Intrinsic solid-state ion mobility testing method and apparatus based on optical imaging

Abstract

The application provides an intrinsic solid-state ion mobility testing method and device based on optical imaging, and relates to the technical field of performance testing of solid-state ion electrolyte materials.The method comprises the following steps: assembling a testing sample pool; performing an electrification test on the testing sample pool; extracting size information of solid-state electrolyte powder particles to be tested from an optical image; extracting a curve of optical intensity of the solid-state electrolyte powder particles to be tested changing with time from the optical image, determining time information of optical response of the particles from start to balance in a voltage change process based on the curve; determining an electric field strength under a testing condition according to a voltage size and a total thickness of a thin-layer insulating substrate; and determining intrinsic ion mobility of the solid-state electrolyte powder particles to be tested according to the size information, the time information and the electric field strength.

Description

Technical Field

[0001] This invention relates to the field of performance testing technology for solid-state ion electrolyte materials, and more particularly to an intrinsic solid-state ion mobility testing method and apparatus based on optical imaging. Background Technology

[0002] This section is intended to provide background or context for embodiments of the present invention. The description herein is not intended to imply that it is prior art simply because it is included in this section.

[0003] Solid-state ionic materials have wide applications in modern society, including ion batteries, fuel cells, photovoltaics, and semiconductors. Consequently, the scientific and industrial communities are interested in the migration rate of ions within solid materials and have developed a series of methods for measuring it.

[0004] Taking applications in the ion battery industry as an example (it should be noted that research on ion mobility within solid materials is actually universally applicable; that is, it can be used to test solid-state ion electrolytes used in ion batteries, as well as many solid-state ion materials such as perovskite materials used in photovoltaics), the electrolyte, as a crucial component of ion batteries, has ion mobility as one of its most important indicators. Higher ion mobility allows for higher charge and discharge rates, enabling higher-power applications (such as pure electric aircraft) and faster charging (such as charging to 80% in 5 minutes). Therefore, a persistent and core goal in the field of solid-state ion electrolyte materials is to develop solid-state electrolyte materials with higher ion mobility. Based on this, the ion mobility methods commonly used in the solid-state ion electrolyte industry currently include steady-state DC polarization and electrochemical impedance spectroscopy (EIS). These will be discussed in detail below.

[0005] Taking the constant voltage polarization method as an example, its main drawback lies in the sample preparation stage. The core functional unit of a solid electrolyte is actually a series of material particles ranging in size from hundreds of nanometers to tens of micrometers. Their function in an all-solid-state battery is achieved by dispersing individual particles within the positive electrode material (such as lithium iron phosphate). Therefore, testing the ion mobility of the material at the particle scale is actually more meaningful. However, due to limitations such as the difficulty in fabricating electrodes to the micro-nano scale, the difficulty in achieving current detection accuracy at the single-particle scale (fA~pA level), and the presence of contact resistance at the electrode or particle interface, the constant voltage polarization method cannot test individual ion electrolyte particles. Therefore, a complex and cumbersome method is needed to fabricate the particles into a single thin sheet for further testing. As can be seen from the above description, the biggest problem with this current preparation method is the introduction of numerous interfaces in the process from particles to thin sheets and then to symmetric batteries, including interfaces between particles and between particles and metallic lithium. These interfaces bring three important issues. First, the presence of an interface makes it impossible for this method to obtain the true intrinsic mobility of the material; instead, it can only measure the overall mobility, which is always affected by the resistance to ion transport at the interface. Second, to minimize the influence of the interface, current methods involve a complex sample preparation process. While this can reduce the impact of interface contact quality on the test to some extent, various conditions in the sample preparation process, including the pressure of the tablet, the temperature and time of sintering, the operation during lithium brushing, and the magnitude of the external pressure applied during the final test, all significantly affect the interface contact and thus the test results. This poses a significant challenge to the repeatability and reliability of the method, and is one of the important reasons why the ion mobility results of the same material reported in the literature can differ by several orders of magnitude. Due to the significant impact of sample preparation, even if the mobility of two ion electrolyte materials, A and B, is measured, it is often impossible to directly determine whether the difference lies in the quality of the materials themselves or in the control of the sample preparation conditions. This predicament greatly reduces the value of the test results and also reduces the efficiency of material improvement and development.

[0006] For AC impedance spectroscopy, sample preparation also plays a role. Although under ideal conditions, the trans-interfacial and intraparticle migration of ions can be distinguished spectrally, in actual testing, the highly complex and non-uniform contact between particles or interparticle interfaces makes it difficult to avoid their influence. Furthermore, AC impedance spectroscopy lacks spatial resolution; its final test results are an average of countless particles in a thin film, failing to faithfully reflect the intrinsic properties of the particles.

[0007] In summary, current testing methods based on electricity and electrochemistry all suffer from the following two problems: 1. They involve complex sample preparation processes, greatly increasing operational inconvenience and, more importantly, introducing numerous interfaces, making it impossible for test results to reflect the intrinsic properties of the material itself; 2. The tests are significantly affected by sample preparation conditions, resulting in unsatisfactory repeatability and accuracy. When test results differ for different materials, it is difficult to determine whether the difference is due to variations in the material's inherent properties or poor control of sample preparation conditions, greatly reducing the efficiency of testing in guiding material optimization and development. Therefore, a technical solution that can overcome these shortcomings is urgently needed. Summary of the Invention

[0008] To address the problems existing in the prior art, this invention proposes a method and apparatus for testing intrinsic solid-state ion mobility based on optical imaging.

