An electrochemical in-situ cell and system suitable for spectroscopic microscopic measurements

Abstract

The application provides an electrochemical in-situ cell and system suitable for spectral imaging microscopy testing, a working electrode is arranged in a first recess, an upper cover is further provided with a second through hole in a first direction, and the upper cover is further provided with an inclined groove and a first connecting hole along a first plane. One end of a conductive tab is in contact with the working electrode, and the other end of the conductive tab extends to the outside of the upper cover. One end of a counter electrode is located in the second through hole, and the other end of the counter electrode extends to the outside of the upper cover. The second through hole is configured to accommodate a solution, and the conductive tab is configured to apply an external potential to the working electrode. The part of the working electrode accommodated in the first through hole is a transparent material, external light passes through the working electrode to irradiate the solution in the second through hole, and an external microscope device is configured to obtain spectral imaging information during the reaction process of the solution. The electrochemical in-situ cell of the application can be compatible with external light characterization and electrochemical testing, expand the function of spectral microscopy technology, and provide microscopic chemical information for electrochemical process testing.

Description

Technical Field

[0001] This application relates to the field of spectral and imaging testing, and more specifically, to an electrochemical in-situ cell and system suitable for spectral microscopy measurements. Background Technology

[0002] An in-situ cell is a specialized experimental device used to place samples under specific environmental conditions for real-time observation and analysis. Spectroscopic microscopy is a technique that can simultaneously acquire sample surface morphology and nanometer-resolution infrared spectral imaging information at the same location. Combining spectroscopic microscopy with an electrochemical in-situ cell allows for the spectroscopic imaging measurement of interfacial reaction processes under different conditions such as temperature, pressure, atmosphere, potential, and solution. However, currently, there are no commercially available in-situ cells specifically designed for spectroscopic microscopy measurements. Summary of the Invention

[0003] In view of this, the purpose of the embodiments of this application is to provide an electrochemical in-situ cell and system suitable for spectroscopic microscopy measurements, which is hardware compatible with nano-infrared spectroscopic microscopy measurements and electrochemical measurement and control.

[0004] In a first aspect, embodiments of this application provide an electrochemical in-situ cell suitable for spectroscopic microscopy measurements, comprising: a base, a top cover, a working electrode, a conductive contact, and a counter electrode; the top cover is fixedly disposed on the base; a first groove is provided on the base, and a first through hole is provided at the bottom of the first groove; the working electrode is disposed in the first groove, and the first through hole is located on the side of the working electrode away from the top cover; the top cover is also provided with a second through hole along a first direction, and an inclined groove and a first connecting hole are provided on the top cover along a first plane; wherein, the first direction is perpendicular to the first plane; the inclined groove penetrates the outside of the top cover and the first groove, and the first connecting hole penetrates the outside of the top cover and the second through hole; the conductive contact is disposed on the base; the top cover is fixedly disposed on the base; the top cover is provided with a first groove, and the first through hole is provided with a first through hole; the first through hole is provided with a second through hole; the second through hole is provided with a second through hole; the conductive contact is disposed with a second through hole; the first through hole is provided with a second through hole; the second through hole is provided with a second through hole; the second through hole is provided with a second through hole; the third through hole is provided with a second through hole; the fourth through hole is provided with a second through hole; the fifth through hole is provided with a second through hole; the sixth through hole is provided with a second through hole; the seventh through hole is provided with a second through hole; the fifth through hole is provided with a second through hole; the sixth through hole is provided with a second through hole; the seventh through hole is provided with a second through hole; the fifth through hole is provided with a second through hole; the sixth through hole is provided with a second through hole; the seventh through hole is provided with a second through hole; the eighth ... Within the inclined groove, one end of the conductive contact is in contact with the working electrode, and the other end of the conductive contact extends to the outside of the upper cover; the counter electrode is disposed within the first connecting hole, one end of the counter electrode is located within the second through hole, and the other end of the counter electrode extends to the outside of the upper cover; wherein, the second through hole is configured to contain a solution, and the conductive contact is configured to apply an external potential to the working electrode; the working electrode, the counter electrode, and the solution undergo an electrochemical reaction under the action of the applied potential; the portion of the working electrode contained within the first through hole is made of a transparent material; wherein, external light passes through the working electrode and irradiates the solution in the second through hole; an external microscope is configured to acquire spectral imaging information during the reaction process of the solution.

[0005] In the above implementation process, a first groove for accommodating the working electrode is provided on the base, and a second through hole is provided on the top cover. A solution-accommodating space is formed based on the working electrode and the second through hole to hold the solution. Then, an inclined groove and a first connecting hole are provided on the top cover for placing the conductive contact and the counter electrode, respectively. Thus, a complete in-situ cell for electrochemical reactions is formed based on the working electrode, solution, counter electrode, and conductive contact. External light is then emitted to the working electrode through the first through hole, resulting in an in-situ cell compatible with external light characterization and electrochemical testing, expanding the functionality of spectroscopic microscopy and enriching the types of information on interfacial electrochemical processes. Furthermore, since the first through hole is located on one side of the working electrode, the pulsed light from external light, after adjustment by the external optical path, can vertically irradiate the surface of the working electrode through the first through hole. This electrochemical in-situ cell is suitable for spectroscopic microscopes with a bottom vertical excitation configuration, which can obtain a stronger signal compared to oblique excitation, thus facilitating the acquisition of a stronger detection signal.

[0006] In one embodiment, the upper cover is further provided with a second groove along the first plane; the second groove is located on the inner surface of the second through hole; the shape of one end of the counter electrode accommodated in the second through hole matches the shape of the second groove; one end of the counter electrode accommodated in the second through hole is wholly or partially disposed in the second groove.

[0007] In the above implementation process, by setting a second groove around the inner surface of the second through hole and placing all or part of the counter electrode at one end of the second through hole in the second groove, a longer counter electrode can be accommodated in the second through hole, increasing the surface area of ​​the counter electrode participating in the reaction, and ensuring that the current in the circuit is limited only by the electrochemical reaction on the surface of the working electrode, thereby improving the accuracy of the reaction.

