In-situ characterization method for nucleation and growth of metal dendrites and application thereof
By employing a multi-technology combined in-situ characterization method, multi-dimensional dynamic monitoring of the metal dendrite growth process was achieved, overcoming the shortcomings in information acquisition in existing technologies and improving the safety and self-healing capabilities of electrochemical devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUN YAT SEN UNIV
- Filing Date
- 2026-04-16
- Publication Date
- 2026-06-12
AI Technical Summary
Existing technologies struggle to simultaneously acquire dynamic information on morphological evolution, microstructure, crystal orientation, and stress-strain distribution during the growth of metal dendrites without damaging the original state of the battery or electrochemical system. Furthermore, existing in-situ characterization techniques are unable to capture the transient process of rapid dendrite growth.
By combining multiple technologies such as three-dimensional digital microscope, scanning electron microscope, X-ray diffractometer and digital image correlation system, multi-dimensional dynamic monitoring of metal dendrite morphology, crystal structure and stress-strain distribution can be achieved.
It provides comprehensive characterization methods, enabling real-time monitoring of dendrite growth without damaging the original state of the battery or electrochemical system, thereby improving the safety and self-healing capabilities of electrochemical devices.
Smart Images
Figure CN122193210A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of in-situ characterization technology of metal dendrites, specifically relating to an in-situ characterization method for the nucleation and growth of metal dendrites and its application. Background Technology
[0002] Dendritic growth is a common non-equilibrium phenomenon in electrochemical deposition, dominated by diffusion field instability and anisotropy, forming a tree-like structure with fractal characteristics. In fields such as metal electrodeposition, secondary battery charging and discharging, electrochemical sensors, and microelectronic interconnects, the growth behavior of metal dendrites directly affects the performance, lifespan, and safety of devices. Especially in high-energy-density electrochemical energy storage systems such as lithium-ion batteries, lithium metal batteries, sodium batteries, and zinc batteries, the disordered growth of lithium, sodium, and zinc dendrites on the negative electrode surface can penetrate the separator, causing internal short circuits, leading to thermal runaway or even serious safety accidents such as fires and explosions. Furthermore, the rational utilization of metal dendrites can be used to develop conductive self-healing metal circuits, thereby fabricating self-healing printed circuit boards. Therefore, in-depth research on the nucleation and growth of metal dendrites, revealing their growth mechanisms and influencing factors, and correctly utilizing and suppressing metal dendrites have become important topics in the fields of electrochemistry and materials science.
[0003] Currently, research on metal dendrites mainly relies on various characterization techniques to analyze the morphology, structure, composition, and interface properties of the dendrites. Based on the different characterization methods, these techniques can be divided into two main categories: non-in-situ characterization and in-situ characterization.
[0004] In non-in-situ characterization, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) can provide sub-nanometer spatial resolution, enabling the observation of fine dendrite morphology, tip structure, and microscopic features of the solid electrolyte interphase (SEI) layer. SEM is widely used for imaging analysis of dendrite morphology on the negative electrode surface, obtaining high-fidelity morphology images to study the influence of surface roughness, electrolyte composition, and deposition kinetics on dendrite growth. Energy-dispersive spectroscopy (EDS) can be coupled with SEM to analyze the elemental composition of dendrites. X-ray diffraction (XRD) is used to analyze the crystal structure, crystal orientation, and grain size of dendrites, revealing the intrinsic relationship between crystallographic features and growth behavior. However, these characterization methods typically require sample disassembly, cleaning, and drying pretreatment, disrupting the original state of the battery or electrochemical system. This makes it impossible to obtain dynamic evolution information during dendrite growth and also has limitations such as insufficient sample representativeness and inability to track the growth process in the same region.
[0005] In terms of in-situ characterization, a series of in-situ characterization techniques have been developed in recent years. Optical microscopy (OM) utilizes the principles of light reflection and refraction to achieve a spatial resolution of approximately 1 micrometer and a temporal resolution of approximately 1 second, enabling real-time observation of dendrite morphology evolution over large areas. However, limited by the optical diffraction limit, it is difficult to resolve fine structures at the submicrometer scale. X-ray tomography can provide spatial resolution from submicrometer to several micrometers, enabling non-destructive three-dimensional imaging of hidden dendrite structures. However, its temporal resolution is typically on the order of seconds to minutes, making it difficult to capture the transient processes of rapid dendrite growth. Raman spectroscopy can provide information on molecular vibrational modes, used to monitor chemical changes such as SEI formation, new species generation, and phase transitions. However, its spatial resolution is relatively low, making it difficult to achieve precise correlation with dendrite morphology.