[0009] In a first aspect of the present invention, a method for measuring the intrinsic solid-state ion mobility based on optical imaging is proposed, the method comprising:

[0010] Assemble a test sample cell; wherein, the solid electrolyte powder particles to be tested are modified and fixed on the insulating side surface of a first thin-layer insulating substrate, and the solid electrolyte powder particles to be tested do not contact the conductive coating on the first thin-layer insulating substrate; a second thin-layer insulating substrate is placed on top of the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested, forming a three-layer structure, with the conductive coatings of the two thin-layer insulating substrates located on the outer sides of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode;

[0011] The test sample cell is subjected to an electrical test; wherein, the packaged test sample cell is placed within the observation range of the optical imaging device; a voltage is applied to the conductive coating of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation, and the optical image of the solid electrolyte powder particles under test is acquired in real time by the optical imaging device.

[0012] Extract the size information of the solid electrolyte powder particles to be tested from the optical image;

[0013] The optical intensity curve of the solid electrolyte powder particles under test as a function of time is extracted from the optical image, and the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change is determined based on the curve.

[0014] The electric field strength under test conditions is determined based on the applied voltage and the total thickness of the thin insulating substrate.

[0015] The intrinsic ion mobility of the solid electrolyte powder particles under test is determined based on the size information, time information, and electric field strength.

[0016] In a second aspect of the present invention, an intrinsic solid-state ion mobility testing device based on optical imaging is provided. This device includes: an applied testing device, an optical imaging device, and a data processing device; wherein...

[0017] The power-on testing device is used to perform power-on testing on the test sample cell; wherein, the packaged test sample cell is placed within the observation range of the optical imaging device; a voltage is applied to the conductive plating layer of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation, and the optical imaging device acquires optical images of the solid electrolyte powder particles under test in real time.

[0018] The assembly process of the test sample cell includes: modifying and fixing the solid electrolyte powder particles to be tested onto the insulating side surface of a first thin-layer insulating substrate, wherein the solid electrolyte powder particles to be tested do not contact the conductive coating on the first thin-layer insulating substrate; covering the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested onto a second thin-layer insulating substrate, forming a three-layer structure, wherein the conductive coatings of the two thin-layer insulating substrates are respectively located on the outer side of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode.

[0019] The data processing device is used to extract the size information of the solid electrolyte powder particles to be tested from the optical image;

[0020] The optical intensity curve of the solid electrolyte powder particles under test as a function of time is extracted from the optical image, and the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change is determined based on the curve.

[0021] The electric field strength under test conditions is determined based on the applied voltage and the total thickness of the thin insulating substrate.

[0022] The intrinsic ion mobility of the solid electrolyte powder particles under test is determined based on the size information, time information, and electric field strength.

[0023] This invention proposes an intrinsic solid-state ion mobility testing method and apparatus based on optical imaging, enabling precise measurement of the intrinsic mobility of solid-state ion electrolyte materials. This invention fundamentally solves the problems of inaccurate results and poor repeatability caused by complex sample preparation processes and limited testing conditions in traditional methods. The overall scheme can measure the intrinsic ion mobility of ion conductor materials, and the test results are no longer affected by sample preparation processes and testing conditions, maximizing the reflection of the material's inherent performance. It can serve as an effective supplement to traditional methods, thereby further improving the efficiency of material optimization and development. Compared with traditional methods, this invention eliminates the need for cumbersome sample preparation, making operation simpler and testing more efficient. Furthermore, it has spatial resolution, enabling separate measurement of the performance of different individuals within a batch of material particles, increasing the depth and breadth of information obtained through testing, thus acquiring richer material performance information and greatly improving the efficiency of material optimization and development. Attached Figure Description

[0024] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a schematic diagram of the intrinsic solid-state ion mobility testing method based on optical imaging according to an embodiment of the present invention.

[0026] Figure 2 This is a schematic diagram of the sample preparation process of a longitudinal electric field device according to an embodiment of the present invention.

[0027] Figure 3 This is a schematic diagram of the architecture of a longitudinal electric field device according to an embodiment of the present invention.

[0028] Figure 4 This is a schematic diagram of the sample preparation process of a transverse electric field device according to an embodiment of the present invention.

[0029] Figure 5 This is a schematic diagram of the architecture of a transverse electric field device according to an embodiment of the present invention.

[0030] Figure 6 This is a schematic diagram of the intrinsic solid-state ion mobility testing method based on optical imaging, according to another embodiment of the present invention.

[0031] Figure 7 This is a schematic diagram of the test results of a lithium lanthanum zirconium oxide powder sample according to a specific embodiment of the present invention.

