Metal nanostructure 3d printing device and method integrated with ring electrode showerhead

Abstract

The application discloses a metal nanostructure 3D printing device and method integrated with a ring electrode nozzle, and belongs to the field of additive manufacturing. The device comprises a printing platform, and a spraying system for material spraying is arranged above the printing platform. The spraying system comprises a printing nozzle, and the printing nozzle is connected with a storage cylinder. The printing nozzle comprises an electrospray printing nozzle and an electric field focusing module. The electric field focusing module comprises a ring electrode assembly arranged above the printing platform. The ring electrode assembly comprises a plurality of ring electrodes which are sequentially and spacedly arranged from top to bottom. The ring electrodes are provided with through holes, and the inner diameters of the through holes of the plurality of ring electrodes sequentially decrease from top to bottom.

Description

Technical Field

[0001] This invention belongs to the field of additive manufacturing, specifically relating to a 3D printing device and method for metal nanostructures with an integrated annular electrode nozzle. Background Technology

[0002] The statements herein provide only background information in relation to this invention and do not necessarily constitute prior art.

[0003] Metal nanostructures play a crucial role in advanced electronics / optoelectronics, aerospace, micro / nano-electromechanical systems, soft robotics, new energy, and metamaterials. However, current technologies severely limit the fabrication and application of nanostructures due to factors such as manufacturing costs, process complexity, and material limitations. Currently, the main methods for manufacturing nanoscale metal structures include photolithography, etching, nanoimprinting, aerosol jetting, and electrohydrodynamic jetting. Among these, optical photolithography offers advantages such as high yield, good repeatability, and ease of industrial application, but suffers from problems such as complex mask fabrication, high manufacturing costs, small area, and the inability to achieve complex nanoscale three-dimensional structures. Nanoimprinting offers advantages such as high production efficiency, high resolution, and suitability for mass production, but template fabrication requires technologies such as electron beam lithography, resulting in high costs and difficulties in large-area fabrication. Etching technology also faces challenges such as complex and difficult template fabrication, and the manufacturing process causes significant environmental pollution. Compared to traditional subtractive and equal-material manufacturing technologies, micro / nano 3D printing technology has already seen widespread application in nanostructure printing, offering advantages such as low cost, simple structure, the ability to print complex three-dimensional micro / nano structures, and direct forming without masks / molds. Aerosol jet printing, a typical micro / nano 3D printing technology, can achieve the printing of structures with feature sizes as small as 1 μm. Faraday 3D printing, driven by a composite electric field, can achieve the printing of nanoscale metal structures. However, the limited viscosity range of materials printed using aerosol jet printing restricts the range of printable materials.

[0004] Electrospray printing is a printing technology based on electrohydrodynamics. It uses an external electric field to drive a functional liquid to generate a fine jet at the nozzle exit. This method, relying on a strong electric field to "pull" out the jet of liquid droplets from the nozzle's curved surface, boasts extremely high resolution, with jet diameters less than 100 nm, far smaller than the nozzle's inner diameter. However, due to limitations in the fineness of the conductive ink, it can currently only achieve the fabrication of sub-microscale metal structures, and its printing efficiency is relatively low. Although electrospray technology can manufacture nanoscale particles, the ejected nanoparticles are disordered, making it impossible to achieve precise shaping of nanoscale three-dimensional structures. Furthermore, the uneven size distribution of particles generated by electrospray limits its ability to manufacture ordered nanoscale structures.

[0005] Therefore, existing printing technologies have many shortcomings and limitations in terms of printing materials, printing stability, and printing resolution. In particular, current processes still face significant challenges in printing nanoscale electrodes. Therefore, there is an urgent need to develop technologies capable of printing nanoscale electrodes, improving the stability, consistency, and material applicability of printed structures. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a metal nanostructure 3D printing device and method with an integrated annular electrode nozzle. This device overcomes the limitations of existing printing technologies in terms of printing resolution, printing stability, and printing materials, and realizes the manufacturing of metal structures at the nanoscale.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0008] In a first aspect, the present invention provides a 3D printing device for metal nanostructures with an integrated annular electrode nozzle, comprising a printing platform and an injection system for material injection disposed above the printing platform; the injection system includes a printing nozzle connected to a material storage cylinder; the printing nozzle includes an electrospray printing nozzle and an electric field focusing module, the electric field focusing module including an annular electrode assembly disposed above the printing platform; the annular electrode assembly includes a plurality of annular electrodes arranged sequentially from top to bottom, the annular electrodes having internal through holes, and the inner diameter of the through holes of the plurality of annular electrodes decreasing sequentially from top to bottom.

