-ceramic electrolyte.

[0045] As preferred, the substrate material is silicon nitride or silicon dioxide or a flexible material such as polydimethylsiloxane (PDMS).

[0046] The application also discloses the application of the micro-nano battery, and has the characteristics that the micro-nano battery is applied to a semiconductor micro-nano electronic device or used for energy supply of a micro-nano electronic device and a wearable electronic device.

[0047] The one or more technical solutions provided in the application have at least the following technical effects or advantages:

[0048] 1. The application is based on the preparation process of the existing nanowire electrode micro-battery, and combines nanowires with high theoretical energy density to propose a novel nanowire electrode micro-battery which can be precisely positioned and a preparation method thereof.

[0049] 2. The application positions the nanowire electrode through an in-situ growth technology, realizes accurate electrode spacing control in the nanometer to micrometer scale, significantly reduces the size of the battery, and is suitable for the integration application of micro-nano electronic device functions and large-scale high-density micro-batteries.

[0050] 3. The nanowire electrode micro-battery prepared by the application realizes a smaller electrolyte area compared with the traditional micro-battery, significantly improves the energy density of the micro-battery, and is suitable for the application in a remote wireless scene.

[0051] 4. The micro-battery prepared by the application does not need additional steps for nanowire selection and transfer, reduces the preparation cost and improves the processing efficiency, and is suitable for large-scale industrial production.

[0052] 5. The preparation method of the application realizes the customized design of the nanowire form, makes the design of the nanowire electrode more flexible, and improves the application potential of the nanowire electrode in the micro-battery. BRIEF DESCRIPTION OF DRAWINGS

[0053] Figure 1 The figure is a preparation flowchart of the silicon nanowire electrode micro-battery in Embodiment 1 of the application.

[0054] Figure 2 The figure is a main view of the structure of the silicon nanowire electrode micro-battery device in Embodiment 1 of the application.

[0055] Figure 3 The figure is a cross-sectional view of the silicon nanowire electrode micro-battery device in Embodiment 1 of the application.

[0056] Figure 4This is a flowchart illustrating the fabrication process of the silicon nanowire electrode microcell in Example 2 of the present invention.

[0057] Figure 5 This is a flowchart illustrating the fabrication process of the micro-battery array in Embodiment 3 of the present invention.

[0058] Figure 6 This is a flowchart illustrating the fabrication process of the silicon nanowire electrode microcell in Example 4 of the present invention.

[0059] Figure 7 This is a flowchart illustrating the fabrication process of the silicon nanowire electrode microcell in Example 5 of the present invention. Detailed Implementation

[0060] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific implementation methods. Example

[0061] This embodiment provides a micro / nano battery based on a nanowire gap structure, such as Figures 2-3 As shown, the device includes a silicon dioxide substrate 1, on which nanowire materials with gaps are grown in situ as micro battery anode 2 and micro battery cathode 3. Micro battery anode metal current collector 4 and micro battery cathode metal current collector 5 are deposited at both ends of micro battery anode 2 and micro battery cathode 3, respectively, for connecting external test circuits. Micro battery electrolyte 6 is provided on micro battery anode 2 and micro battery cathode 3 and in the gaps between them.

[0062] This embodiment also provides a method for fabricating silicon nanowire electrode microcells, such as... Figure 1 As shown, it includes the following steps:

[0063] A. Guide steps are defined on a silicon dioxide substrate using photolithography; then, the step structure is etched onto the substrate using inductively coupled plasma (ICP) etching. O2 gas can be used for etching, and factors such as ICP power and gas flow rate can be adjusted during the process. The etching channel depth is 50 nm. Figure 1 As shown in (a);

[0064] B. Using photolithography and evaporation sputtering metal deposition processes, an indium gallium alloy catalytic metal layer is prepared at one end of two orthogonal steps. This endpoint serves as the growth starting point for the nanowires. Subsequently, under the influence of a reducing gas H2 plasma, the nanowires are treated at a temperature higher than the metal's melting point, transforming the indium gallium alloy catalytic metal layer covering the guiding channel into separated indium gallium alloy metal nanoparticles, such as... Figure 1 As shown in (b);

[0065] C. Amorphous silicon is covered on the surface of the sample by plasma enhanced chemical vapor deposition (PECVD) technology, and two silicon nanowires with high theoretical energy density gaps are directly grown at 280℃, to realize precise positioning of the nanowire electrode, and the gap control range is 10 nm. The residual amorphous silicon layer is removed by reactive ion etching (RIE) process, as shown in Figure 1 (c) shown;