[0032] Figure 8 This is a schematic diagram of a computer device structure according to an embodiment of the present invention. Detailed Implementation

[0033] The principles and spirit of the invention will now be described with reference to several exemplary embodiments. It should be understood that these embodiments are given merely to enable those skilled in the art to better understand and implement the invention, and are not intended to limit the scope of the invention in any way. Rather, these embodiments are provided to make this disclosure more thorough and complete, and to fully convey the scope of this disclosure to those skilled in the art.

[0034] Those skilled in the art will recognize that embodiments of the present invention can be implemented as a system, apparatus, device, method, or computer program product. Therefore, this disclosure can be specifically implemented in the following forms: entirely hardware, entirely software (including firmware, resident software, microcode, etc.), or a combination of hardware and software.

[0035] According to embodiments of the present invention, a method and apparatus for testing intrinsic solid-state ion mobility based on optical imaging are proposed, relating to the field of performance testing technology for solid-state ion electrolyte materials. It should be noted that the intrinsic solid-state ion mobility test of this application has universality for materials, and can be applied to the testing of solid-state ion electrolytes in the ion battery industry, as well as to the testing of many solid-state ion materials such as perovskite materials used in the photovoltaic field, and also to the testing of ion conductor materials in other fields.

[0036] The principles and spirit of the present invention will be explained in detail below with reference to several representative embodiments.

[0037] Figure 1 This is a schematic flowchart of an embodiment of the intrinsic solid-state ion mobility testing method based on optical imaging according to the present invention. Figure 1 As shown, the method includes:

[0038] S101, Assembly and testing sample cell;

[0039] In this process, the solid electrolyte powder particles to be tested are modified and fixed on the insulating side surface of the first thin-layer insulating substrate, and the solid electrolyte powder particles to be tested do not contact the conductive coating on the first thin-layer insulating substrate; a second thin-layer insulating substrate is placed on top of the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested, forming a three-layer structure, with the conductive coatings of the two thin-layer insulating substrates located on the outer sides of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode.

[0040] S102, Perform an electrical test on the test sample cell;

[0041] The process involves placing the encapsulated test sample cell within the observation range of an optical imaging device; applying voltage to the conductive plating layers of the thin insulating substrates on both sides of the test sample cell to perform periodic electrical excitation; and using the optical imaging device to acquire optical images of the solid electrolyte powder particles under test in real time.

[0042] S103, extract the size information of the solid electrolyte powder particles to be tested from the optical image.

[0043] S104, extract the curve of the optical intensity of the solid electrolyte powder particles under test changing with time from the optical image, and determine the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change process based on the curve.

[0044] S105, determine the electric field strength under test conditions based on the applied voltage and the total thickness of the thin insulating substrate.

[0045] S106. Based on the size information, time information, and electric field strength, determine the intrinsic ion mobility of the solid electrolyte powder particles to be tested.

[0046] To provide a clearer explanation of the above-described intrinsic solid-state ion mobility testing method based on optical imaging, each step will be described in detail below.

[0047] In one embodiment, for S101, the test sample cell is assembled. The solid electrolyte powder particles to be tested are modified and fixed to the insulating side surface of a first thin-layer insulating substrate, and the solid electrolyte powder particles to be tested do not contact the conductive plating on the first thin-layer insulating substrate; a second thin-layer insulating substrate is placed over the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested, forming a three-layer structure, with the conductive plating on the two thin-layer insulating substrates located on the outer sides of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode.

[0048] Specifically, the solid electrolyte powder particles to be tested are modified on the insulating side surface of the first thin-layer insulating substrate in a certain way, and the solid electrolyte powder particles to be tested do not contact the conductive plating layer on the first thin-layer insulating substrate.

[0049] The modification method is at least one of sieving, spin coating, and drop coating.

[0050] The conductive coating is made of at least one of gold, aluminum, copper, and indium tin oxide;

[0051] The thin insulating substrate is made of at least one of glass, polyethylene terephthalate (PET), polymethylsiloxane (PDMS), and polyimide (PI);

[0052] Thin-layer insulation materials can be made of materials such as glass, polyethylene terephthalate (PET), polymethylsiloxane (PDMS), and polyimide (PI).

[0053] A second thin insulating substrate is placed over a first thin insulating substrate modified with the solid electrolyte powder particles to be tested, forming a three-layer structure ("sandwich" structure). The conductive plating layers of the two thin insulating substrates are located on the outer sides of the three-layer structure. This method simplifies the sample preparation process, avoids the complex sample preparation steps in traditional methods, and reduces the introduction of interfaces, thereby improving the accuracy and repeatability of the test results.

[0054] The three-layer structure is a "sandwich" structure consisting of a first thin insulating substrate, the solid electrolyte powder particles to be tested, and a second thin insulating substrate. The particles to be tested are sandwiched in the middle of the insulating material. This design places the particles to be tested at the center of the parallel plate capacitor. When a voltage is applied to the metal on both sides, an electric field is formed between the metals. When the electric field strength reaches a certain level, the ions inside the ionic electrolyte particles will be redistributed inside the particles under the drive of the electric field, thus creating high-concentration and low-concentration ion sites inside the particles, which is the source of the optical signal to be tested.

[0055] The following section provides a detailed explanation of the vertical electric field architecture mode and the horizontal electric field architecture mode.