[0009] As a further technical solution, multiple ring electrodes are coaxially arranged, and a ring-shaped baffle plate is provided at the through hole of the ring electrode. The baffle plate is disposed on the surface of the ring electrode and has a set height; each ring electrode is externally connected to the positive terminal of a high-voltage pulse power supply.

[0010] As a further technical solution, each annular electrode is connected to the storage cylinder through an electrode holder, and the outer diameter of the multiple annular electrodes increases sequentially from top to bottom; the electrode holder is made of transparent material and has a cylindrical structure.

[0011] As a further technical solution, a solution outlet is provided at the bottom annular electrode. The solution outlet is connected to the discharge unit, which includes a discharge pipe and a syringe. The discharge pipe is connected to the solution outlet of the annular electrode, and the discharge pipe and the syringe are connected.

[0012] As a further technical solution, the electrospray printing nozzle includes a metal nozzle and a quartz glass nozzle, with the quartz glass nozzle fitted over the metal nozzle; the electrospray printing nozzle is connected to the lower end of the storage cylinder and is connected to the positive terminal of a high-voltage pulse power supply.

[0013] As a further technical solution, the tip of the electrospray printing nozzle is positioned above the annular electrode; the voltage difference applied between the electrospray printing nozzle and the annular electrode ranges from 2000 to 2500V.

[0014] As a further technical solution, an observation unit is also included, which is aligned with the position of the electrospray printing nozzle.

[0015] As a further technical solution, the injection system also includes a back pressure control unit and a feeding unit. The back pressure control unit includes a pneumatic pipe connected to the storage cylinder, and the pneumatic pipe is equipped with a precision pressure regulating valve. The feeding unit includes a feeding pipe connected to the storage cylinder, and the feeding pipe is connected to a micro-injection pump.

[0016] As a further technical solution, the printing platform has a printing substrate fixed on top, and the storage cylinder is fixed to the Z-axis worktable by a fixing frame. The Z-axis worktable controls the height difference between the printing nozzle and the printing substrate. The printing platform is connected to the negative terminal of a high-voltage pulse power supply.

[0017] Secondly, the present invention also provides a method for operating the metal nanostructure 3D printing device with the integrated annular electrode nozzle as described above, comprising the following steps:

[0018] Prepare the printhead by connecting the electro-spray printhead to the lower end of the storage cylinder, placing the storage cylinder on the Z-axis worktable, and adjusting the position of the observation unit to facilitate observation of the printhead printing process.

[0019] The annular electrode is fixed to ensure that the electro-spray printing nozzle is at a set distance from the annular electrode. The electro-spray printing nozzle and the annular electrode are respectively connected to a high-voltage pulse power supply. The discharge tube and the syringe are connected to the discharge port of the lowest annular electrode.

[0020] A printing substrate is placed on the printing platform, and the printing platform and Z-axis stage are moved to the printing position. The high-voltage pulse power supply is turned on. Under the action of the electric field, the printing material is ejected from the electrospray printing nozzle as droplets. Under the focusing action of the electric field of the ring electrode, the droplets gather to form a conical jet that is ejected from the through hole of the ring electrode. Combined with the movement of the printing platform, the material is deposited on the substrate to realize the fabrication of micro and nano structures. During the printing process, the deposition of solution on the ring electrode is observed in real time. If too much solution is deposited, the solution is extracted with a syringe.

[0021] After printing is complete, turn off the high-voltage pulse power supply, move the printing platform and Z-axis worktable to the original position, and remove the printed workpiece from the printing platform.