[0066] D. Gold electrodes are selectively deposited as metal current collectors at both ends of the positive and negative electrodes by photolithography and electron beam evaporation (EBE) process, with a thickness of 30 nm; the electrode is in good contact with the silicon nanowire, as shown in Figure 1 (d) shown;

[0067] E. A dense solid electrolyte interface such as LiPON (lithium phosphorus oxynitride) is deposited between the positive and negative electrodes and the gap by atomic layer deposition (ALD) technology, with a thickness of 100 nm, to ensure ion conduction and isolate the electron path, as shown in Figure 1 (e) shown.

[0068] The micro-battery prepared by the nanowire electrode with the shape programming capability and precise positioning characteristics provided by the embodiment of the application can be mass-integrated, has a wide application range, and provides high-efficiency power supply for micro-nano electronic devices and flexible electronic devices. Embodiment

[0069] The embodiment provides a preparation method of a silicon nanowire electrode micro-battery, as shown in Figure 4 , and the specific steps are as follows:

[0070] A. Photolithography technology is used to define two orthogonal guide steps on a silicon dioxide substrate; then an inductively coupled plasma (ICP) etching method is used to etch the step structure on the substrate; O2 gas can be used for etching during the etching process, and factors such as ICP power and gas flow can be adjusted during the process, and the etching channel depth is 80 nm, as shown in Figure 4 (a) shown;

[0071] B. Indium-gallium alloy catalytic metal layers are prepared at both ends of the two perpendicular steps by using photolithography and evaporation and sputtering metal deposition processes, and the end point is used as the growth starting position of the nanowire; then, under the plasma action of reducing gas H2, the indium-gallium alloy catalytic metal layer covering the guide channel is converted into separated indium-gallium alloy metal nanoparticles at a temperature higher than the melting point of the metal, as shown in Figure 4 (b) shown;

[0072] C. Amorphous silicon is covered on the surface of the sample by plasma enhanced chemical vapor deposition (PECVD) technology, and high-theoretical energy density gap silicon nanowires are directly grown at 280°C to realize the preparation of precisely positioned nanowire positive and negative electrodes, with a gap control range of 30 nm. The residual amorphous silicon layer is removed by a reactive ion etching (RIE) process, as shown in Figure 4 (c);

[0073] D. Gold electrodes are selectively deposited as metal current collectors on both ends of the positive and negative nanowires by photolithography and electron beam evaporation (EBE) processes, with a thickness of 50 nm. The electrodes are in good contact with the silicon nanowires, as shown in Figure 4 (d);

[0074] E. A dense solid electrolyte interface such as LiPON (lithium phosphorus oxynitride) is deposited on the opposite ends of the positive and negative electrodes and between the gaps by atomic layer deposition (ALD) technology, with a thickness controlled at 230 nm to ensure ion conduction and isolate the electron path, as shown in Figure 4 (e). Embodiment

[0075] The preparation method of a germanium-silicon nanowire electrode micro-battery array provided by the embodiment is shown in Figure 5 , and includes the following steps:

[0076] A. Photolithography technology is used to define a guide for several orthogonal steps on a silicon dioxide substrate. Inductively coupled plasma (ICP) etching method is used to etch the step structure on the substrate. O2 gas can be used for etching during the etching process, and factors such as ICP power and gas flow can be adjusted. The etching channel depth is 110 nm, as shown in Figure 5 (a);

[0077] B. Indium-gallium alloy catalytic metal layers are prepared at one end of the several orthogonal steps by photolithography process and evaporation and sputtering metal deposition process. This end point serves as the growth starting position of the nanowires. Then, under the plasma action of reducing gas H2, the indium-gallium alloy catalytic metal layer covering the guide channel is converted into separated indium-gallium alloy metal nanoparticles at a temperature higher than the melting point of the metal, as shown in Figure 5 (b);

[0078] C. Germanium-doped amorphous silicon is covered on the surface of the sample by plasma enhanced chemical vapor deposition (PECVD) technology, and high-theoretical energy density gap germanium-silicon nanowires are directly grown at 280°C to realize the preparation of precisely positioned nanowire positive and negative electrodes, with a gap control range of 8 nm. The residual germanium-doped amorphous silicon layer is removed by a reactive ion etching (RIE) process, as shown in Figure 5 (c);