[0056] refer to Figures 2 to 3 This is a schematic diagram of the sample preparation process and architecture of a longitudinal electric field device according to an embodiment of the present invention. Figure 2 As shown, the upper yellow structure is a substrate with a conductive coating, which can be made of materials such as gold, aluminum, copper, or ITO (indium tin oxide). The lower light-colored structure is an insulating thin layer, which can be made of materials such as glass, PET, PDMS, or PI. The solid electrolyte powder particles to be tested are loaded onto the surface of the insulating thin layer through methods such as sieving, drop coating, or spin coating (avoiding contact with the conductive coating to eliminate interface interference), forming a substrate that supports the particles on the insulating side.

[0057] like Figure 3 As shown, after assembly into a sandwich structure (first thin insulating substrate, solid electrolyte powder particles to be tested, and second thin insulating substrate), the conductive coatings on the upper and lower substrates are connected to the positive and negative electrodes, respectively (only the upper electrode is connected to the positive electrode, and only the lower electrode is connected to the negative electrode). After applying a voltage, an electric field is formed between the upper and lower conductive coatings. The ions inside the particles are redistributed due to the electric field, providing a physical basis for subsequent optical imaging to capture the optical signals of ion migration.

[0058] refer to Figures 4 to 5 This is a schematic diagram of sample preparation and architecture of a transverse electric field device according to an embodiment of the present invention.

[0059] like Figure 4As shown, a conductive partition design is adopted in the sample preparation process of the transverse electric field device. The gold-plated PET substrate achieves selective conductivity through conductive copper tape, insulating tape, and gaskets: some areas are connected to the top or bottom cover of the battery to achieve conductivity, while some areas are isolated by insulation to achieve non-conductivity, ultimately forming partitions where only the top is conductive (connected to the positive electrode) and only the bottom is conductive (connected to the negative electrode), ensuring that the electric field acts precisely on the intermediate particles. gap: 60μm indicates the gap, reflecting the gap control of the conductive coating (affecting the electric field distribution range).

[0060] like Figure 5 As shown, after applying voltage, the charges of the upper and lower conductive coatings form an electric field in the gap region, driving ion migration within the particles and providing a prerequisite for the correlation between ion movement and changes in optical signals for optical imaging detection.

[0061] S101 drives the redistribution of ions within the particle, forming high-concentration and low-concentration sites, providing a foundation for subsequent optical imaging. It should be noted that, because commonly used solid electrolyte particles are sensitive to water and oxygen in the air, the three-layer structure is assembled under an inert atmosphere and encapsulated in a sealed cavity. The use of an inert atmosphere effectively protects the solid electrolyte particles from the effects of water and oxygen in the air, ensuring the stability and reliability of the test. The inert gas can be Ar2 or N2.

[0062] In one embodiment, for step S102, an electrical test is performed on the test sample cell. The packaged test sample cell is placed within the observation range of the optical imaging device; a voltage is applied to the conductive plating of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation, and the optical imaging device acquires optical images of the solid electrolyte powder particles under test in real time.

[0063] In one embodiment, the waveform of the voltage applied to the conductive plating of the thin insulating substrate on both sides of the test sample cell is at least one of a periodic electrical excitation, including a square wave, a sine wave, and a triangular wave. In practical applications, other waveforms may also be used to apply the voltage, and the present invention does not impose strict limitations on this.

[0064] In one embodiment, the applied voltage is a pulse voltage, ranging from 0V to a preset test voltage. This preset test voltage is used to drive the redistribution of ions within the solid electrolyte powder particles under test. This method allows for real-time observation of changes in the ion distribution within the particles, thereby obtaining detailed optical response information.

[0065] Specifically, the encapsulated test sample cell is placed within the observation range of an optical imaging device, which can be an optical microscope, a stereo microscope, a lens camera assembly, etc. These devices can resolve solid electrolyte powder particles of 100 nanometers to 20 micrometers in size and record optical images in real time.

[0066] Taking the application of a square wave as an example of periodic electrical excitation, a voltage is applied to the conductive plating of a thin insulating substrate on both sides of the test sample cell. The voltage is cyclically switched between on and off states, and optical images of the solid electrolyte powder particles under test are acquired in real time using the optical imaging device. When the applied voltage meets a certain value, the ions inside the particles will rearrange under the drive of the electric field, forming high-concentration and low-concentration ion sites. This process leads to changes in the optical properties of different sites inside the particles, thereby affecting the interaction between light and particles. Observed from the recorded images, these changes will manifest as changes in the overall optical intensity of the particles, the local optical intensity inside the particles, and the overall optical intensity distribution of the particles. Accordingly, by repeatedly applying and removing the voltage, the particles will repeatedly switch between a voltage-free state and a voltage-enabled state. By recording the image information of the particles during this process, the test can be completed.

[0067] For periodic electrical excitation of other waveforms (sine wave, triangular wave, etc.) with applied voltage, the principle is similar to the above. The core is to apply power to the test sample cell and acquire optical images of the solid electrolyte powder particles to be tested, which will not be elaborated here.

[0068] In one embodiment, for S103, the size information of the solid electrolyte powder particles to be tested is extracted from the optical image.