[0008] In one embodiment, the system further includes: a reference electrode; a second connection hole is provided on the upper cover along the first direction, and a third groove is provided on the upper cover along the first plane; one end of the second connection hole communicates with one end of the third groove, and the third groove is configured to accommodate the solution; one end of the reference electrode is accommodated in the second connection hole; wherein, when the in-situ pool is in working condition, the end of the reference electrode accommodated in the second connection hole is in contact with the solution in the third groove.

[0009] In the above implementation process, the accuracy of the potential applied to the working electrode can be improved by setting a reference electrode. Furthermore, by setting a reference electrode, working electrode, and counter electrode, a three-electrode in-situ cell can be formed, making the electrochemical detection under in-situ nano-infrared instrument detection conditions more consistent with conventional electrochemical detection conditions. This, in turn, makes the in-situ detection results comparable to those of conventional chemical testing methods, improving the accuracy of electrochemical detection under in-situ nano-infrared instrument detection conditions.

[0010] In one embodiment, it further includes: a reference sleeve; wherein the reference sleeve is one or more, and the plurality of reference sleeves correspond to a plurality of specifications; the reference sleeve is configured to be sleeved on the outer surface of the reference electrode; wherein various reference electrodes are fixed in the second connection hole by sleeved with reference sleeves of corresponding specifications.

[0011] In the above implementation process, by setting up reference sleeves of various specifications, a reference sleeve of the appropriate specification can be selected according to the size of the reference electrode and fitted onto its outer surface, so that the outer surface of the reference sleeve is in close contact with the inner surface of the second connecting hole, thereby fixing the reference electrode in the second connecting hole. This increases the size of the reference electrode that can be compatible with the in-situ cell, expanding the application scenarios of the in-situ cell.

[0012] In one embodiment, the top cover is further provided with a first flow hole and a second flow hole along the first direction; the first flow hole penetrates the outside of the top cover and the second flow hole, and the second flow hole penetrates the outside of the top cover and the second flow hole; wherein the first flow hole and the second flow hole are configured to input the solution into the second flow hole and / or output the solution into the second flow hole.

[0013] In the above implementation process, by setting a first flow hole and a second flow hole on the top cover, during the electrochemical reaction in the in-situ cell, air bubbles in the solution flow path are removed based on the cooperation of the first and second flow holes, thus ensuring the stability of the electrochemical reaction. Furthermore, the cooperation of the first and second flow holes allows for the replacement of the solution in the in-situ cell, thereby expanding the application scenarios of the in-situ cell. Additionally, the thickness of the diffusion layer on the working electrode surface can be controlled by adjusting the flow rate of the solution in the first and second flow holes, improving the accuracy of the reaction.

[0014] In one embodiment, the system further includes: a first sealing ring; a fourth groove is provided on the upper cover along the first plane, and the fourth groove is located on the side of the upper cover near the base; the first sealing ring is connected to the fourth groove, and the first sealing ring is in contact with the working electrode; wherein the first sealing ring is configured to fix the contact area between the solution and the working electrode.

[0015] In the above implementation process, by setting a first sealing ring between the top cover and the working electrode, the tiny gap between the top cover and the working electrode can be filled to prevent solution leakage and improve the sealing performance of the solution in the in-situ cell. On the other hand, the first sealing ring can also fix the contact area between the solution and the working electrode. Therefore, by setting different specifications of the first sealing ring, the surface area of ​​the working electrode surrounded by the first sealing ring can be changed, thereby changing the contact area between the working electrode and the solution, so as to adjust the electrochemical reaction efficiency. This not only makes the reaction adjustable, but also expands the application scenarios of the in-situ cell.

[0016] In one embodiment, it further includes: a top cover and a cap; the top cover is disposed on the side of the top cover away from the base; the top cover is provided with a third through hole along the first direction; the cap is detachably accommodated in the third through hole; wherein, when the cap is accommodated in the third through hole, the cap and the top cover seal the second through hole by cooperating.

[0017] In the above implementation process, by setting a top cover and a cap, the in-situ cell can be switched between a semi-sealed and open state according to the sealing requirements of different test tasks when performing different test tasks. This allows for adjustment of the in-situ cell's sealing performance, thereby reducing electrolyte evaporation and expanding the application scenarios of the in-situ cell. Furthermore, only the structure of the in-situ cell is changed during different tests; battery testing and nano-infrared testing do not require replacing the sample cell. This avoids damage to the sample during transfer, preserves the original properties of the test sample, and improves test accuracy.

[0018] In one embodiment, the device further includes: a second sealing ring; a fifth groove is provided on the top cover along the first plane, and the fifth groove is located on the side of the top cover near the upper cover; the second sealing ring is connected to the fifth groove; wherein the second sealing ring is configured to seal the second through hole.

[0019] In the above implementation process, by setting a second sealing ring on the top cover to seal the second through hole, solution leakage can be prevented, thus improving the sealing performance of the solution in the in-situ tank. Furthermore, improving the sealing performance of the in-situ tank through the second sealing ring can prevent solution evaporation and increased solution concentration during long-term testing, which would affect the accuracy of the reaction.

[0020] In one embodiment, the top cover and / or the cap is made of a transparent material.

[0021] In the above implementation process, by setting the top cover and / or cap to a transparent material, the electrochemical reaction inside the in-situ cell can be observed through the transparent material even when the in-situ cell is sealed, which helps to observe the situation during the electrochemical reaction process and enhances the user experience.

[0022] In one embodiment, it further includes: a connector; wherein the conductive contact is provided with a connecting groove; the connector fixes the conductive contact in the inclined groove through the connecting groove.

[0023] In the above implementation process, by setting a connecting groove on the conductive contact piece and fixing the conductive contact piece in the inclined groove through the connecting groove, the stability of the conductive contact piece in the inclined groove can be improved, thereby improving the stability of the in-situ pool structure.