[0079] D. Gold electrodes are selectively deposited on both ends of the positive and negative nanowires as metal current collectors by photolithography and electron beam evaporation (EBE) process, with a thickness of 80 nm; the electrodes are in good contact with the silicon nanowires, as shown in Figure 5 (d);

[0080] E. Liquid electrolyte such as LiClO4 (lithium perchlorate) is drop-casted between the opposite ends of the positive and negative electrodes and the gap to ensure ion conduction and isolate the electron path, as shown in Figure 5 (e). Embodiment

[0081] The embodiment provides a preparation method of a silicon nanowire electrode micro-battery, as shown in Figure 6 , and specifically includes the following steps:

[0082] A. Photolithography is used to define guide two orthogonal steps on a silicon dioxide substrate; then an inductively coupled plasma (ICP) etching method is used to etch the step structure on the substrate; during the etching process, O2 gas can be used for etching, and factors such as ICP power and gas flow can be adjusted during the process; the etching channel depth is 110 nm, as shown in Figure 6 (a);

[0083] B. Photolithography and evaporation and sputtering metal deposition processes are used to prepare an indium-gallium alloy catalytic metal layer at one end of the two mutually perpendicular steps, and the end point is used as the growth starting position of the nanowires; then, under the plasma action of a reducing gas H2, the indium-gallium alloy catalytic metal layer covering the guide channel is converted into separated indium-gallium alloy metal nanoparticles at a temperature higher than the melting point of the metal, as shown in Figure 6 (b);

[0084] C. Amorphous silicon is covered on the sample surface by a plasma enhanced chemical vapor deposition (PECVD) technology, and high-theoretical-energy-density gap-presenting silicon nanowires are directly grown at 280°C to realize the preparation of precisely positioned positive and negative electrodes of the nanowires, with a gap control range of 5 um; the residual amorphous silicon layer is removed by a reactive ion etching (RIE) process, as shown in Figure 6 (c);

[0085] D. Gold electrodes are selectively deposited on both ends of the positive and negative nanowires as metal current collectors by photolithography and electron beam evaporation (EBE) process, with a thickness of 100 nm; the electrodes are in good contact with the silicon nanowires, as shown in Figure 6 (d);

[0086] E. A dense solid electrolyte interface, such as LiPON (lithium phosphorous oxynitride), is deposited at the opposite ends and the gap between the positive and negative electrodes by atomic layer deposition (ALD) technology, with a thickness of 500 nm to ensure ion conduction and isolate the electron path, such as Figure 6 (e) shown. Embodiment

[0087] The embodiment provides a micro-nano battery based on a nanowire gap structure, which comprises a polydimethylsiloxane (PDMS) substrate, a serpentine-shaped silicon nanowire material is grown in situ on the methylsiloxane substrate as a micro-battery electrode, a lithium-containing metal layer electrode is deposited at a position 30 nm away from the serpentine-shaped silicon nanowire electrode, a solid electrolyte interface is deposited at the opposite ends and the gap between the serpentine-shaped silicon nanowire electrode and the lithium-containing metal electrode, and a metal current collector is deposited at the outer end for connecting an external test circuit.

[0088] The embodiment also provides a preparation method of a flexible silicon nanowire electrode micro-battery, as shown in Figure 7 The embodiment also provides a preparation method of a flexible silicon nanowire electrode micro-battery, as shown in

[0089] A. A serpentine-shaped step is defined on a polydimethylsiloxane (PDMS) substrate by using a photolithography technology; then, an inductively coupled plasma (ICP) etching method is used to etch the step structure on the substrate; during the etching process, O2 gas can be used for etching, and factors such as ICP power and gas flow can be adjusted during the process, and the etching channel depth is 110 nm, as shown in Figure 7 (a) shown;

[0090] B. An indium-gallium alloy catalytic metal layer is prepared at one end of the step by using a photolithography process and an evaporation sputtering metal deposition process, and the end point serves as a growth starting position of the nanowire; then, under the plasma action of a reducing gas H2, the indium-gallium alloy catalytic metal layer covering the guide channel is converted into separated indium-gallium alloy metal nanoparticles at a temperature higher than the melting point of the metal, as shown in Figure 7 (b) shown;

[0091] C. Amorphous silicon is covered on the surface of the sample by using a plasma enhanced chemical vapor deposition (PECVD) technology, and high-theoretical-energy-density silicon nanowires are directly grown at 280 DEG C to realize preparation of precisely positioned nanowire electrodes, and a residual amorphous silicon layer is removed by a reactive ion etching (RIE) process, as shown in Figure 7 (c) shown;

[0092] D. Lithium metal layers are selectively deposited as micro-battery metal electrodes at a distance of 3 microns from the silicon nanowires by using a photolithography and electron beam evaporation (EBE) process, and the thickness is 30 nm, as shown in Figure 7 (d) shown;

[0093] E. Gold electrodes as metal current collectors with thickness of 50 nm are selectively deposited on the silicon nanowire electrodes and lithium metal electrodes by lithography, electron beam evaporation (EBE) process. The electrodes are in good contact with the silicon nanowires, as shown in Figure 7 (e).