[0069] The size information of the solid electrolyte powder particles under test is extracted from the optical image and quantified using the equivalent circle radius to obtain the size information r. This step allows for accurate acquisition of the particle size, providing accurate data support for subsequent calculations.

[0070] In one embodiment, for S104, the curve of the optical intensity of the solid electrolyte powder particles to be tested changing with time is extracted from the optical image, and the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change is determined based on the curve.

[0071] Specifically, the time information is quantified using a time constant to obtain the time information. This step allows for the accurate acquisition of the particle's optical response time, providing a crucial parameter for calculating intrinsic ion mobility.

[0072] In one embodiment, for S105, the electric field strength under the test conditions is determined based on the magnitude of the applied voltage and the total thickness of the thin insulating substrate.

[0073] The electric field strength is determined using the following formula:

[0074]

[0075] In the formula, E represents the electric field strength; U represents the applied voltage; and d represents the total thickness of the thin insulating substrate.

[0076] It should be noted that the total thickness of the thin insulating substrate mentioned here refers to the sum of the thicknesses of the two thin insulating substrates (i.e., the sum of the thicknesses of the first and second thin insulating substrates). This step allows for the accurate calculation of the electric field strength under the test conditions, providing precise parameters for subsequent calculations.

[0077] In one embodiment, for S106, the intrinsic ion mobility of the solid electrolyte powder particles to be tested is determined based on the size information, time information, and electric field strength.

[0078] The specific calculation formula is as follows:

[0079]

[0080] In the formula, μ represents the intrinsic ion mobility; r represents the size information; τ represents the time information; and E represents the electric field strength.

[0081] This step allows for the accurate calculation of the intrinsic ion mobility of the solid electrolyte powder particles under test, thereby enabling precise measurement of the intrinsic properties of the material.

[0082] In another embodiment, reference Figure 6 This is a schematic diagram of a method for testing the intrinsic solid-state ion mobility based on optical imaging, according to another embodiment of the present invention. Figure 6 As shown, the method also includes:

[0083] S107, the intrinsic ion solid mobility of different particles in the same group of solid electrolyte powders to be tested is tested to obtain the intrinsic ion mobility of different particles corresponding to the group of solid electrolyte powders to be tested.

[0084] This step allows for the separate measurement of the properties of different individual particles within a batch of material, increasing the depth and breadth of information obtained from the test and helping to more comprehensively evaluate the material's performance.

[0085] The intrinsic ion solid-state mobility testing method based on optical imaging proposed in this invention enables accurate measurement of the intrinsic mobility of solid-state ion electrolyte materials. Compared with existing technologies, this invention fundamentally solves the problems of inaccurate test results and poor repeatability caused by the complexity of sample preparation processes and limited testing conditions in traditional methods. This invention is simple to operate, highly efficient, and can detect individual ion electrolyte particles, providing spatial resolution and thus obtaining richer material performance information, greatly improving the efficiency of material optimization and development.

[0086] The intrinsic solid-state ion mobility testing method based on optical imaging of the present invention will be described below with reference to a specific embodiment.

[0087] Assembly and testing of sample cells:

[0088] The lithium lanthanum zirconium oxide (LLZO) powder particles to be tested were sieved and coated onto a 50-micrometer-thick gold-plated PET film. Then, another 50-micrometer-thick gold-plated PET film was placed over the particles, forming a "sandwich" structure. The LLZO particles were sandwiched in the middle of the PET film, with conductive gold plating on both sides, and the entire structure was encapsulated in a sealed cavity. All of these operations were performed in a glove box. This completes the assembly of the test sample cell.

[0089] Power-on test:

[0090] The LLZO sample cell described above is placed under an optical imaging device, and a pulsed voltage of 120V-0V is applied to it while the optical image of the particle under test is recorded in real time. As mentioned above, by repeatedly applying voltage (120V) and removing voltage (0V), the particle will repeatedly switch between a voltage-enabled state and a voltage-free state. The image information of the particle is recorded during this process, thus completing the test.

[0091] Data processing:

[0092] The radius of the target LLZO particle in the image can be directly identified as 2.7 μm through optical imaging;

[0093] By extracting the curve of the optical intensity of the particle changing with time, and further obtaining from the curve the time taken for the optical response of the particle to go from the no-voltage state to the voltage-enabled state from the beginning to equilibrium. ), the particle The value is 1.7s;

[0094] The electric field strength under the test conditions can be calculated by the magnitude of the applied voltage and the thickness of the thin material used, and is denoted as E. The calculated value under the experimental conditions in this case is 1.2 × 10⁴ V / cm.

[0095] The calculated ion mobility μ of the particles is approximately 1.32 × 10⁻⁴ cm² / V·s, which is consistent with the data.

[0096] refer to Figure 7 This is a schematic diagram illustrating the test results of a lithium lanthanum zirconium oxide powder sample according to a specific embodiment of the present invention. Figure 7 As shown, in Figure 7 In the schematic diagram of particle imaging (fundamentals of optical observation) in Part A, the bright spots against the black background represent the solid electrolyte particles to be measured. The red dashed circles mark the ROI (region of interest), which is used to focus and analyze the optical signals of single / local particles. The scale bar of 5 μm indicates that the observed particle size is at the micrometer level, reflecting the ability of optical imaging to resolve tiny particles.