[0022] The beneficial effects of the present invention are as follows:

[0023] The metal nanostructure 3D printing device of the present invention is equipped with an electrospray printing nozzle and an electric field focusing module. Utilizing the principle of electrospray, it can realize the spraying of nanoscale droplets. Due to the limitation of the focusing effect of the annular electrode, only droplets within a specific size range can be ejected from the nozzle. Therefore, the present invention, combined with the annular electrode, can effectively focus the electric field, so that the high-intensity electric field drives the droplets to be ejected from the through hole of the annular electrode, which greatly improves the printing resolution and realizes the manufacturing of nanoscale metal structures.

[0024] The metal nanostructure 3D printing device of the present invention is provided with multiple annular electrodes, which are arranged at intervals from top to bottom, and the inner diameter of the through holes of the annular electrodes decreases from top to bottom. This can effectively focus the electric field and gather the droplets ejected from the electrospray nozzle into a smaller inner diameter range, thereby improving the printing resolution.

[0025] The metal nanostructure 3D printing device of the present invention can effectively utilize the electric field between electrospray, ring electrode and printing substrate, and control the direction of electric field force and ion movement between the three by changing different pressure differences, so as to achieve precise control of printing size.

[0026] The metal nanostructure 3D printing device of the present invention has a wide range of printing material viscosity, and can achieve the printing of conductive materials with a viscosity of 0-10000 mPa·s. The fabrication of micro and nano structures is simple, and only the printing process is required to form two-dimensional / three-dimensional structures, which greatly reduces various production costs.

[0027] The metal nanostructure 3D printing device of the present invention improves the material utilization rate through the additive manufacturing process. The deposition solution of the ring electrode is extracted by the discharge unit, so that the material can be recycled and no waste liquid / waste gas is generated, which is environmentally friendly. Attached Figure Description

[0028] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0029] Figure 1 This is a schematic diagram of the printing principle of the nanoscale metal structure 3D printing device with integrated ring electrode nozzle in this invention.

[0030] Figure 2 This is a schematic diagram of the nanoscale metal structure 3D printing device with integrated annular electrode nozzle of the present invention.

[0031] Figure 3 This is a cross-sectional view of the printing nozzle of the nanoscale metal structure 3D printing device with integrated annular electrode nozzle of the present invention.

[0032] Figure 4This is an enlarged view of the printing nozzle of the nanoscale metal structure 3D printing device with integrated annular electrode nozzle of the present invention.

[0033] In the diagram: the spacing or dimensions between parts have been exaggerated to show their positions; the diagram is for illustrative purposes only.

[0034] The components include: 1. Printing platform; 2. Printing substrate; 3. Ring electrode; 4. Electrode holder; 5. Discharge unit; 6. Electrospray printing nozzle; 7. Holder; 8. Storage cylinder; 9. Z-axis worktable; 10. Microscope; 11. Precision pressure regulating valve; 12. Air pressure pipe; 13. Feed pipe; 14. Micro-injection pump; and 15. High-voltage pulse power supply. Detailed Implementation

[0035] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0036] As described in the background section, in order to address the shortcomings and limitations of existing micro-nano 3D printing technologies and solve the aforementioned technical problems, this invention proposes a metal structure 3D printing device and method with an integrated annular electrode nozzle.

[0037] Example 1

[0038] In a typical embodiment of the present invention, such as Figure 2 As shown, a metal nanostructure 3D printing device with an integrated annular electrode nozzle is proposed, which includes a printing platform 1, a jetting system for material jetting, and an observation unit; the jetting system includes a printing nozzle, a back pressure control unit, a feeding unit, a storage cylinder 8, and a high-voltage pulse power supply 15; the printing nozzle includes an electrospray printing nozzle 6 and an electric field focusing module; the electric field focusing module includes an annular electrode assembly, an electrode fixing frame 4, and a material discharge unit 5.