[0006] In summary, there is an urgent need in this field to establish a multi-dimensional in-situ characterization method that can simultaneously acquire the morphological evolution, microstructure, crystal orientation, and stress-strain distribution during the growth of metal dendrites. This method should be applied to the evaluation and risk warning of dendrite suppression strategies in the development of novel conductive self-healing printed circuit boards or batteries, thereby providing technical support for a deeper understanding of dendrite growth mechanisms, efficient screening of suppression strategies, and improvement of the safety of electrochemical devices. Summary of the Invention
[0007] To address the problems existing in the prior art, this invention provides an in-situ characterization method for metal dendrite nucleation and growth, and its application. By combining multiple technologies such as three-dimensional digital microscopy, scanning electron microscopy, X-ray diffraction, and digital image correlation systems, multi-dimensional dynamic monitoring of metal dendrite morphology, crystal structure, and stress-strain distribution is achieved. This method provides a comprehensive characterization tool for studying the growth mechanism of metal dendrites and can be applied to the fabrication of self-healing printed circuit boards and battery research.
[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of the present invention provides an in-situ characterization method for the nucleation and growth of metal dendrites, including a three-dimensional microscope in-situ characterization method and a digital image correlation (DIC) system in-situ characterization method.
[0009] Furthermore, the three-dimensional microscope in-situ characterization method includes the following steps: Step X1: Cut the metal material into a working electrode of a predetermined size, place it in the in-situ cell, and add an electrolyte containing metal ions; Step X2: Connect the in-situ cell to the electrochemical workstation to perform electrochemical deposition of metal dendrites; Step X3: Place the in-situ cell on the stage of a three-dimensional digital microscope to observe the nucleation and growth process of metal dendrites in real time.
[0010] Furthermore, the in-situ characterization method of the digital image correlation system includes the following steps: Step Y1: Use the same metal material coating as the positive and negative electrodes, and add an electrolyte containing metal ions to assemble a galvanic cell; Step Y2: Connect the galvanic cell to an electrochemical workstation to perform electrochemical deposition of metal dendrites; Step Y3: Use a pre-installed CCD camera to capture real-time images of metal dendrite nucleation and growth at regular intervals; Step Y4: After the shooting is completed, the data analysis software equipped in the DIC system is used to analyze the data and obtain the stress-strain distribution map of the nucleation and growth process of metal dendrites under different conditions.
[0011] Further, in steps X1 and Y1, the metallic material is at least one selected from copper, silver, lithium, sodium, and zinc; the metal ion is Ag. + Cu + Li + Na + or Zn 2+ At least one of them.
[0012] Furthermore, in steps X1 and Y1, the concentration of the electrolyte is 0~0.4 mol / L.
[0013] Furthermore, in steps X2 and Y2, the current density of the electrochemical deposition is not less than 0.1 mA cm⁻¹. -2 .
[0014] Furthermore, in steps X2 and Y2, the temperature of the electrochemical deposition is 25~80°C. o C.
[0015] Furthermore, in step Y3, the shooting time interval of the CCD camera is no greater than 1 / 2 of the total test time.
[0016] A second aspect of the present invention provides an application of the above-described in-situ characterization method in evaluating dendrite suppression strategies in solar cells, the application comprising the following steps: The dendrite suppression scheme to be evaluated is introduced into the in-situ characterization method. The morphological evolution, microstructure, crystal orientation and stress-strain distribution data of metal dendrites are obtained by three-dimensional digital microscope, scanning electron microscope, X-ray diffractometer and digital image correlation system, respectively. The data are used as evaluation index to judge the effectiveness of the dendrite suppression scheme.
[0017] A third aspect of the present invention provides an application of the above-described in-situ characterization method in conductive self-healing flexible printed circuit boards, the application comprising the following steps: The growth process of metal dendrites during the conductive self-healing process of flexible printed circuit boards is directly observed using in-situ monitoring technology. By adjusting the parameters of conductive self-healing, the conductive self-healing efficiency of flexible printed circuit boards can be improved.
[0018] Compared with the prior art, the beneficial effects of the present invention are: This invention provides an in-situ characterization method for the nucleation and growth of metal dendrites and its applications. The in-situ characterization method includes a three-dimensional microscopy in-situ characterization method and a digital image correlation system in-situ characterization method. Under a certain voltage, metal dendrites nucleate and grow in an electrolyte. The three-dimensional microscopy in-situ characterization method involved in this invention can observe the nucleation and growth of metal dendrites in situ. Combined with the in-situ characterization method using a digital image correlation system, it can determine the relative size of metal dendrite grains and the density of dendrites under different conditions. By adjusting the nucleation and growth conditions according to different application scenarios, it is possible to both inhibit and promote the growth of metal dendrites in batteries, achieving conductive self-repair of metallic materials. Attached Figure Description
[0019] Figure 1 This is a schematic diagram of the DIC testing device.
