All-solid-state battery three-dimensional electrode preparation method based on aerosol jet printing

Abstract

The invention provides an all-solid-state battery three-dimensional electrode preparation method based on aerosol jet printing, and the method comprises the following steps: constructing a three-dimensional porous frame by using a conductive skeleton material through an aerosol jet printing technology; depositing an active material and a solid electrolyte on the surface of the frame layer by layer to form a gradient distribution layer; generating an interface transition layer by adopting ultraviolet curing or rapid heat treatment; and in combination with a closed-loop feedback control system, deposition parameters are dynamically adjusted. A conductive active material and a solid electrolyte are uniformly distributed on the surface of a three-dimensional porous framework in a layer-by-layer deposition manner through an aerosol jet printing method, and the solid electrolyte and an electrode material form a close contact interface by accurately controlling a jet path, a nozzle diameter and a material deposition rate; the interface side reaction easily caused by traditional high-temperature sintering is eliminated, and the interface impedance is reduced; and furthermore, the transmission efficiency of the lithium ions at the interface is improved through an ultraviolet curing or rapid heat treatment process.

Description

Technical Field

[0001] The present invention relates to the technical field of electrode preparation for all-solid-state batteries, and particularly to a method for preparing a three-dimensional electrode of an all-solid-state battery based on aerosol jet printing. Background Art

[0002] As a key research and development direction of a new generation of energy storage technologies, all-solid-state batteries are receiving extensive attention due to their high energy density, high safety, long cycle life, etc. Compared with traditional liquid electrolyte batteries, all-solid-state batteries can fundamentally avoid safety hazards such as liquid leakage and flammability by using solid electrolytes, and also have obvious advantages in chemical and thermal stability. However, there are currently some problems: Due to the high rigidity of solid materials, traditional coating methods often have difficulty achieving tight bonding between the electrode and the solid electrolyte. There may be voids or rough surfaces at the interface, which will increase the internal resistance of the battery, limit the effective transmission of lithium ions, and ultimately lead to a decrease in battery efficiency and life; The ion transport efficiency in all-solid-state batteries depends on the design and internal structure of the electrode material. In a traditional planar electrode structure, lithium ions need to pass through a long diffusion path to reach the electrode-electrolyte interface. Especially during high-rate charge and discharge, limited ion transport will lead to significant polarization phenomena, seriously affecting power performance and cycle life; Existing mixing and coating processes cannot achieve material uniformity at the micron or even nanometer level, resulting in problems of mismatched conductivity and uneven electrochemical reactions in local areas of the electrode, which will directly cause local overheating or increased polarization of the battery, accelerate battery aging, and thus significantly shorten the cycle life of the battery; Therefore, a method for preparing a three-dimensional electrode of an all-solid-state battery based on aerosol jet printing is proposed. Summary of the Invention

[0003] In view of this, the present invention provides a method for preparing a three-dimensional electrode of an all-solid-state battery based on aerosol jet printing to solve or alleviate the technical problems existing in the prior art, and at least provide a beneficial option.

[0004] The technical solution of the present invention is realized as follows: A method for preparing a three-dimensional electrode of an all-solid-state battery based on aerosol jet printing, the method consists of the following steps: S1. Through aerosol jet printing technology, a three-dimensional porous framework is constructed based on a conductive skeleton material, and the porosity of the framework is determined according to the formula ; Determine; Wherein, is the actual density of the three-dimensional framework, , are the theoretical densities of the materials; The porosity of the frame ranges from 30% to 60%, the pore diameter ranges from 1 to 10 microns, the nozzle diameter is in the range of 30 to 50 microns, the air pressure is controlled at 20 to 50 psi, the particle concentration is in the range of 0.5% to 2%, and the deposition rate is 10 to 30 mm / s; S2. On the surface of the porous frame, a composite material is deposited layer by layer using aerosol jet printing to form a gradient distribution layer; The gradient distribution layer is composed of a highly conductive active material and a solid electrolyte. The particle size of the outermost layer is 50 to 100 nanometers. The proportion of the active material and the solid electrolyte gradually increases according to the inner and outer layer ratio, and finally reaches 80%. The effective conductivity and ionic conductivity of the gradient distribution layer are calculated by the following formulas: ; ; where and are the material distribution weights, and are the conductivity and ionic conductivity of each layer respectively; S3. During the deposition of the gradient distribution layer, the printing speed, nozzle diameter, and particle dispersibility are adjusted in real time to optimize the material distribution. After deposition, an interfacial transition layer with a thickness of 50 to 200 nanometers is formed between the frame and the deposition layer through ultraviolet light curing or rapid heat treatment. The ionic conductivity ratio of the cured interfacial transition layer is characterized by the following formula: ; where and are the interfacial ionic conductivities before and after curing respectively; By precisely controlling the spraying path, nozzle diameter, and material deposition rate, a tightly contacting interface between the solid electrolyte and the electrode material is formed, eliminating the interfacial side reactions easily caused by traditional high-temperature sintering, reducing the interfacial impedance. Through the ultraviolet light curing or rapid heat treatment process, the interfacial material is cured immediately after printing, enhancing the mechanical bonding strength and chemical stability of the interface and reducing the interfacial voids.