[0024] Secondly, embodiments of this application also provide a spectroscopic microscopy measurement system, comprising: a light emitter, a spectroscopic imaging microscope, and an electrochemical in-situ cell as described in the first aspect above, or in any possible embodiment of the first aspect; the light emitter is disposed on one side of the base of the electrochemical in-situ cell, and the light emitter is configured to emit external light to the sample in the electrochemical in-situ cell through a first through-hole of the electrochemical in-situ cell; the scanner of the spectroscopic imaging microscope is disposed on one side of the upper cover of the electrochemical in-situ cell, and the scanner is configured to control a probe to approach the sample surface and scan the sample surface through the probe; wherein, the microscope acquires the absorption of the external light by the sample during the chemical reaction; the absorption of the external light by the sample during the chemical reaction is configured to detect the sample.

[0025] In the aforementioned implementation process, by setting up a spectral microscopy measurement system including a light emitter, a spectral imaging microscope, and an electrochemical in-situ cell, and by vertically emitting external light into the electrochemical in-situ cell, a stronger signal can be obtained compared to oblique excitation, which is beneficial for obtaining a stronger detection signal. Furthermore, this spectral microscopy measurement system can be compatible with external light characterization and electrochemical testing, or both simultaneously, which can improve testing efficiency and expand the application scenarios of this spectral microscopy measurement system.

[0026] To make the above-mentioned objectives, features and advantages of this application more apparent and understandable, specific embodiments are described below in conjunction with the accompanying drawings. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 Exploded view of the electrochemical in-situ cell provided in the embodiments of this application;

[0029] Figure 2 A cross-sectional view of the electrochemical in-situ cell provided in an embodiment of this application;

[0030] Figure 3 A three-dimensional image of an electrochemical in-situ cell under sealed condition provided in an embodiment of this application;

[0031] Figure 4 This is a schematic diagram of the conductive contact structure provided in an embodiment of this application;

[0032] Figure 5 This is a schematic diagram of the spectroscopic microscopy measurement system provided in the embodiments of this application. Description of the figures: 10-Electrochemical in-situ cell, 100-Base, 110-First groove, 120-First through hole, 200-Top cover, 210-Second through hole, 220-Second connecting hole, 230-First flow hole, 240-Second flow hole, 300-Working electrode, 400-Conductive contact, 410-Connecting groove, 500-Counter electrode, 600-Reference electrode, 700-First sealing ring, 810-Top cover, 820-Cap, 900-Second sealing ring, 20-Light emitter, 30-Spectroscopic imaging microscope, 40-Scanner, 50-Probe, 60-Deflecting light emitting device, 70-Four-quadrant detector, 80 Reflecting mirror group, 90-Focusing objective lens. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The components of the embodiments of this application described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0034] Therefore, the following detailed description of the embodiments of this application provided in the accompanying drawings is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments of the application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0035] It should be noted that similar reference numerals and letters in the following figures indicate similar items; therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures. Furthermore, in the description of this application, terms such as "first," "second," etc., are used only to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0036] In the description of this application, it should be noted that the terms "upper", "lower", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly visited when the product is used. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations of this application.

[0037] In the description of this application, it should also be noted that, unless otherwise expressly specified and limited, the terms "set," "install," and "connect" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection between two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0038] With the development of fields such as batteries, solar energy, and catalysis, increasingly higher demands are being placed on materials characterization techniques. On the one hand, it is necessary to obtain the morphological and mechanical characteristics of materials, which can be achieved using characterization techniques such as atomic force microscopy or scanning electron microscopy. On the other hand, it is necessary to identify the chemical composition of materials, which can be achieved using characterization techniques such as infrared spectroscopy and Raman spectroscopy. In addition, if it is necessary to study the properties of materials in a certain state, it is also necessary to place the materials in a special environment, apply a certain potential and current, and then perform detection. Nano-infrared (or peak force infrared, infrared atomic force microscopy) technology is a technique that can simultaneously obtain information on the morphological and mechanical characteristics and chemical composition of materials.

[0039] Through long-term research, the inventors of this application have discovered that there is currently a lack of in-situ cells designed specifically for nano-infrared technology. As a result, there are problems such as low efficiency in the use of nano-infrared technology and the inability to use nano-infrared technology to detect samples under the required solution and potential.

[0040] In view of this, this application proposes an in-situ electrochemical cell. A first groove is provided on the base to accommodate the working electrode, and a second through-hole is provided on the top cover. A solution-accommodating space is formed based on the working electrode and the second through-hole to hold the solution. Then, an inclined groove and a first connecting hole are provided on the top cover for placing a conductive contact and a counter electrode, respectively. Thus, a complete in-situ cell for electrochemical reactions is formed based on the working electrode, solution, counter electrode, and conductive contact. Nano-infrared laser light is emitted to the working electrode through the first through-hole, resulting in an in-situ cell compatible with both nano-infrared characterization and electrochemical testing, improving the efficiency of nano-infrared technology and electrochemical testing. Furthermore, since the first through-hole is located on one side of the working electrode, the laser light from the nano-infrared source, after external optical path adjustment, can vertically irradiate the surface of the working electrode through the first through-hole. This in-situ cell is suitable for nano-infrared instruments with bottom vertical excitation mode, and compared to inclined excitation, it can obtain a stronger signal, which is beneficial for obtaining a stronger detection signal.

[0041] like Figure 1 , Figure 2 The diagram shown is a schematic of an in-situ cell provided in an embodiment of this application, including: a base 100, a top cover 200, a working electrode 300, a conductive contact 400, and a counter electrode 500.

[0042] The top cover 200 is fixedly mounted on the base 100.

[0043] Optionally, the upper cover 200 and the base 100 can be connected by screws, bolts, snap-fit, or other means. The connection method between the upper cover 200 and the base 100 can be selected according to the actual situation.