[0039] The printing platform 1 is located at the bottom, and the printing substrate 2 is placed on the printing platform 1 and fixed to the printing platform 1 by vacuum adsorption. A ring electrode assembly is arranged above the printing substrate 2, and the solution outlet at the bottom of the ring electrode assembly is connected to the dispensing unit 5. The ring electrode assembly is fixed to the bottom of the storage cylinder 8 by the electrode fixing bracket 4. The electrospray printing nozzle 6 is connected to the lower end of the storage cylinder 8. The storage cylinder 8 and the microscope 10 are fixed to the Z-axis stage 9 by the fixing bracket 7. A precision pressure regulating valve 11 and a pressure pipe 12 form a back pressure control unit, and a feed pipe 13 and a micro-injection pump 14 form a feed unit. Both the feed unit and the back pressure control unit are connected to the storage cylinder; specifically, the upper end of the storage cylinder 8 is connected to the pressure pipe 12 and the feed pipe 13. The electrospray printing nozzle 6 and the ring electrode 3 are connected to a high-voltage pulse power supply 15 to provide the required printing electric field. The printing platform 1 is connected to the negative terminal of the high-voltage pulse power supply.

[0040] In this embodiment, the printing platform 1 is a two-dimensional working platform with a maximum displacement of 400×400mm, controlling the movement in the XY direction.

[0041] In this embodiment, the printing substrate 2 is a conductive or non-conductive substrate, such as silicone, glass, silicon wafer or resin.

[0042] Specifically, the annular electrode assembly consists of three annular electrodes 3, each with a built-in through hole. The three annular electrodes 3 are coaxially arranged and spaced apart from top to bottom, with the inner diameter of the through hole decreasing from top to bottom.

[0043] The annular electrode assembly, through the above-described configuration, effectively focuses the electric field, enabling a high-intensity electric field to drive droplets out of the annular electrode's through-hole. Simultaneously, the annular electrode assembly gradually blocks larger droplets, allowing only droplets of a specific size to exit through the through-hole. A circular baffle plate is located at the through-hole of the annular electrode, positioned on the surface of the electrode at a certain height, effectively preventing solution from flowing out of the through-hole and affecting print resolution.

[0044] Each annular electrode 3 is connected to the storage cylinder 8 via an electrode holder 4. The outer diameters of the three annular electrodes increase sequentially from top to bottom, facilitating their sequential installation. Each annular electrode is connected to the positive terminal of a high-voltage pulse power supply 15, and the applied voltage is adjusted according to the application range of the electrospray glass printing head.

[0045] Ring electrodes with different inner and outer diameters were fabricated using metal 3D printing technology. The ring electrodes were then fixed on a ring electrode holder, and an electric field focusing effect was achieved by applying an external power supply to the three ring electrodes respectively.

[0046] The annular electrode 3 is fabricated using metal 3D printing, with materials such as copper, aluminum, and silver being optional. The inner diameter of the three annular electrodes can range from 30-400 μm, the outer diameter from 1-50 mm, and the thickness from 1-500 μm. In this embodiment, the inner diameters of the through-holes in the three annular electrodes are 200 μm, 150 μm, and 100 μm from top to bottom.

[0047] A solution outlet is provided at the bottom ring electrode 3, which is connected to the discharge unit 5. The discharge unit 5 includes a discharge pipe and a syringe. The discharge pipe is connected to the solution outlet of the ring electrode, and the discharge pipe and syringe are connected to facilitate material recovery. When too much solution is deposited on the ring electrode, the solution is promptly extracted from the discharge pipe using the syringe.

[0048] Electrode holder 4 is fixed to the bottom of the storage cylinder. The electrode holder is made of a transparent material, with options including PP, PC, and silicone, facilitating observation of the electrospray pattern. The electrode holder's dimensions are set according to the annular electrode dimensions. It is cylindrical, detachable, and sealed to prevent solution leakage. An outlet is provided at the connection point between the annular electrode and the discharge unit, corresponding to the solution outlet of the annular electrode, allowing solution to flow out. A through hole is provided at the connection point between the annular electrode and the power supply, facilitating connection to a high-voltage pulse power supply.