[0005] S4. During the deposition process, a closed-loop feedback control and a PID control algorithm are used to adjust the deposition parameters in real time. The PID control formula is: ; where is the deviation value between the target thickness and the actual thickness, , , are the proportional, integral, and differential gain coefficients; S5. Verify the performance indicators of the completed three-dimensional electrode through electrochemical performance tests. The performance tests include impedance spectroscopy analysis and cyclic voltammetry, which are used to measure the interfacial resistance. and the cycle stability of the active material. The reduction value of the interfacial resistance is determined by the formula. where is the bulk resistance of the solid electrolyte, is the difference in the optimized interfacial impedance.

[0006] Further preferably, the conductive framework material includes carbon nanotubes and metal oxides. The diameter of the carbon nanotubes is 10 to 20 nanometers, the length is 1 to 5 micrometers, and the particle size of the metal oxide is 50 to 200 nanometers. It is prepared by a method combining ultrasonic dispersion and high-speed stirring, where the ultrasonic power is 200 watts, the stirring speed is 1500 revolutions per minute, and the time is 2 hours.

[0007] Further preferably, the porosity of the porous framework is controlled within 30% to 40%. By adjusting the nozzle diameter to 40 to 50 micrometers, the air pressure to 30 to 50 psi, the particle concentration to 1% to 2%, and the deposition speed to 10 millimeters per second, the porosity of the porous framework is controlled within the range and made uniform.

[0008] Further preferably, the particle size range of the active material in the outer layer of the gradient distribution layer is 60 to 100 nanometers, and the particle size range of the inner layer solid electrolyte material is 200 to 300 nanometers. The thickness of each layer is controlled to be 2 to 5 micrometers, and the hierarchical nature of the gradient distribution is achieved by gradually increasing the ratio of the active material to the solid electrolyte; where the proportion of the solid electrolyte in the middle layer increases by 10% for each layer.

[0009] Further preferably, a UV light source with a wavelength of 365 nanometers is used during the UV curing process, and the light power is set to 15 milliwatts per square centimeter, and the curing time is 20 seconds; The temperature of the rapid heat treatment is controlled at 180 degrees Celsius, and the time is 7 minutes, so that the thickness of the interfacial transition layer is stabilized within 100 to 150 nanometers.

[0010] Further preferably, the closed-loop feedback control system includes a laser thickness gauge for measuring the thickness of the deposition layer, a pressure sensor for monitoring the stability of the jet airflow, and a control unit; The control unit is connected to the laser thickness gauge and the pressure sensor, receives the thickness measurement data and the airflow stability data, and performs real-time analysis on the measurement data through a built-in processor, calculates the thickness deviation of the deposition layer and the air pressure fluctuation, and dynamically adjusts the movement path and spraying rate of the nozzle based on the calculation results, so that the deposition thickness of each layer of material is controlled within the range of ±5%.

[0011] More preferably, the cyclic voltammetry test measures the reversibility and capacity retention rate of the electrode in the range of 0.2C to 1C rate; the impedance spectrum analysis measures the interfacial impedance of the battery in the frequency range of 10 Hz to 1 MHz.

[0012] More preferably, the material layer with gradient distribution adopts a core-shell structure, and the core layer is the cathode active material , and the shell layer is solid electrolyte.