[0044] In one embodiment, both the upper cover 200 and the base 100 include a first plane and a first direction, and the first direction is perpendicular to the first plane. The first directions of the upper cover 200 and the base 100 are the same, and the first planes of the upper cover 200 and the base 100 are parallel planes.

[0045] The base 100 here is provided with a first groove 110, and the bottom of the first groove 110 is provided with a first through hole 120.

[0046] The working electrode 300 is disposed in the first groove 110, and the first through hole 120 is located on the side of the working electrode 300 away from the upper cover 200.

[0047] The working electrode 300 refers to an electrode that can cause a significant change in the composition or content of the analyte loaded on the surface of the working electrode during the test. In electrochemical analysis and electrochemical reactions, the working electrode 300 is used to transfer electrons and ions to react.

[0048] In one embodiment, the working electrode 300 is an extremely thin electrode, such as a 10 nm gold film. The working electrode 300 is transparent to external light sources.

[0049] Optionally, the working electrode 300 can be a metal electrode, a semiconductor electrode, a conductive polymer electrode, or a composite electrode, etc., and the specific type of the working electrode 300 can be selected according to the actual situation.

[0050] The working electrode 300 here is a gold-plated barium fluoride window. This barium fluoride is transparent, allowing nano-infrared excitation light to irradiate the sample. The gold plating ensures the electrode surface is conductive, applying a specified potential to the sample on the working electrode 300. Furthermore, the surface plasmon resonance effect of gold enhances the infrared signal of the sample on the electrode surface.

[0051] In one embodiment, the working electrode 300 is fixedly disposed within the first groove 110. For example, the working electrode 300 is fixed within the first groove 110 by means of screw connection, bolt connection, welding, etc.

[0052] It should be understood that one side of the working electrode 300 is exposed outside the in-situ cell through the first through hole 120, and the other side of the working electrode 300 is in contact with the upper cover 200. The laser from the nano-infrared light source, after external optical path adjustment, can vertically irradiate the surface of the working electrode 300 through the first through hole 120.

[0053] The aforementioned top cover 200 is also provided with a second through hole 210 along the first direction, and the top cover 200 is provided with an inclined groove and a first connecting hole along the first plane.

[0054] The second through hole 210 is located on the side of the working electrode 300 away from the first through hole 120. The second through hole 210 and the working electrode 300 together form a receiving space for containing the solution.

[0055] The inclined groove here penetrates the outside of the upper cover 200 and the first groove 110, and the first connecting hole penetrates the outside of the upper cover 200 and the second through hole 210.

[0056] In one embodiment, the first connection hole is parallel to the first plane.

[0057] The conductive contact 400 is disposed in the inclined groove, with one end of the conductive contact 400 in contact with the working electrode 300 and the other end of the conductive contact 400 extending to the outside of the upper cover 200. The counter electrode 500 is disposed in the first connecting hole, with one end of the counter electrode 500 located in the second through hole 210 and the other end of the counter electrode 500 extending to the outside of the upper cover 200.

[0058] The conductive contact 400 refers to a sheet of metal or conductive material that is in direct contact with the working electrode 300. This conductive contact 400 is used to transmit current, detect potential, or collect data during the reaction process. For example, the conductive contact 400 can be made of copper, aluminum, platinum, 304 stainless steel, etc.

[0059] The counter electrode 500 is the electrode opposite to the working electrode 300, and is used to form a complete current loop with the working electrode 300.

[0060] The second through hole 210 is configured to contain a solution, and the conductive contact 400 is configured to apply an external potential to the working electrode 300; the working electrode 300, the counter electrode 500, and the solution undergo an electrochemical reaction under the action of the applied potential.

[0061] Understandably, when working in the in-situ cell, power is transmitted to the working electrode 300 through the conductive contact 400. The working electrode 300 and the counter electrode 500 form a closed current loop through the solution. Electron transfer occurs in the solution in the second through hole 210 on the surface of the working electrode 300, and the reaction process is transmitted to the external monitoring device through the conductive contact 400.

[0062] In one embodiment, the portion of the working electrode 300 housed in the first through hole 120 is made of a transparent material.

[0063] Alternatively, the transparent material can be transparent glass, transparent plastic, transparent acrylic sheet, etc., and the transparent material can be selected according to the actual situation.

[0064] External light shines through the working electrode 300 onto the solution in the second through-hole 210. The external microscope is configured to acquire spectral imaging information of the solution reaction process.

[0065] It should be understood that when the portion of the working electrode 300 housed within the first through-hole 120 is made of a transparent material, external light can pass through the transparent portion of the working electrode 300 and irradiate the solution inside the in-situ cell. In this case, an external microscope can acquire spectral imaging information of the solution during the reaction process.

[0066] The spectral imaging information here can be the spectral absorption information of the solution to external light. This spectral information can be infrared spectral information, Raman spectral information, etc. The spectral information can be selected according to the actual situation.

[0067] The aforementioned spectral imaging information is used to determine the properties of the solution. In the above implementation process, a first groove 110 for accommodating the working electrode 300 is provided on the base 100, and a second through-hole 210 is provided on the upper cover 200. Based on the working electrode 300 and the second through-hole 210, a solution-accommodating space is formed to hold the solution. Then, an inclined groove and a first connecting hole are provided on the upper cover 200 for placing the conductive contact 400 and the counter electrode 500, respectively. Furthermore, a complete in-situ cell for electrochemical reactions is formed based on the working electrode 300, the solution, the counter electrode 500, and the conductive contact 400. External light is then emitted to the working electrode 300 through the first through-hole 120, thereby obtaining an in-situ cell compatible with external light characterization and electrochemical testing, expanding the functionality of spectral microscopy and enriching the types of information on interfacial electrochemical processes. In addition, since the first through-hole 120 is located on one side of the working electrode 300, pulsed external light, after being adjusted by an external optical path, can be perpendicularly irradiated onto the surface of the working electrode 300 through the first through-hole 120. This in-situ cell is suitable for spectral microscopy with bottom vertical excitation mode. Compared with oblique excitation, it can obtain a stronger signal, which is beneficial for obtaining a stronger detection signal.