[0049] Specifically, the electrospray printing nozzle 6 includes a metal nozzle and a quartz glass nozzle. The quartz glass nozzle is fitted over the metal nozzle. The quartz glass nozzle is fabricated using a needle forging apparatus, and then fixed to the metal nozzle with photoresist to achieve electrospray deposition. The metal nozzle can have an inner diameter of 250-220 μm and an outer diameter of 400-450 μm. The quartz glass nozzle is fabricated using a capillary tube. In this embodiment, the capillary inner diameter can be selected from 400-500 μm, and the inner diameter of the tip of the quartz glass nozzle after high-temperature fabrication using a needle forging apparatus can be selected from 10-50 μm.

[0050] The tip of the electrospray printing nozzle 6 is positioned above the annular electrode. The electrospray printing nozzle 6 is connected to the positive terminal of the high-voltage pulse power supply 15, and the voltage difference between the voltage applied to the electrospray printing nozzle and the voltage applied to the annular electrode is 2000-2500V.

[0051] The microscope 10 constitutes the observation unit. The microscope 10 is aligned with the position of the electro-spray printing nozzle 6, and the printing situation of the nozzle is observed through the microscope.

[0052] The Z-axis stage 9 controls the height difference between the printhead and the substrate. By changing the height difference, the electric field distribution between the printhead and the substrate can be controlled, thereby changing the deposition size of the conical jet.

[0053] The feeding unit and back pressure control unit enable continuous material supply during the printing process. A precision pressure regulating valve 11 is installed on the air pressure pipe 12 to adjust the air pressure. The feeding pipe 13 is connected to a micro-injection pump 14 and a storage cylinder 8 at both ends, respectively. The flow rate of the micro-injection pump is adjusted in real time according to the viscosity of the printing material. When the material viscosity is low, the back pressure control unit is turned off, and material deposition can be achieved simply by controlling the flow rate of the injection pump. The selectable flow rate range for this is 0-10 ml / h. When the material viscosity is too high, air pressure must be supplied to the storage cylinder via the air pressure pipe to facilitate material extrusion. The precision pressure regulating valve has a selectable range of 0-100 kPa, with a selectable pressure range of 0-50 kPa for printing materials with a viscosity of 0-1000 cp.

[0054] The working principle of the printing device of this invention is as follows:

[0055] like Figure 1 As shown, by applying high pressure to the electrospray printing nozzle, liquid material is forced to form a Taylor cone at the nozzle. When the applied positive pressure causes the Taylor cone to reach the Rayleigh upper limit (where the surface charge Coulomb repulsion and surface tension are equal at the critical point), charged ions separate from the tip of the Taylor cone. As the solvent continuously evaporates, the charge density of large droplets increases, causing them to break down into smaller droplets, forming an electrospray. By adding a ring electrode, a high-intensity electric field is created around the spray. When the droplet diameter is less than 10 nm, the high-intensity electric field drives the droplets to be ejected from the through-hole of the ring electrode. The ring electrode, with its gradually decreasing inner diameter, can concentrate the droplets into a smaller inner diameter range. Simultaneously, under the electric field force of the printing platform electrode, the cone jet is precisely deposited onto the printing substrate, thereby achieving nanoscale 3D printing of conductive or non-conductive structures.

[0056] Example 2

[0057] In another typical embodiment of this application, a method for operating the 3D printing apparatus as described above is provided, with the specific process steps as follows:

[0058] Step 1: Printer preparation. Place printing material in the micro-injection pump, connect the feed tube and air pressure tube of the injection pump to the upper end of the storage cylinder, connect the electro-spray printing nozzle to the lower end of the storage cylinder, and then place the storage cylinder on the fixed frame of the Z-axis worktable. Adjust the microscope position to facilitate observation of the print head printing.

[0059] Step 2: Fix the annular electrode. Fix the annular electrode to the storage cylinder using the electrode holder, and ensure that the electrospray printing nozzle is a certain distance away from the annular electrode. Then, connect the high-voltage pulse power supply to the electrospray printing nozzle and the annular electrode respectively. Connect the discharge tube and the syringe to the discharge port of the outermost annular electrode.