[0097] exist Figure 7 Part B shows a schematic diagram of the relationship between the average gray value of the ROI and time, the relationship between the applied voltage and time, and the relationship between the average FFT spectrum of the ROI, which are used to perform correlation analysis of voltage stimulation, optical response, and frequency characteristics.

[0098] Among them, Figure 7 In the diagram illustrating the relationship between the average gray value of the ROI and time (Part B), the vertical axis ΔI represents the gray value change (reflecting the optical intensity of the particles), and the horizontal axis t(s) represents time. The periodic fluctuations of the curve are synchronized with the applied voltage, indicating that voltage stimulation causes ion migration within the particles, thereby altering the optical properties (gray value) of the particles. The red dashed box in the diagram marks the response segment under voltage application. (Reference) Figure 7 Part C shows a partially enlarged schematic diagram, which is a... Figure 7 The diagram in Part B showing the relationship between the average grayscale value of the ROI and time is enlarged to reveal the content shown within the red dashed box. (Reference) Figure 7 Part C presents the dynamic analysis of the optical response (extracting the time constant). The vertical axis represents the normalized light intensity (I / I0, where I0 is the initial light intensity), and the horizontal axis represents time t (s). The curve illustrates the process of particle light intensity recovering from a non-equilibrium state to an equilibrium state after voltage switching. τ = 1.50s and τ = 1.76s are time constants, reflecting the speed at which ion migration reaches equilibrium; the smaller the τ, the faster the ion migration rate. (Time constants) It is the core parameter for calculating intrinsic ion mobility.

[0099] exist Figure 7In the schematic diagram of the relationship between applied voltage and time in part B (Applied Voltage Over Time), the red square wave is a periodic pulse voltage (the voltage cycles between on and off), which is the external stimulus source that drives the migration of ions within the particle and is used to observe the dynamic response process of the particle.

[0100] exist Figure 7 In the diagram showing the relationship between the ROI average FFT spectrum in Part B (ROI Average FFTS pectrum), the horizontal axis represents frequency (mHz) and the vertical axis represents amplitude. The peak value of the spectrum corresponds to the periodic frequency of the applied voltage, verifying the frequency correlation between the optical response and the voltage stimulus (i.e., the optical change is directly caused by voltage-driven ion migration).

[0101] Ion migration within solid electrolyte particles is driven by periodic voltage stimulation. Optical imaging captures the changes in particle optical intensity over time. Key parameters (such as time constant) are then extracted through time-series analysis, frequency analysis, and kinetic fitting. This ultimately provides data support for calculating intrinsic ion mobility.

[0102] Compared to existing technologies, the main improvements of this application are:

[0103] This invention presents a complete approach to intrinsic solid-state ion mobility testing based on optical imaging. The overall scheme eliminates the need for electrical modulation, using optical imaging to detect the response of a particle under electrical modulation. This approach significantly differs from the core logic of all traditional methods that rely on electrical modulation and detection, making it possible to characterize intrinsic properties at the particle scale and offering numerous advantages such as high throughput, high sensitivity, non-contact operation, and ease of use. The specific implementation employs a sandwich structure and particle modification. This invention improves the optical image processing method, including the quantization of the time constant after local intensity extraction. Furthermore, this application is applicable to the testing of ion-conducting materials in various fields, and its practical applications are not limited to the field of ion batteries.

[0104] It should be noted that although the operation of the method of the present invention has been described in a specific order in the above embodiments and figures, this does not require or imply that the operations must be performed in that specific order, or that all the operations shown must be performed to achieve the desired result. Additionally or alternatively, certain steps may be omitted, multiple steps may be combined into one step, and / or one step may be broken down into multiple steps.

[0105] After introducing the method of the exemplary embodiments of the present invention, the intrinsic solid-state ion mobility testing device based on optical imaging of the exemplary embodiments of the present invention will be introduced next.

[0106] The implementation of the intrinsic solid-state ion mobility testing device based on optical imaging can refer to the implementation of the above method, and the repeated parts will not be described again. The term "module" or "unit" used below can be a combination of software and / or hardware to achieve a predetermined function. Although the device described in the following embodiments is preferably implemented in software, hardware implementation, or a combination of software and hardware, is also possible and contemplated.

[0107] Based on the same inventive concept, this invention also proposes an intrinsic solid-state ion mobility testing device based on optical imaging. This device includes: an applied testing device, an optical imaging device, and a data processing device; wherein...

[0108] The power-on testing device is used to perform power-on testing on the test sample cell; wherein, the packaged test sample cell is placed within the observation range of the optical imaging device; a voltage is applied to the conductive plating layer of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation, and the optical imaging device acquires optical images of the solid electrolyte powder particles under test in real time.

[0109] The assembly process of the test sample cell includes: modifying and fixing the solid electrolyte powder particles to be tested onto the insulating side surface of a first thin-layer insulating substrate, wherein the solid electrolyte powder particles to be tested do not contact the conductive coating on the first thin-layer insulating substrate; covering the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested onto a second thin-layer insulating substrate, forming a three-layer structure, wherein the conductive coatings of the two thin-layer insulating substrates are respectively located on the outer side of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode.