[0068] In one possible implementation, the top cover 200 is further provided with a second groove along the first plane.

[0069] The second groove is located on the inner surface of the second through hole 210.

[0070] The shape of one end of the counter electrode 500, which is accommodated in the second through hole 210, matches the shape of the second groove. The one end of the counter electrode 500, which is accommodated in the second through hole 210, is wholly or partially disposed in the second groove.

[0071] For example, if the second through hole 210 is circular, then the second groove is also circular, and the corresponding end of the counter electrode 500 that is accommodated in the second through hole 210 is also circular. If the second through hole 210 is square, then the second groove is also square, and the corresponding end of the counter electrode 500 that is accommodated in the second through hole 210 is also square.

[0072] In one embodiment, one end of the electrode 500 housed in the second through hole 210 is entirely or partially made of a deformable material, and the shape of one end of the electrode 500 housed in the second through hole 210 can be adjusted according to the shape of the second groove.

[0073] The counter electrode 500 here is used to react with species in the solution to establish a current loop. The counter electrode 500 can be made of a material with the capacity of the battery's active material.

[0074] In the above implementation process, by setting a second groove around the inner surface of the second through hole 210, and placing all or part of the counter electrode 500 in one end of the second through hole 210 in the second groove, the second through hole 210 can accommodate a longer counter electrode 500, increasing the surface area of ​​the counter electrode participating in the reaction, and ensuring that the current in the circuit is limited only by the electrochemical reaction on the surface of the working electrode, thereby improving the accuracy of the reaction.

[0075] In one possible implementation, the in-situ cell also includes a reference electrode 600.

[0076] The upper cover 200 is provided with a second connecting hole 220 along the first direction, and the upper cover 200 is provided with a third groove along the first plane; one end of the second connecting hole 220 is connected to one end of the third groove.

[0077] In one embodiment, the second connection hole 220 is tilted, that is, the two ends of the second connection hole 220 are at different horizontal planes, in order to avoid the reference electrode 600 being too long and colliding with the nanometer external instrument.

[0078] The horizontal plane at the end of the second connecting hole 220 away from the second through hole 210 is higher than the horizontal plane at the end of the second connecting hole 220 close to the second through hole 210.

[0079] The third groove here is configured to contain a solution, and the third groove is connected to the second through hole 210, so that the solution in the second through hole 210 can flow into the third groove.

[0080] One end of the reference electrode 600 is housed in the second connection hole 220, and the other end of the reference electrode 600 extends to the outside of the upper cover 200.

[0081] When the in-situ pool is in operation, the end of the reference electrode 600 housed in the second connection hole 220 comes into contact with the solution in the third groove.

[0082] In one embodiment, the end of the reference electrode 600 housed within the second connection hole 220 is immersed in a solution.

[0083] The aforementioned reference electrode 600 is an electrode used as a reference comparison in electrochemical measurements. This reference electrode 600 avoids the problem of inaccurate potential measurement of the working electrode 300 caused by electrode polarization due to current passing through the working electrode 300 and the counter electrode 500. Furthermore, this reference electrode 600 allows the electrochemical testing conditions to closely approximate those of standard three-electrode cell electrochemical testing.

[0084] In the above implementation process, by setting a reference electrode 600, the accuracy of the potential applied to the working electrode can be improved. Furthermore, by setting the reference electrode 600, the working electrode 300, and the counter electrode 500, a three-electrode in-situ cell can be formed. This makes the electrochemical detection under in-situ nano-infrared instrument detection conditions more consistent with conventional electrochemical detection conditions, thereby making the in-situ detection results comparable to conventional chemical testing results and improving the accuracy of electrochemical detection under in-situ nano-infrared instrument detection conditions.

[0085] In one possible implementation, the in-situ pool also includes a reference set.

[0086] Optionally, there may be one or more reference sleeves, with multiple reference sleeves corresponding to multiple specifications. The quantity of the reference sleeves can be selected according to the actual situation.

[0087] The reference sleeve is configured to be sleeved on the outer surface of the reference electrode 600, and various reference electrodes 600 are fixed in the second connection hole 220 by sleeved with reference sleeves of corresponding specifications.

[0088] The reference sleeve here is an independent structure separate from the reference electrode 600 and the in-situ cell body.

[0089] Understandably, the second connecting hole 220 on the top cover 200 is usually a through hole of a fixed size, but the size of the reference electrode 600 from different manufacturers or different types from the same manufacturer may vary. By setting up reference sleeves of various specifications, the appropriate specification of the reference sleeve is selected according to the size of the reference electrode 600 and fitted onto its outer surface, so that the outer surface of the reference sleeve and the inner surface of the second connecting hole 220 are in close contact, thereby fixing the reference electrode 600 in the second connecting hole 220.

[0090] For example, when the size of the reference electrode 600 is small, a larger size reference sleeve can be selected and fitted onto the outer surface of the reference electrode 600. When the size of the reference electrode 600 is large, a smaller size reference sleeve can be selected and fitted onto the outer surface of the reference electrode 600.

[0091] In the above implementation process, by setting up reference sleeves of various specifications, a reference sleeve of the appropriate specification can be selected according to the size of the reference electrode 600 and fitted onto its outer surface, so that the outer surface of the reference sleeve is in close contact with the inner surface of the second connecting hole 220, thereby fixing the reference electrode 600 in the second connecting hole 220. This increases the size of the reference electrode 600 that can be compatible with the in-situ cell, expanding the application scenarios of the in-situ cell.

[0092] In one possible implementation, the top cover 200 is further provided with a first flow hole 230 and a second flow hole 240 along the first direction.