[0013] More preferably, a transverse reinforcement layer is added to the internal structure of the three-dimensional porous framework. The transverse reinforcement layer is metal nanowires or conductive polymer fibers, and the reinforcement layer is integrally formed with the framework skeleton through spray deposition technology; The spacing of the reinforcement layer is controlled within 50 to 100 microns to form a grid-like support structure; The transverse reinforcement layer is composed of metal nanowires or conductive polymer fibers, and its material is used because of its excellent mechanical properties and electrical conductivity. Integrating the reinforcement layer with the framework skeleton through spray deposition technology reduces the use of additional support materials on the one hand and maintains the light weight of the framework on the other hand. On the other hand, the metal nanowires and conductive polymer fibers themselves provide additional conduction paths, which helps to reduce the overall electronic impedance of the framework.

[0014] Since too small a spacing will increase the material usage and processing complexity, while too large a spacing may not fully support the mechanical strength of the framework, the reinforcement layer is distributed in a grid-like manner with a spacing of 50 to 100 microns. The spacing of 50 to 100 microns enables the grid structure to provide sufficient support force without affecting the pore distribution characteristics of the framework, ensuring the continuity and uniformity of the ion transport channels of the electrode.

[0015] More preferably, during the aerosol jet printing process, the overlap rate and particle distribution density of the deposition path are adjusted so that the pore structure of the three-dimensional electrode has multi-level channels, where the overlap rate of the initial path is 70% to 90% to form a main channel network, while the overlap rate of the secondary path is reduced to 50% to 70% to generate auxiliary channels, and the ratio of the main channels to the auxiliary channels in the finally formed pore structure is 3:1 to 4:1; By dynamically adjusting the overlap rate and particle distribution density of the deposition path during the aerosol jet printing process, the internal pore structure of the three-dimensional electrode is effectively optimized. The overlap rate of the initial path is set between 70% and 90%, and adjacent deposition trajectories have a large overlapping area to form a main channel network. The main channels have larger pore sizes and permeability and are the main ion transport paths. The overlap rate of the secondary path is controlled between 50% and 70%, and the overlapping area is smaller to form auxiliary channels.

[0016] Due to the above technical solutions adopted in the embodiments of the present invention, it has the following advantages: 1. Through the aerosol jet printing method, the present invention uniformly distributes conductive active materials and solid electrolytes on the surface of a three-dimensional porous framework in a layer-by-layer deposition manner. By precisely controlling the jet path, nozzle diameter, and material deposition rate, a tightly contacted interface between the solid electrolyte and the electrode material is formed, eliminating the interfacial side reactions easily caused by traditional high-temperature sintering and reducing the interfacial impedance. Further, through ultraviolet light curing or rapid heat treatment processes, the interfacial materials are cured immediately after printing, enhancing the mechanical bonding strength and chemical stability of the interface, reducing interfacial voids, and improving the transport efficiency of lithium ions at the interface.

[0017] 2. By constructing a three-dimensional porous framework structure, optimizing the pore distribution within the framework, and combining with the gradient deposition design of materials, the present invention forms multi-level ion channels. By gradually changing the ratio of active materials to solid electrolytes layer by layer, the content of solid electrolytes is higher in the inner layer, and the active materials are more abundant in the outer layer. Due to the gradient distribution, ions can quickly reach the electrode / electrolyte interface, significantly shortening the transport path, and enabling the electrode to still provide stable output power under high-rate conditions.

[0018] 3. Through the aerosol jet printing technology, the present invention controls the material deposition process at the micron or even nanometer level, enabling the distribution of active materials and solid electrolytes to reach a highly uniform state. During the printing process, by precisely adjusting the particle concentration, jet rate, and path overlap rate layer by layer, it is ensured that the material distribution of each layer is uniform; this not only increases the transport channels for ions and electrons but also avoids the common problems of material accumulation or sparseness in traditional coating methods, reducing local polarization and overheating phenomena, and significantly extending the battery cycle life.

[0019] The above summary is only for the purpose of the specification and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of the present invention will be readily apparent by reference to the drawings and the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0021] Figure 1 It is a flowchart of the preparation method of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0022] In the following text, only some exemplary embodiments are briefly described. As those skilled in the art can recognize, the described embodiments can be modified in various different ways without departing from the spirit or scope of the present invention. Therefore, the drawings and the description are considered to be exemplary in nature rather than restrictive.