[0110] The data processing device is used to extract the size information of the solid electrolyte powder particles to be tested from the optical image;

[0111] The optical intensity curve of the solid electrolyte powder particles under test as a function of time is extracted from the optical image, and the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change is determined based on the curve.

[0112] The electric field strength under test conditions is determined based on the applied voltage and the total thickness of the thin insulating substrate.

[0113] The intrinsic ion mobility of the solid electrolyte powder particles under test is determined based on the size information, time information, and electric field strength.

[0114] It should be noted that although several modules of the intrinsic solid-state ion mobility testing device based on optical imaging have been mentioned in the detailed description above, this division is merely exemplary and not mandatory. In fact, according to embodiments of the invention, the features and functions of two or more modules described above can be embodied in a single module. Conversely, the features and functions of a single module described above can be further divided and embodied by multiple modules.

[0115] Based on the aforementioned inventive concept, such as Figure 8 As shown, the present invention also proposes a computer device 800, including a memory 810, a processor 820, and a computer program 830 stored in the memory 810 and executable on the processor 820. When the processor 820 executes the computer program 830, it implements the aforementioned intrinsic solid-state ion mobility testing method based on optical imaging.

[0116] Based on the aforementioned inventive concept, the present invention proposes a computer-readable storage medium storing a computer program, which, when executed by a processor, implements the aforementioned intrinsic solid-state ion mobility testing method based on optical imaging.

[0117] Based on the aforementioned inventive concept, the present invention proposes a computer program product, which includes a computer program that, when executed by a processor, implements an intrinsic solid-state ion mobility testing method based on optical imaging.

[0118] This invention proposes an intrinsic solid-state ion mobility testing method and apparatus based on optical imaging, enabling precise measurement of the intrinsic mobility of solid-state ion electrolyte materials. Compared with existing technologies, this invention fundamentally solves the problems of inaccurate test results and poor repeatability caused by complex sample preparation processes and limited testing conditions in traditional methods. This invention achieves the measurement of the intrinsic ion mobility of ion-conducting materials, and the test results are no longer affected by sample preparation processes, testing conditions, etc., maximizing the reflection of the material's inherent performance. It can serve as an effective supplement to traditional methods, thereby further improving the efficiency of material optimization and development. Compared with traditional methods, this invention eliminates the need for cumbersome sample preparation, making operation simpler and testing more efficient. Furthermore, it has spatial resolution, enabling separate measurement of the performance of different individuals within a batch of material particles, increasing the depth and breadth of information obtained through testing, thus acquiring richer material performance information and greatly improving the efficiency of material optimization and development.

[0119] The acquisition, storage, use, and processing of data in this application all comply with relevant laws and regulations.

[0120] Those skilled in the art will understand that embodiments of the present invention can be provided as methods, apparatus, or computer program products. Therefore, the present invention can take the form of a completely hardware embodiment, a completely software embodiment, or an embodiment combining software and hardware aspects. Furthermore, the present invention can take the form of a computer program product embodied on one or more computer-usable storage media (including, but not limited to, disk storage, CD-ROM, optical storage, etc.) containing computer-usable program code.

[0121] This invention is described with reference to flowchart illustrations and / or block diagrams of methods and computer program products according to embodiments of the invention. It will be understood that each block of the flowchart illustrations and / or block diagrams, and combinations of blocks in the flowchart illustrations and / or block diagrams, can be implemented by computer program instructions. These computer program instructions can be provided to a processor of a general-purpose computer, special-purpose computer, embedded processor, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, generate instructions for implementing the flowchart illustrations and / or block diagrams. Figure 1 One or more processes and / or boxes Figure 1 A device that provides the functions specified in one or more boxes.

[0122] These computer program instructions may also be stored in a computer-readable storage medium that can direct a computer or other programmable data processing device to function in a particular manner, such that the instructions stored in the computer-readable storage medium produce an article of manufacture including instruction means, which are implemented in a process Figure 1 One or more processes and / or boxes Figure 1 The function specified in one or more boxes.

[0123] These computer program instructions may also be loaded onto a computer or other programmable data processing equipment to cause a series of operational steps to be performed on the computer or other programmable equipment to produce a computer-implemented process, thereby providing instructions that execute on the computer or other programmable equipment for implementing the process. Figure 1 One or more processes and / or boxes Figure 1 The steps of the function specified in one or more boxes.