[0093] The first flow hole 230 penetrates the outside of the upper cover 200 and the second flow hole 210, and the second flow hole 240 penetrates the outside of the upper cover 200 and the second flow hole 210.

[0094] The first flow-through orifice 230 and the second flow-through orifice 240 are configured to allow solution to enter the second flow-through orifice 210 and / or allow solution to exit the second flow-through orifice 210.

[0095] The configuration of the first flow hole 230 and the second flow hole 240 described above can include the following methods:

[0096] Method 1: The first flow hole 230 is configured to input the solution into the second flow hole 210, and the second flow hole 240 is configured to output the solution into the second flow hole 210.

[0097] Method 2: The first flow hole 230 is configured to output the solution to the second flow hole 210, and the second flow hole 240 is configured to input the solution to the second flow hole 210.

[0098] Method 3: Both the first flow hole 230 and the second flow hole 240 are configured to input the solution into the second through hole 210.

[0099] Method 4: Both the first flow hole 230 and the second flow hole 240 are configured to output the solution through the second through hole 210.

[0100] The configuration of the first flow hole 230 and the second flow hole 240 is merely exemplary, and the configuration of the first flow hole 230 and the second flow hole 240 can be selected according to the actual situation.

[0101] It should be understood that when the first flow-through hole 230 and the second flow-through hole 240 are configured in Mode 1, if solution flow is required during the electrochemical reaction in the in-situ cell, flexible tubes can be inserted into the first flow-through hole 230 and the second flow-through hole 240 respectively, and the side of the flexible tubes away from the first flow-through hole 230 and the second flow-through hole 240 can be connected to the power device. By turning on the power device, solution is continuously added to the second through hole 210 through the first flow-through hole 230 and discharged through the second flow-through hole 240 until the solution purges the air from the first flow-through hole 230, the second flow-through hole 240, the second through hole 210, and the flexible tubes, and fills the second through hole 210.

[0102] In one embodiment, the first flow hole 230 and the second flow hole 240 are respectively disposed on both sides of the reference electrode 600.

[0103] In the above implementation process, by providing a first flow hole 230 and a second flow hole 240 on the upper cover 200, during the electrochemical reaction in the in-situ cell, the cooperation of the first flow hole 230 and the second flow hole 240 can remove air bubbles from the solution flow path, thus ensuring the stability of the electrochemical reaction. Furthermore, the cooperation of the first flow hole 230 and the second flow hole 240 allows for solution replacement and flow rate control in the in-situ cell, expanding the application scenarios of the in-situ cell. Additionally, controlling the flow rate of the solution in the first flow hole 230 and the second flow hole 240 can control the thickness of the diffusion layer on the surface of the working electrode 300, improving the accuracy of the reaction.

[0104] In one possible implementation, the in-situ pool further includes a first sealing ring 700.

[0105] The upper cover 200 has a fourth groove along the first plane, and the fourth groove is located on the side of the upper cover 200 near the base 100; the first sealing ring 700 is connected to the fourth groove, and the first sealing ring 700 is in contact with the working electrode 300.

[0106] It should be understood that when the upper cover 200 is fixed together with the base 100, the side of the first sealing ring 700 away from the upper cover 200 contacts the side of the working electrode 300 close to the upper cover 200, and the first sealing ring 700 is pressed tightly against the surface of the working electrode 300, forming a sealed space with the working electrode 300.

[0107] The shape of the first sealing ring 700 matches the shape of the second through hole 210. The first sealing ring 700 is disposed at the bottom of the second through hole 210. The first sealing ring 700, the second through hole 210 and the surface of the working electrode 300 surrounded by the first sealing ring 700 together form a space for containing the solution.

[0108] In one embodiment, the first sealing ring 700 may be an O-ring. The O-ring has a circular cross-sectional shape, simple structure, small size, and is easy to install. It can withstand high pressure and temperature and has good compressibility and resilience.

[0109] The first sealing ring 700 described above is configured to fix the contact area between the solution and the working electrode 300.

[0110] Understandably, the first sealing ring 700, the second through hole 210, and the surface of the working electrode 300 surrounded by the first sealing ring 700 together form a space for containing the solution. Therefore, by setting the first sealing ring 700 of different specifications, the surface area of ​​the working electrode 300 surrounded by the first sealing ring 700 can be changed, and the contact area between the working electrode 300 and the solution can be changed.

[0111] In the above implementation process, by setting a first sealing ring 700 between the upper cover 200 and the working electrode 300, on the one hand, the first sealing ring 700 can fill the tiny gap between the upper cover 200 and the working electrode 300 to prevent solution leakage and improve the sealing performance of the solution in the in-situ cell. On the other hand, the first sealing ring 700 can also fix the contact area between the solution and the working electrode 300. Therefore, by setting different specifications of the first sealing ring 700, the surface area of ​​the working electrode 300 surrounded by the first sealing ring 700 can be changed, thereby changing the contact area between the working electrode 300 and the solution, so as to adjust the electrochemical reaction efficiency. This achieves adjustable reaction and expands the application scenarios of the in-situ cell.

[0112] In one possible implementation, the in-situ pool also includes a top cover 810 and a cap 820.

[0113] The top cover 810 is located on the side of the upper cover 200 away from the base 100; the top cover 810 has a third through hole along the first direction; the cap 820 is detachably accommodated in the third through hole. When the cap 820 is accommodated in the third through hole, the cap 820 and the top cover 810 seal the second through hole 210 by mating.

[0114] The top cover 810 and the upper cover 200 are detachably connected. For example... Figure 3 As shown, when the in-situ pool needs to be sealed, the top cover 810 is installed on the side of the upper cover 200 away from the base 100. When the in-situ pool does not need to be sealed, the top cover 810 is removed from the side of the upper cover 200 away from the base 100.

[0115] Optionally, the top cover 810 and the upper cover 200 can be connected by screws, bolts, snap-fit, or other means. The connection method between the top cover 810 and the upper cover 200 can be selected according to the actual situation.