[0023] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0024] As Figure 1 shown, the embodiments of the present invention provide a method for preparing a three-dimensional electrode of a all-solid-state battery based on aerosol jet printing, and the method consists of the following steps: S1. Construction of a three-dimensional porous framework: Using an aerosol jet printing device (Optomec Aerosol Jet system), a three-dimensional porous framework is constructed with a composite material of tin oxide (metal oxide) and carbon nanotubes as the conductive skeleton material; by mixing tin oxide with a particle size of 100 nanometers and carbon nanotubes with a diameter of 15 nanometers and a length of 2 micrometers in a mass ratio of 3:1, and using an ultrasonic device to process the mixture at a power of 200 watts for 10 minutes to ensure uniform material distribution; then, the ultrasonically treated material forms a uniform suspension, and is subsequently deposited through an aerosol jet printing system. Printing settings: The nozzle diameter is 40 micrometers, the jet pressure is controlled at 30 psi, the jet speed is set at 15 millimeters per second, the particle concentration is maintained at 1%. During the printing process, through real-time monitoring and feedback control, the stability of the deposition process is ensured, and situations such as nozzle blockage or unstable air flow are avoided. The printing path is carried out at a uniform spacing to ensure the flatness and continuity of the material layer. After multiple depositions, a three-dimensional framework structure with a regular pore distribution is formed. The porosity of the framework is a key parameter affecting the electrode performance, and the porosity is calculated by the following formula: ; wherein, is the actual density of the three-dimensional framework, is the theoretical density of the material. By adjusting the printing path, nozzle diameter and jet parameters, a three-dimensional porous framework with a porosity of 40% and an average pore diameter of 5 micrometers is finally obtained.

[0025] S2. Layer-by-layer deposition of the gradient distribution layer: On the surface of the three-dimensional framework constructed above, the composite material is deposited layer by layer using aerosol jet printing technology. The composite material consists of an active material , with a particle size of 80 nanometers and a solid-state electrolyte , with a particle size of 200 nanometers. The material ratio of the initial layer is solid-state electrolyte: active material = 3:1. For each additional layer, the proportion of the active material increases by 10% until the outermost layer reaches a ratio of 1:1. The deposition thickness of each layer of material is precisely controlled to be 3 microns, and a total of 10 layers are deposited, with a total thickness of approximately 30 microns. During the deposition process, the following formulas are used to calculate the effective conductivity and ionic conductivity of each gradient distribution layer: ; ; Where: is the effective conductivity of the gradient layer, is the effective ionic conductivity of the gradient layer; and are the material distribution weights, and are the conductivity and ionic conductivity of each layer respectively; After the deposition of each layer, the material ratio and deposition thickness are recorded in real time and input into the closed-loop feedback control system to ensure the uniform distribution of each layer of material and form a three-dimensional porous electrode with gradient distribution characteristics.

[0026] S3. Formation of the interface transition layer. After the deposition of the gradient distribution layer is completed, an interface transition layer is generated by using an ultraviolet curing process. The specific steps are as follows: S31. Use an ultraviolet light source with a wavelength of 365 nm, and set the light power to 15 mW / cm²; S32. Set the curing time to 20 seconds; S33. After ultraviolet curing treatment, a transition layer with a thickness of approximately 100 nm is formed at the interface. This transition layer enhances the bonding strength between the solid electrolyte and the active material at the microscopic level and further improves the interfacial ion conduction performance; S34. After the formation of the transition layer, the improvement effect of the interfacial ion conductivity before and after curing is evaluated by the following formula: ; Where, and are the interfacial ion conductivities before and after curing respectively; After being processed by the above steps, the ion conduction performance of the interface transition layer is improved and the interface impedance is reduced.