[0094] F. A dense solid electrolyte interface such as LiPON (lithium phosphorous oxynitride) is deposited on the opposite ends and gaps of the silicon nanowire electrodes and lithium metal electrodes by atomic layer deposition (ALD) technique. The thickness is controlled at 400 nm to ensure ion conduction and isolate the electron path, as shown in Figure 7 (f).

[0095] The above only describes the preferred embodiments of the present application. It should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements can be made, such as different shape design of nanowires, heavy doping materials, selection of hard or flexible substrate materials, and selection of metal electrode deposition materials, etc. These improvements should also be considered as the protection scope of the present application.

Claims

1. A method for fabricating a micro-nano battery based on a nanowire gap structure, characterized in that, Comprising the following steps: A. Defining a guide step on the substrate using photolithography technology, and then etching a step structure on the substrate using inductively coupled plasma etching method; B. Preparing a metal or metal alloy catalytic layer at the end of the step as the growth starting position of the nanowire using photolithography process and evaporation sputtering metal deposition process; then treating at a temperature higher than the melting point of the metal under the plasma action of reducing gas H2, so that the metal or metal alloy catalytic layer covering the guide channel is converted into separate nanoparticles; C. Covering the sample surface with a precursor by plasma enhanced chemical vapor deposition technology, and at 200-300℃, 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 a gold electrode as a metal current collector at both ends of the positive and negative electrode nanowires by photolithography and electron beam evaporation process, Or, depositing a lithium-containing metal layer as a metal electrode at a position 10 nm-10 μm away from the independent nanowire electrode, and then depositing a gold electrode as a metal current collector at both ends of the independent nanowire electrode and the lithium-containing metal electrode; E. Depositing a layer of solid electrolyte interface at the end where the positive and negative electrodes are close to each other and in the gap by atomic layer deposition technology, or performing drop dispensing of liquid electrolyte by inkjet printing technology, i.e. completing the preparation of the micro-nano battery.

2. A method for fabricating a micro-nano battery based on a nanowire gap structure, characterized in that, Comprising the following steps: A. Defining two orthogonal guide steps on the substrate using photolithography technology, and then etching a step structure on the substrate using inductively coupled plasma etching method, and the etching channel depth is 50-200 nm; B. Preparing a metal or metal alloy catalytic layer at one end or both ends of the step as the growth starting position of the nanowire using photolithography process and evaporation sputtering metal deposition process; then treating at a temperature higher than the melting point of the metal under the plasma action of reducing gas H2, so that the metal or metal alloy catalytic layer covering the guide channel is converted into separate nanoparticles; C. Covering the sample surface with a precursor by plasma enhanced chemical vapor deposition technology, and at 200-300℃, the metal or metal alloy nanoparticles absorb the precursor to generate two nanowires with gaps, realize precise positioning of the positive and negative nanowire electrodes, and the gap control range is 10 nm-10 um, and the residual precursor layer is removed by reactive ion etching process; D. Selectively depositing a gold electrode as a metal current collector at both ends of the positive and negative nanowire electrodes by photolithography and electron beam evaporation process, and the thickness is 30-100 nm; E. Depositing a layer of solid electrolyte interface at the end where the positive and negative electrodes are close to each other and in the gap by atomic layer deposition technology, or performing drop dispensing of liquid electrolyte by inkjet printing technology, i.e. completing the preparation of the micro-nano battery; the thickness of the electrolyte is controlled at 100-500 nm to ensure ion conduction and isolate the electron path.