[0116] It should be understood that when performing battery cycle performance testing in an in-situ cell, the top cover 810 can be fixed to the upper cover 200 using a connector, and the cap 820 can be inserted into the top cover 810. When performing nano-infrared testing in an in-situ cell, the top cover 810 can be removed from the side of the upper cover 200 away from the base 100.

[0117] In the above implementation process, by setting the top cover 810 and the cap 820, when performing different test tasks in the in-situ cell, the in-situ cell can be switched between a semi-sealed state and an open state according to the sealing requirements of different test tasks, thereby adjusting the sealing performance of the in-situ cell. This reduces electrolyte evaporation and expands the application scenarios of the in-situ cell. Furthermore, when performing different tests, only the structure of the in-situ cell is changed; battery testing and nano-infrared testing do not require replacing the sample cell, thus avoiding damage to the sample during transfer, preserving the original properties of the test sample, and improving test accuracy.

[0118] In one possible implementation, the in-situ pool further includes a second sealing ring 900.

[0119] The top cover 810 has a fifth groove along the first plane, and the fifth groove is located on the side of the top cover 810 close to the upper cover 200; the second sealing ring 900 is connected to the fifth groove.

[0120] It should be understood that when the top cover 810 is fixed together with the upper cover 200, the side of the second sealing ring 900 away from the top cover 810 contacts the upper cover 200, and the second sealing ring 900 is pressed tightly against the surface of the upper cover 200, forming a sealed space with the upper cover 200.

[0121] The shape of the second sealing ring 900 matches the shape of the second through hole 210, and the second sealing ring 900 is disposed on the upper part of the second through hole 210.

[0122] In one embodiment, the second sealing ring 900 may be an O-ring. The O-ring has a circular cross-sectional shape, simple structure, small size, and is easy to install. It can withstand high pressure and temperature and has good compressibility and resilience.

[0123] The second sealing ring 900 described above is configured to seal the second through hole 210.

[0124] In the above implementation process, by providing a second sealing ring 900 on the top cover 810, which seals the second through hole 210, solution leakage can be prevented, thus improving the sealing performance of the solution in the in-situ tank. Furthermore, by improving the sealing performance of the in-situ tank through the second sealing ring 900, solution evaporation and increased solution concentration during long-term testing can be avoided, which would affect the accuracy of the reaction.

[0125] In one possible implementation, the top cover 810 and / or the cap 820 are made of a transparent material.

[0126] The transparent material here can be transparent glass, transparent plastic, transparent acrylic sheet, etc., and the transparent material can be selected according to the actual situation.

[0127] In the above implementation process, by setting the top cover 810 and / or the cap 820 to a transparent material, the electrochemical reaction inside the in-situ cell can be observed through the transparent material even when the in-situ cell is sealed, which helps to observe the situation during the electrochemical reaction process and enhances the user experience.

[0128] In one possible implementation, the in-situ pool also includes a connector.

[0129] Among them, such as Figure 4As shown, the conductive contact 400 is provided with a connecting groove 410, and the connector fixes the conductive contact 400 in the inclined groove through the connecting groove 410.

[0130] Optionally, the connector can be a screw, bolt, bolt, etc., and the connector can be selected according to the actual situation.

[0131] In the above implementation process, by providing a connecting groove 410 on the conductive contact 400, and by fixing the conductive contact 400 in the inclined groove through the connecting groove 410, the stability of the conductive contact 400 in the inclined groove can be improved, thereby improving the stability of the in-situ pool structure.

[0132] like Figure 5 The diagram shown is a schematic diagram of the spectral microscopy measurement system provided in the embodiments of this application, including: a light emitter 20, a spectral imaging microscope 30, and the electrochemical in-situ cell 10 in the above embodiments.

[0133] The light emitter 20 is located on one side of the base of the electrochemical in-situ cell 10, and the scanner 40 of the spectral imaging microscope 30 is located on one side of the top cover of the electrochemical in-situ cell 10.

[0134] The light emitter 20 here is configured to emit external light into the sample in the electrochemical in-situ cell 10 through the first through-hole of the electrochemical in-situ cell 10. The external light can be infrared light, laser light, etc., and can be selected according to the actual situation.

[0135] It should be understood that the sample in the electrochemical in-situ cell 10 is controlled by the three-electrode electrical connection between the working electrode, the counter electrode, and the reference electrode to control the reaction process in the electrochemical in-situ cell 10 or to control the electrochemical in-situ cell 10 to a constant state.

[0136] The scanner 40 described above is configured to control the probe 50 to approach the sample surface and scan the sample surface through the probe 50. The minute displacement of the probe 50 can be amplified by an optical lever system consisting of the over-polarized light emitting device 60, the probe 50, and the quadrant detector 70, and output to the computer by the quadrant detector 70.

[0137] The deflecting light emitting device 60 is located on one side of the upper cover of the electrochemical in-situ cell 10. The deflecting light emitting device 60 is configured to emit deflected light to the probe 50, and the probe 50 scans the sample surface under the illumination of the deflected light.

[0138] In one embodiment, the probe 50 is an atomic force probe. The atomic force probe is configured to scan the sample surface in real time.

[0139] Optionally, the spectral microscopy system also includes a mirror group 80 and a focusing objective lens 90.

[0140] The mirror assembly 80 and the focusing objective lens 90 are both located on one side of the first through-hole, with the mirror assembly 80 located on the side of the focusing objective lens 90 away from the first through-hole. The light emitter 20 is located on one side of the mirror assembly 80, and the light emitter 20 is positioned perpendicular to the direction of the mirror assembly 80 and the focusing objective lens 90.

[0141] The external light emitted by the light emitter 20 is reflected by the mirror group 80, then focused by the focusing objective lens 90, and then shines onto the sample through the first through hole.

[0142] The microscope is configured to acquire information about the absorption of external light by the sample during the chemical reaction process; the information about the absorption of external light by the sample during the chemical reaction process is configured to detect the sample.