[0060] Step 3: Printing program setup. Place the processed printing substrate on the printing platform, move the printing platform and Z-axis stage to the printing position, set appropriate printing parameters, turn on the high-voltage pulse power supply, and open the pre-designed printing pattern or circuit structure program. Under the action of the electric field, the printing material is ejected from the electrospray printing nozzle as droplets. Under the focusing action of the electric field of the ring electrode, the droplets gather to form a conical jet that is ejected from the through-hole of the ring electrode. Combined with the movement of the printing platform, the material is deposited on the substrate to realize the fabrication of micro-nano structures. During the printing process, observe the solution deposition on the ring electrode in real time. If too much solution is deposited, use a syringe to remove the solution in time.

[0061] Step 4: After printing is complete, turn off the high-voltage pulse power supply, precision pressure regulating valve, micro injection pump, etc., move the printing platform and Z-axis worktable to the original position, and remove the printed workpiece from the printing platform.

[0062] Furthermore, in step 1, the flow rate of the micro-injection pump can be selected as 0-50 mL / h.

[0063] Furthermore, the printing material in step 1 is not limited to nano silver ink, nano conductive silver paste, silica suspension, PEDOT:PSS, PVP, etc., and the viscosity range of the printing material is 0-10000mPa·s.

[0064] Furthermore, in step 1, the positive pressure applied to the electrospray printing nozzle ranges from 0-3KV, and the positive pressure applied to the annular electrode ranges from 300-900V. The voltage difference between the electrospray printing nozzle and the annular electrode ranges from 2000-2500V, at which point the spraying system can obtain a stable conical jet.

[0065] Furthermore, in step 2, the printing platform corresponds to the ground electrode, and the printing substrate can be made of rigid or flexible materials. Rigid substrates include, but are not limited to, glass sheets, silicon wafers, and acrylic sheets, while flexible substrates include, but are not limited to, PET films and PI films.

[0066] To enable those skilled in the art to better understand the technical solutions of this application, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.

[0067] Using nano-silver ink as the printing material and float glass as the printing substrate, and employing the aforementioned 3D printing equipment, high-resolution metal electrode fabrication was achieved. The specific steps are as follows:

[0068] Step 1: Printhead preparation. Place nano-silver ink in the micro-injection pump, connect the feed tube and air pressure tube of the injection pump to the upper end of the storage cylinder, and set the flow rate of the micro-injection pump to 4 mL / h. Connect the electrospray printing head to the lower end of the storage cylinder, and then place the storage cylinder on the fixed frame of the Z-axis worktable. Adjust the microscope position to facilitate observation of the printhead printing.

[0069] Step 2: Fix the annular electrode. Fix the annular electrode to the storage cylinder using the electrode holder, and ensure that the electrospray printing nozzle is 2cm away from the annular electrode. Then, connect a high-voltage pulse power supply to the electrospray printing nozzle and the annular electrode respectively. Connect the discharge tube and syringe to the discharge port of the outermost annular electrode.

[0070] Step 3: Printing program settings. Place the float glass in isopropanol solution and deionized water for ultrasonic cleaning for 5 minutes each, then dry it with inert gas. Next, place the treated float glass on the printing platform. Set the printing platform and Z-axis stage to appropriate printing positions and adjust suitable printing parameters (printing pressure 50 kPa, printing speed 20 mm / s) to ensure a stable conical jet. Set the electrospray printer nozzle voltage to 2500V and the ring electrode voltage to 500V. Turn on the high-voltage pulse power supply and open the pre-designed printing pattern or circuit structure program. Run the printing program. Under the action of the electric field, nano-silver ink is precisely deposited onto the float glass surface. During printing, observe the nano-silver ink deposited on the ring electrode in real time. If too much nano-silver ink is deposited, remove it with a syringe.

[0071] Step 4: After printing is complete, turn off the high-voltage pulse power supply, precision pressure regulating valve, and micro-injection pump. Move the printing platform and Z-axis worktable to the original position and remove the printed nano-silver electrode from the printing platform.