3. A method for fabricating a micro-nano battery based on a nanowire gap structure, characterized in that, Comprising the following steps: A. Defining the curved shape of the step on the flexible substrate by using photolithography technology; then etching the step structure on the flexible substrate by using inductively coupled plasma etching method; B. Preparing the indium-gallium alloy catalytic metal layer at one end of the step by using photolithography process and evaporation sputtering metal deposition process, and the end point is used as the growth starting position of the nanowire; then, under the plasma action of reducing gas H2, the indium-gallium alloy catalytic metal layer covering the guide channel is converted into separated indium-gallium alloy metal nanoparticles by processing at a temperature higher than the melting point of the metal; C. Covering the precursor on the surface of the sample by using plasma enhanced chemical vapor deposition technology, and the metal or metal alloy nanoparticles absorb the precursor to generate the curved shape of the nanowire electrode at 200-300℃; D. Selectively depositing the lithium-containing metal layer as the metal electrode of the micro-battery at a distance of 10 nm-10 um from the nanowire electrode by using photolithography and electron beam evaporation process; E. Selectively depositing the gold electrode as the metal current collector at both ends of the nanowire electrode and the lithium-containing metal electrode by using photolithography and electron beam evaporation process; F. Depositing a layer of solid electrolyte interface at the opposite ends and gaps of the nanowire electrode and the lithium-containing metal electrode by using atomic layer deposition technology, or performing drop dispensing of the liquid electrolyte by using inkjet printing technology, thereby completing the preparation of the micro-nano battery.

4. The method of claim 1-3, wherein the method further comprises: The precursor is an amorphous silicon precursor or an amorphous silicon / amorphous germanium laminated film precursor.

5. A preparation method of an integrated micro-nano battery based on a nanowire gap structure, characterized in that, A. Defining the guide of several steps on the substrate by using photolithography technology, and then etching the step structure on the substrate by using inductively coupled plasma etching method; the etching channel depth is 50-200 nm; B. Preparing the metal or metal alloy catalytic layer at the end of each step by using photolithography process and evaporation sputtering metal deposition process, which is used as the growth starting position of the nanowire; then, under the plasma action of reducing gas H2, the metal or metal alloy catalytic layer covering the guide channel is converted into separated nanoparticles by processing at a temperature higher than the melting point of the metal; C. Covering the precursor on the surface of the sample by using plasma enhanced chemical vapor deposition technology, and the metal or metal alloy nanoparticles absorb the precursor to generate several pairs of nanowire arrays with gaps, thereby realizing the preparation of precisely positioned positive and negative nanowire electrodes, and the gap control range is 10 nm-10 um, or generating several independent nanowire arrays, and the residual precursor layer is removed by using reactive ion etching process; D. Selectively depositing the gold electrode as the metal current collector at both ends of each pair of positive and negative nanowire electrodes by using photolithography and electron beam evaporation process, and the thickness is 30-100 nm; Or, depositing the lithium-containing metal layer electrode at a distance of 10 nm-10 um from the independent nanowire electrode, and then depositing the gold electrode as the metal current collector at both ends of each independent nanowire electrode and the lithium-containing metal electrode. The preparation of the integrated micro-nano battery array is completed by depositing a layer of solid electrolyte interface on the end of each pair of positive and negative electrodes close to each other and the gap by atomic layer deposition technology or by drop dispensing of liquid electrolyte by inkjet printing technology; the thickness of the electrolyte is controlled to be 100-500 nm to ensure ion conduction and isolate the electron path.

6. The method of claim 5, wherein the method further comprises: The precursor is an amorphous silicon precursor or an amorphous silicon / amorphous germanium laminated film precursor.

7. A micro- or nano-battery based on a nanowire gap structure, characterized in that, It is prepared by the method of any one of claims 1-3.

8. The micro-nano battery according to claim 7, wherein: The material of the nanowire is a heavily doped silicon nanowire material.

9. The micro-nano battery of claim 7, wherein: The material of the nanowire is a semiconductor material.

10. An integrated micro-nano battery based on nanowire gap structure, characterized in that, It is prepared by the method of claim 5.

11. The integrated micro- and nano-battery of claim 10, wherein: The material of the nanowire is a heavily doped silicon nanowire material.

12. The integrated micro- and nano-battery of claim 10, wherein: The material of the nanowire is a semiconductor material.

13. Use of a micro- or nanobattery produced by the production method according to any one of claims 1 to 3 or of an integrated micro- or nanobattery produced by the production method according to claim 5, characterized in that: The micro-nano battery or the integrated micro-nano battery is applied to the energy supply of a micro-nano electronic device or a wearable electronic device.

14. Use according to claim 13, characterized in that, The micro-nano electronic device is a semiconductor micro-nano electronic device.

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