[0124] Finally, it should be noted that the above-described embodiments are merely specific implementations of the present invention, used to illustrate the technical solutions of the present invention, and not to limit it. The scope of protection of the present invention is not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any person skilled in the art can still modify or easily conceive of changes to the technical solutions described in the foregoing embodiments within the technical scope disclosed in the present invention, or make equivalent substitutions for some of the technical features; and these modifications, changes, or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for measuring intrinsic solid-state ion mobility based on optical imaging, characterized in that, The method includes: Assemble a test sample cell; wherein, the solid electrolyte powder particles to be tested are modified and fixed on the insulating side surface of a first thin-layer insulating substrate, and the solid electrolyte powder particles to be tested do not contact the conductive coating on the first thin-layer insulating substrate; a second thin-layer insulating substrate is placed on top of the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested, forming a three-layer structure, with the conductive coatings of the two thin-layer insulating substrates located on the outer sides of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode; The test sample cell is subjected to an electrical test; wherein, the packaged test sample cell is placed within the observation range of the optical imaging device; a voltage is applied to the conductive coating of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation, and the optical image of the solid electrolyte powder particles under test is acquired in real time by the optical imaging device. Extract the size information of the solid electrolyte powder particles to be tested from the optical image; The optical intensity curve of the solid electrolyte powder particles under test as a function of time is extracted from the optical image, and the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change is determined based on the curve. The electric field strength under test conditions is determined based on the applied voltage and the total thickness of the thin insulating substrate. The intrinsic ion mobility of the solid electrolyte powder particles to be tested is determined based on the size information, time information, and electric field strength. The formula for calculating the intrinsic ion mobility is as follows: In the formula, μ represents the intrinsic ion mobility; r represents the size information; τ represents the time information; and E represents the electric field strength.

2. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, The method also includes: The intrinsic ion solid mobility of different particles in the same group of solid electrolyte powders was tested to obtain the intrinsic ion mobility of different particles corresponding to the same group of solid electrolyte powders.

3. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, The three-layer structure consists of a first thin-layer insulating substrate, solid electrolyte powder particles to be tested, and a second thin-layer insulating substrate.

4. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, The method also includes: The three-layer structure is assembled under an inert atmosphere and encapsulated in a sealed cavity.

5. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, The modification method is at least one of sieving, spin coating and drop coating; The conductive coating is made of at least one of gold, aluminum, copper, and indium tin oxide; The material of the thin insulating substrate is at least one of glass, polyethylene terephthalate, polymethylsiloxane, and polyimide; The optical imaging device is at least one of an optical microscope, a stereo microscope, and a lens camera assembly.

6. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, A voltage is applied to the conductive plating of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation. Optical images of the solid electrolyte powder particles under test are acquired in real time using the optical imaging device, including: The applied voltage is a pulse voltage, with a voltage range from 0V to a preset test voltage. The preset test voltage is used to drive the redistribution of ions inside the solid electrolyte powder particles under test.

7. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, A voltage is applied to the conductive plating of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation. Optical images of the solid electrolyte powder particles under test are acquired in real time using the optical imaging device, including: The waveform of the voltage applied to the conductive plating of the thin insulating substrate on both sides of the test sample cell is at least one of the periodic electrical excitations, including square wave, sine wave, and triangle wave.

8. The intrinsic solid-state ion mobility testing method based on optical imaging according to claim 1, characterized in that, Extracting the size information of the solid electrolyte powder particles to be tested from the optical image includes: The dimensional information is quantified using the equivalent circle radius to obtain the dimensional information r; The process includes extracting a curve of the optical intensity of the solid electrolyte powder particles under test changing over time from the optical image, and determining the time information of the optical response of the particles from the start to equilibrium during voltage changes based on this curve, including: The time information is quantified using a time constant to obtain the time information τ; The electric field strength under test conditions is determined based on the applied voltage and the total thickness of the thin insulating substrate, including: The electric field strength is determined using the following formula: In the formula, E represents the electric field strength; U represents the applied voltage; and d represents the total thickness of the thin insulating substrate.

9. An intrinsic solid-state ion mobility testing device based on optical imaging, characterized in that, The device includes: a power-on testing device, an optical imaging device, and a data processing device; among which... The power-on testing device is used to perform power-on testing on the test sample cell; wherein, the packaged test sample cell is placed within the observation range of the optical imaging device; voltage is applied to the conductive plating layer of the thin insulating substrate on both sides of the test sample cell to perform periodic electrical excitation, and the optical imaging device acquires optical images of the solid electrolyte powder particles under test in real time. The assembly process of the test sample cell includes: modifying and fixing the solid electrolyte powder particles to be tested onto the insulating side surface of a first thin-layer insulating substrate, wherein the solid electrolyte powder particles to be tested do not contact the conductive coating on the first thin-layer insulating substrate; covering the first thin-layer insulating substrate modified with the solid electrolyte powder particles to be tested onto a second thin-layer insulating substrate, forming a three-layer structure, wherein the conductive coatings of the two thin-layer insulating substrates are respectively located on the outer side of the three-layer structure; the test sample cell includes at least a transverse electric field architecture mode and a longitudinal electric field architecture mode. The data processing device is used to extract the size information of the solid electrolyte powder particles to be tested from the optical image; The optical intensity curve of the solid electrolyte powder particles under test as a function of time is extracted from the optical image, and the time information of the optical response of the particles from the beginning to the equilibrium during the voltage change is determined based on the curve. The electric field strength under test conditions is determined based on the applied voltage and the total thickness of the thin insulating substrate. The intrinsic ion mobility of the solid electrolyte powder particles to be tested is determined based on the size information, time information, and electric field strength. The formula for calculating the intrinsic ion mobility is as follows: In the formula, μ represents the intrinsic ion mobility; r represents the size information; τ represents the time information; and E represents the electric field strength.

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