[0072] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A 3D printing device for metal nanostructures with an integrated annular electrode nozzle, characterized in that, The device includes a printing platform, with a spraying system for material spraying mounted on top of the printing platform. The spraying system includes a print head connected to a material storage cylinder. The print head includes an electrospray printing print head and an electric field focusing module. The electric field focusing module includes an annular electrode assembly mounted on top of the printing platform. The annular electrode assembly includes multiple annular electrodes spaced apart from top to bottom. The annular electrodes have internal through holes, and the inner diameter of the through holes of the multiple annular electrodes decreases from top to bottom. Multiple ring electrodes are coaxially arranged, each ring electrode is externally connected to the positive terminal of a high-voltage pulse power supply, the outer diameter of the multiple ring electrodes increases sequentially from top to bottom, the electrospray printing nozzle is connected to the positive terminal of the high-voltage pulse power supply, the tip of the electrospray printing nozzle is located above the ring electrode, and the voltage difference applied between the electrospray printing nozzle and the ring electrode is 2000-2500V. The printing platform has a printing substrate fixed on top, and the storage cylinder is fixed to the Z-axis worktable by a fixing frame. The Z-axis worktable controls the height difference between the printing nozzle and the printing substrate. The printing platform is connected to the negative terminal of a high-voltage pulse power supply.

2. The 3D printing device for metal nanostructures with an integrated annular electrode nozzle as described in claim 1, characterized in that, A ring-shaped baffle plate is provided at the through hole of the ring electrode. The baffle plate is set on the surface of the ring electrode and has a set height.

3. The 3D printing device for metal nanostructures with an integrated annular electrode nozzle as described in claim 1, characterized in that, Each annular electrode is connected to the storage cylinder via an electrode holder made of transparent material and has a cylindrical structure.

4. The 3D printing device for metal nanostructures with an integrated annular electrode nozzle as described in claim 1, characterized in that, The bottom ring electrode has a solution outlet, which is connected to the discharge unit. The discharge unit includes a discharge tube and a syringe. The discharge tube is connected to the solution outlet of the ring electrode, and the discharge tube and the syringe are connected.

5. The 3D printing device for metal nanostructures with an integrated annular electrode nozzle as described in claim 1, characterized in that, The electrospray printing nozzle includes a metal nozzle and a quartz glass nozzle, with the quartz glass nozzle fitted over the metal nozzle; the electrospray printing nozzle is connected to the lower end of the storage cylinder.

6. The 3D printing device for metal nanostructures with an integrated annular electrode nozzle as described in claim 1, characterized in that, It also includes an observation unit, which is aligned with the position of the electrospray printer nozzle.

7. The 3D printing device for metal nanostructures with an integrated annular electrode nozzle as described in claim 1, characterized in that, The injection system also includes a back pressure control unit and a feeding unit. The back pressure control unit includes a pneumatic pipe connected to the storage cylinder, and the pneumatic pipe is equipped with a precision pressure regulating valve. The feeding unit includes a feeding pipe connected to the storage cylinder, and the feeding pipe is connected to a micro-injection pump.

8. The method of operating the metal nanostructure 3D printing device with integrated annular electrode nozzle as described in any one of claims 1-7, characterized in that, Includes the following steps: Prepare the printhead by connecting the electro-spray printhead to the lower end of the storage cylinder, placing the storage cylinder on the Z-axis worktable, and adjusting the position of the observation unit to facilitate observation of the printhead printing process. The annular electrode is fixed to ensure that the electro-spray printing nozzle is at a set distance from the annular electrode. The electro-spray printing nozzle and the annular electrode are respectively connected to a high-voltage pulse power supply. The discharge tube and the syringe are connected to the discharge port of the lowest annular electrode. Place the printing substrate on the printing platform, move the printing platform and Z-axis stage to the printing position, turn on the high-voltage pulse power supply, and under the action of the electric field, the printing material is ejected from the electrospray printing nozzle as droplets. Under the focusing action of the electric field of the ring electrode, the droplets gather to form a cone jet that is ejected from the through hole of the ring electrode. By combining the movement of the printing platform, materials are deposited onto the substrate to achieve the fabrication of micro and nano structures; During the printing process, the solution deposition on the ring electrode is observed in real time. If too much solution is deposited, the solution is extracted with a syringe. After printing is complete, turn off the high-voltage pulse power supply, move the printing platform and Z-axis worktable to the original position, and remove the printed workpiece from the printing platform.

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