[0020] Figure 2 Optical digital photographs of silver dendrites grown at different current densities, where a) 0.5 mA cm⁻¹ -2 b) 1mA cm -2 c) 2 mA cm -2 .
[0021] Figure 3 The DIC diagrams are shown for silver dendrites grown at different current densities, where a) 0.5 mA cm⁻¹ -2 b) 1 mA cm -2 c) 2 mA cm -2 .
[0022] Figure 4 Optical digital photographs of copper dendrite nucleation and growth under different current densities, where a) 0.1 mA cm⁻¹ -2 b) 0.2 mA cm -2 c) 0.4 mA cm -2 .
[0023] Figure 5 The DIC diagrams are shown for copper dendrites grown at different current densities, where a) 0.1 mA cm⁻¹ -2 b) 0.2 mA cm -2 c) 0.4 mA cm -2 .
[0024] Figure 6 For different Ag + Optical digital photographs of silver dendrites grown in a high-concentration electrolyte, where a) 0.05 mol L -1 b) 0.1 mol L -1 c) 0.2 mol L -1 .
[0025] Figure 7 For different Ag + DIC diagrams of silver dendrites grown in electrolytes of varying concentrations, where a) 0.05 mol L -1 b) 0.1 mol L -1 c) 0.2 mol L -1 . Detailed Implementation
[0026] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0027] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.
[0028] Example 1: In-situ characterization method for silver dendrite nucleation and growth under different current densities Step X1: Cut the silver coating into a 10 mm × 10 mm working electrode, place it in the in-situ cell, and add a 0.2 mol / L silver nitrate glycerol solution as the electrolyte; Step X2: Connect the in-situ cell to the electrochemical workstation and run it at 25°C. o C at 0.05 mA cm -2 0.1 mA cm -2 0.2 mA cm -2 Electrochemical deposition of silver dendrites was performed using a current density; Step X3: Place the in-situ cell on the stage of a three-dimensional digital microscope to observe the nucleation and growth process of silver dendrites in real time.
[0029] Step Y1: Using a silver coating as both the positive and negative electrodes, add the same silver nitrate glycerol solution as the electrolyte, and proceed according to... Figure 1 Install the electrodeposition apparatus. Connect the installed apparatus to the electrochemical workstation and heat it at 25°C. o C at 0.05 mA cm -2 0.1 mA cm-2 0.2 mA cm -2 Electrochemical deposition of silver dendrites was performed using a current density; Step Y2: Use a pre-positioned CCD camera to capture the nucleation and growth process of silver dendrites in real time at 30-second intervals; Step Y3: After the shooting is completed, the data analysis software equipped in the DIC system is used to perform corresponding analysis to obtain the strain distribution map of the nucleation and growth process of silver dendrites under this condition.
[0030] Optical digital images of silver dendrites grown at different current densities obtained by a three-dimensional digital microscope are shown below. Figure 2 As shown, the silver dendrites grow relatively densely in the initial state. When the deposition time increases to 15 min, the growth of silver dendrites begins to show a branched structure. With the increase of current density, the growth rate of silver dendrites accelerates, the grains become finer, and the structure becomes more dense.
[0031] Further analysis of silver dendrite nucleation and growth was conducted using a digital image correlation system. When the strain distribution resulting from nucleation and growth is more uniform across the substrate, the dendrite grains become finer, and the dendritic structure becomes more compact. Therefore, as... Figure 3 As shown, with the increase of current density, the strain distribution during the nucleation and growth process becomes more uniform, indicating that the silver dendrite grains are refined and the dendritic structure after growth is more compact.
[0032] Example 2: In-situ characterization method for copper dendrite nucleation and growth under different current densities In-situ characterization of copper dendrite nucleation and growth was performed following the same procedures as in Example 1. The copper coating was replaced as the positive and negative electrodes, and copper chloride was added at 0.2 mol / L... -1 The concentration of the solution was dissolved in choline chloride-glycerol as the electrolyte, and the current density and temperature during nucleation growth were the same as in Example 1.
[0033] Optical digital images of copper dendrite nucleation and growth under different current densities obtained by a three-dimensional digital microscope, such as... Figure 4 As shown, in the presence of Cl - In the electrolyte, the nucleation overpotential of copper dendrites increases, resulting in a denser dendrite structure; with increasing current density, the growth rate accelerates, but the density of the copper dendrites does not change significantly. The strain distribution diagram obtained from the digital image correlation system is shown below. Figure 5 As shown, the change in current density has no significant effect on the density of copper dendrite nucleation and growth.