[0027] S4. Real-time feedback and optimization of printing parameters. During the printing process, the closed-loop feedback control system monitors and adjusts the process parameters in real time. The closed-loop feedback control system consists of a laser thickness gauge, a pressure sensor, and a control unit to ensure that the thickness of the deposited layer is uniform; In this embodiment, the laser thickness gauge measures the deposition thickness of the current layer in real time. After the data is transmitted to the control unit, it is compared with the target thickness to calculate the deviation value , Subsequently, the control unit uses the PID control algorithm to adjust the injection rate and the nozzle movement path. The PID control formula is: ; Where: , , are the proportional, integral, and differential gain coefficients, respectively; represents the deposition parameter for adjusting the nozzle injection rate; represents "at time , the instantaneous deviation value between the target thickness and the actual thickness; represents the error accumulation from the start time of control to the current time ; represents an infinitesimal time increment; represents the deviation accumulation from the start to the current time; represents the rate of change of the error with time; The proportional term provides a rapid response to the current deviation. The integral term eliminates systematic errors accumulated over a long time. The derivative term suppresses overshoot caused by too rapid change of the deviation.

[0028] The control unit inputs the initial values of , , into the closed-loop feedback control system, dynamically adjusts the nozzle speed and air pressure according to the measurement data, ensures that the deposition thickness deviation is kept within ±2%, monitors the stability of the air flow through a pressure sensor, and when the pressure fluctuation exceeds ±1 psi, the control unit automatically adjusts the injection rate and restores the air pressure to the target range. Through real-time feedback, the deposition accuracy and material distribution consistency in the printing process are improved.

[0029] S5. Electrochemical performance test: After completing the electrode preparation, a comprehensive electrochemical performance test is carried out. The test device includes an electrochemical impedance spectroscopy analyzer and a cyclic voltammetry instrument; Impedance spectroscopy analysis test: Using a Bio-Logic VSP electrochemical workstation, the measurement frequency range is from 10 mHz to 1 MHz, and the amplitude is 10 mV; The test shows that: the interfacial impedance is reduced from 200 ohm·square centimeter in the traditional process to below 40 ohm·square centimeter. The reduction of the interfacial impedance reflects the improvement of the ionic conductivity in the interfacial transition layer and the interfacial contact.

[0030] Cyclic voltammetry test: The cyclic voltammetry test was carried out using a three-electrode system. The working electrode was the prepared three-dimensional electrode, the reference electrode was Li metal, the auxiliary electrode was a Pt sheet, the electrolyte was a LiTFSI-PEGDME solution, the scanning voltage range was 2.8 - 4.3 V, and the scanning rate was 0.1 mV / s; The test shows that: The electrochemical reaction activity of the electrode is good, the oxidation-reduction peaks are symmetric, and the peak current density is high. At a 0.2C rate, the capacity retention rate reaches 95%, and at a 1C rate, the capacity retention rate is 85%.

[0031] As mentioned above, it is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of various changes or substitutions, and these should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing, characterized in that: The method consists of the following steps: S1. A three-dimensional porous framework is constructed based on a conductive skeleton material by aerosol jet printing technology. The porosity of the framework is calculated according to the formula ； Sure; in, is the actual density of the 3D frame, is the theoretical density of the material; The porosity of the frame ranges from 30% to 60%, the pore size ranges from 1 to 10 microns, the nozzle diameter ranges from 30 to 50 microns, the gas pressure is controlled at 20 to 50 psi, the particle concentration ranges from 0.5% to 2%, and the deposition speed ranges from 10 to 30 mm / sec; S2, depositing the composite material layer by layer on the surface of the porous frame by aerosol jet printing to form a gradient distribution layer; The gradient distribution layer is composed of a high-conductivity active material and a solid electrolyte. The particle size of the outermost layer is 50 to 100 nanometers. The active material and the solid electrolyte are gradually increased in proportion to the inner and outer layers, and finally reach a ratio of 80%. The effective conductivity and ionic conductivity of the gradient distribution layer are calculated by the following formulas: ； ； in, and is the material distribution weight, and are the electrical conductivity and ionic conductivity of each layer, respectively; S3. During the deposition of the gradient distribution layer, the printing speed, nozzle diameter and particle dispersion are adjusted in real time to optimize the material distribution, and after the deposition is completed, an interface transition layer with a thickness of 50 to 200 nanometers is formed between the frame and the deposited layer by ultraviolet curing or rapid thermal treatment. The ionic conductivity ratio of the interface transition layer after curing is characterized by the following formula: ； in, and are the interfacial ionic conductivity before and after curing, respectively; S4. During the deposition process, a closed-loop feedback control system and a PID control algorithm are used to adjust the deposition parameters in real time, wherein the PID control formula is: ； in, is the deviation between the target thickness and the actual thickness, , , are the proportional, integral and differential gain coefficients; It represents the deposition parameter adjusted for the nozzle jet rate; means "at the time When , the instantaneous deviation between the target thickness and the actual thickness; Indicates the time from the start of control To the current time The amount of error accumulation; represents an infinitesimal time increment; Indicates the accumulated deviation from the beginning to the current moment; It represents the rate of change of error over time; S5. The performance index of the completed three-dimensional electrode is verified by electrochemical performance test, wherein the performance test includes impedance spectroscopy analysis and cyclic voltammetry for determining the interface resistance. and the cycling stability of active materials, the reduction of interfacial resistance by Formula determination; in, is the bulk resistance of the solid electrolyte, is the optimized interface impedance difference.

2. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The conductive skeleton material includes carbon nanotubes and metal oxides, wherein the diameter of the carbon nanotubes is 10 to 20 nanometers, the length is 1 to 5 micrometers, and the particle size of the metal oxide is 50 to 200 nanometers. It is prepared by a method combining ultrasonic dispersion and high-speed stirring, wherein the ultrasonic power is 200 watts, the stirring speed is 1500 revolutions per minute, and the time is 2 hours.

3. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The porosity of the porous framework is controlled to be 30% to 40%. The porosity of the porous framework is controlled to be within a range and uniform by adjusting the nozzle diameter to 40 to 50 microns, the air pressure to 30 to 50 psi, the particle concentration to 1% to 2% and the deposition speed to 10 mm / s.

4. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The outer layer of the gradient distribution layer is an active material, the particle size of the active material is in the range of 60 to 100 nanometers, the inner layer of the gradient distribution layer is deposited with a solid electrolyte material, the particle size of the solid electrolyte material is in the range of 200 to 300 nanometers, the thickness of each layer in the gradient distribution layer is controlled to be 2 to 5 microns, and the hierarchical nature of the gradient distribution is achieved by gradually increasing the ratio of the active material to the solid electrolyte material; The proportion of solid electrolyte in the middle layer of the gradient distribution layer increases by 10% per layer.

5. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The UV curing process uses a UV light source with a wavelength of 365 nanometers, and the light power is set to 15 milliwatts per square centimeter, and the curing time is 20 seconds; The temperature of the rapid thermal treatment is controlled at 180 degrees Celsius and the time is 7 minutes, so that the thickness of the interface transition layer is stabilized at 100 to 150 nanometers.

6. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The closed-loop feedback control system includes a laser thickness gauge for measuring the thickness of the deposited layer and a pressure sensor and a control unit for monitoring the stability of the jet gas flow; The control unit is connected to the laser thickness gauge and the pressure sensor, receives thickness measurement data and airflow stability data, and performs real-time analysis on the measurement data through a built-in processor, calculates the thickness deviation and air pressure fluctuation of the deposited layer, and dynamically adjusts the movement path and injection rate of the nozzle based on the calculation results, so that the deposition thickness of each layer of material is controlled within the range of ±5%.

7. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The cyclic voltammetry test measures the reversibility and capacity retention of the electrode within a rate range of 0.2C to 1C; the impedance spectrum analysis measures the interfacial impedance of the battery within a frequency range of 10Hz to 1MHz.

8. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The gradient distribution material layer adopts a core-shell structure, and the core layer is the positive electrode active material , and the shell is Solid electrolyte.

9. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: The three-dimensional porous framework has a transverse reinforcement layer added to the internal structure of the framework, wherein the transverse reinforcement layer is a metal nanowire or a conductive polymer fiber, and the reinforcement layer is composited with the framework skeleton to form an integral body through a spray deposition technology; The spacing between the reinforcement layers is controlled to be 50 to 100 microns, forming a grid-like support structure.

10. The method for preparing three-dimensional electrodes for all-solid-state batteries based on aerosol jet printing according to claim 1, characterized in that: During the aerosol jet printing process, the overlap rate of the deposition paths and the particle distribution density are adjusted to give the pore structure of the three-dimensional electrode a multi-layered channel. The overlap rate of the initial paths is 70% to 90%, forming a main channel network, while the overlap rate of the secondary paths is reduced to 50% to 70%, generating auxiliary channels. The ratio of main channels to auxiliary channels in the final pore structure is 3:1 to 4:1.

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