[0034] Example 3: In-situ characterization method for silver dendrite nucleation and growth under different electrolyte concentrations The nucleation and growth of silver dendrites were characterized in situ using the same methods and steps as in Example 1. The current density during nucleation and growth was 0.1 mA cm⁻¹.-2 The temperature is 25 degrees Celsius. o C, The silver nitrate glycerol solution is used as the electrolyte, and the silver nitrate concentration is 0.05 mol / L. -1 0.1 mol L -1 0.2 mol L -1 .
[0035] The test results of the three-dimensional digital microscope are as follows: Figure 6 As shown, in the initial stage, the silver dendrites grow relatively densely. With prolonged growth time, the dendrites develop a branched structure, and the number of branches increases with increasing silver nitrate concentration. The strain distribution diagram obtained from the digital image correlation system is shown below. Figure 7 As shown in the figure, it can be seen that Ag in the electrolyte + The concentration of Ag in the electrolyte has no significant effect on the nucleation process of silver dendrites; therefore, the concentration of Ag in the electrolyte is not significant. + Concentration has no significant effect on the grain size in silver dendrites.
[0036] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.
Claims
1. An in-situ characterization method for the nucleation and growth of metal dendrites, characterized in that, This includes in-situ characterization methods for three-dimensional microscopy and in-situ characterization methods for digital image correlation systems.
2. The in-situ characterization method for metal dendrite nucleation and growth according to claim 1, characterized in that, The three-dimensional microscope in-situ characterization method includes the following steps: Step X1: Cut the metal material into a working electrode of a predetermined size, place it in the in-situ cell, and add an electrolyte containing metal ions; Step X2: Connect the in-situ cell to the electrochemical workstation to perform electrochemical deposition of metal dendrites; Step X3: Place the in-situ cell on the stage of a three-dimensional digital microscope to observe the nucleation and growth process of metal dendrites in real time.
3. The in-situ characterization method for metal dendrite nucleation and growth according to claim 1, characterized in that, The in-situ characterization method of the digital image correlation system includes the following steps: Step Y1: Use the same metal material coating as the positive and negative electrodes, and add an electrolyte containing metal ions to assemble a galvanic cell; Step Y2: Connect the galvanic cell to an electrochemical workstation to perform electrochemical deposition of metal dendrites; Step Y3: Use a pre-installed CCD camera to capture real-time images of metal dendrite nucleation and growth at regular intervals; Step Y4: After the shooting is completed, the data analysis software equipped in the DIC system is used to analyze the data and obtain the stress-strain distribution map of the nucleation and growth process of metal dendrites under different conditions.
4. The in-situ characterization method for metal dendrite nucleation and growth according to claim 2 or 3, characterized in that, In steps X1 and Y1, the metallic material is at least one selected from copper, silver, lithium, sodium, and zinc; the metal ion is Ag. + Cu + Li + Na + or Zn 2+ At least one of them.
5. The in-situ characterization method for metal dendrite nucleation and growth according to claim 2 or 3, characterized in that, In steps X1 and Y1, the concentration of the electrolyte is 0~0.4 mol / L.
6. The in-situ characterization method for metal dendrite nucleation and growth according to claim 2 or 3, characterized in that, In steps X2 and Y2, the current density of the electrochemical deposition is not less than 0.1 mA cm⁻¹. -2 .
7. The in-situ characterization method for metal dendrite nucleation and growth according to claim 2 or 3, characterized in that, In steps X2 and Y2, the electrochemical deposition temperature is 25~80°C. o C.
8. The in-situ characterization method for metal dendrite nucleation and growth according to claim 3, characterized in that, In step Y3, the shooting time interval of the CCD camera is no more than 1 / 2 of the total test time.
9. The application of the in-situ characterization method according to any one of claims 1-3 in evaluating dendrite suppression strategies in batteries, characterized in that, The application includes the following steps: The dendrite suppression scheme to be evaluated is introduced into the in-situ characterization method. The morphological evolution, microstructure, crystal orientation and stress-strain distribution data of metal dendrites are obtained by three-dimensional digital microscope, scanning electron microscope, X-ray diffractometer and digital image correlation system, respectively. The data are used as evaluation index to judge the effectiveness of the dendrite suppression scheme.
10. The application of the in-situ characterization method according to any one of claims 1-3 in conductive self-healing flexible printed circuit boards, characterized in that, The application includes the following steps: The growth process of metal dendrites during the conductive self-healing process of flexible printed circuit boards is directly observed using in-situ monitoring technology. By adjusting the parameters of conductive self-healing, the conductive self-healing efficiency of flexible printed circuit boards can be improved.