[0143] It should be understood that during the scanning process, the light emitter 20 emits external light through the reflector group 80 and the focusing objective lens 90, through the infrared transparent substrate at the bottom of the electrochemical in-situ cell 10, onto the sample surface focused on the substrate, and the probe 50 scans within the focal range of the focusing objective lens 90.

[0144] Optionally, the scanning method of the probe 50 may include: 1. The probe 50 scans within a small range of the external light focus under the control of the piezoelectric ceramic in the scanner 40, while keeping the bottom nano-displacement stage stationary. 2. Keeping the probe 50 stationary within the sample surface, the electrochemical in-situ cell 10 is moved within the sample surface by moving the nano-displacement stage. Through the cooperation of the electrochemical in-situ cell 10 and the nano-infrared spectroscopy imaging microscope 30, the visualization and measurement of the electrochemical processes on the sample surface can be achieved.

[0145] In the above implementation process, by setting up a spectral microscopy measurement system including a light emitter 20, a spectral imaging microscope 30, and an electrochemical in-situ cell 10, external light is emitted vertically into the electrochemical in-situ cell 10. Compared with oblique excitation, a stronger signal can be obtained, which is beneficial for obtaining a stronger detection signal. In addition, this spectral microscopy measurement system can be compatible with external light characterization and electrochemical testing, or both simultaneously, which can improve testing efficiency and expand the application scenarios of this spectral microscopy measurement system.

[0146] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application. It should be noted that similar reference numerals and letters in the following figures indicate similar items; therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0147] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. An electrochemical in-situ cell suitable for spectroscopic microscopy measurements, characterized in that, include: Base, top cover, working electrode, conductive contact, and counter electrode; The upper cover is fixedly mounted on the base; The base is provided with a first groove, and the bottom of the first groove is provided with a first through hole; The working electrode is disposed in the first groove, and the first through hole is located on the side of the working electrode away from the upper cover; The upper cover is also provided with a second through hole along the first direction, and the upper cover is provided with an inclined groove and a first connecting hole along the first plane; wherein, the first direction is perpendicular to the first plane. The inclined groove penetrates the outside of the upper cover and the first groove, and the first connecting hole penetrates the outside of the upper cover and the second through hole; The conductive contact is disposed in the inclined groove, one end of the conductive contact is in contact with the working electrode, and the other end of the conductive contact extends to the outside of the upper cover; The counter electrode is disposed in the first connecting hole, one end of the counter electrode is located in the second through hole, and the other end of the counter electrode extends to the outside of the upper cover; The second through-hole is configured to contain a solution, and the conductive contact is configured to apply a potential to the working electrode; the working electrode, the counter electrode, and the solution undergo an electrochemical reaction under the applied potential. The portion of the working electrode housed in the first through hole is made of a transparent material; External light shines through the working electrode onto the solution in the second through hole; an external microscope is configured to acquire spectral imaging information of the solution reaction process.

2. The electrochemical in-situ cell according to claim 1, characterized in that, The upper cover is also provided with a second groove along the first plane; The second groove is located on the inner surface of the second through hole; The shape of the counter electrode, which is housed at one end of the second through hole, matches the shape of the second groove. The counter electrode is located entirely or partially within the second groove at one end of the second through hole.

3. The electrochemical in-situ cell according to claim 1, characterized in that, Also includes: Reference electrode; The upper cover is provided with a second connecting hole along the first direction, and the upper cover is provided with a third groove along the first plane; One end of the second connecting hole is connected to one end of the third groove, the third groove being configured to accommodate the solution; One end of the reference electrode is housed within the second connection hole; When the electrochemical in-situ cell is in operation, the end of the reference electrode housed in the second connection hole is in contact with the solution in the third groove.

4. The electrochemical in-situ cell according to claim 3, characterized in that, Also includes: Reference set; The reference sleeve may be one or more, and the multiple reference sleeves may correspond to multiple specifications; The reference sleeve is configured to be sleeved on the outer surface of the reference electrode; The various reference electrodes are fixed in the second connection hole by fitting reference sleeves of corresponding specifications.

5. The electrochemical in-situ cell according to any one of claims 1-4, characterized in that, The upper cover is also provided with a first flow hole and a second flow hole along the first direction; The first flow hole penetrates the outside of the upper cover and the second through hole, and the second flow hole penetrates the outside of the upper cover and the second through hole; The first flow-through hole and the second flow-through hole are configured to allow the solution to enter the second flow-through hole and / or allow the solution to exit the second flow-through hole.

6. The electrochemical in-situ cell according to any one of claims 1-4, characterized in that, Also includes: First sealing ring; The upper cover is provided with a fourth groove along the first plane, and the fourth groove is provided on the side of the upper cover close to the base; The first sealing ring is connected to the fourth groove, and the first sealing ring is in contact with the working electrode; The first sealing ring is configured to fix the contact area between the solution and the working electrode.

7. The electrochemical in-situ cell according to any one of claims 1-4, characterized in that, Also includes: top cover and cap; The top cover is located on the side of the upper cover away from the base; The top cover is provided with a third through hole along the first direction; The cap is detachable and can be accommodated within the third through hole; Wherein, when the cap is accommodated in the third through hole, the cap and the top cover seal the second through hole by fitting together.

8. The electrochemical in-situ cell according to claim 7, characterized in that, Also includes: Second sealing ring; The top cover is provided with a fifth groove along the first plane, and the fifth groove is provided on the side of the top cover close to the upper cover; The second sealing ring is connected to the fifth groove; The second sealing ring is configured to seal the second through hole.

9. The electrochemical in-situ cell according to any one of claims 1-4, characterized in that, Also includes: Connectors; The conductive contact piece is provided with a connection groove; The connector fixes the conductive contact in the inclined groove through the connecting groove.

10. A spectral microscopy measurement system, characterized in that, include: A light emitter, a spectroscopic imaging microscope, and an electrochemical in-situ cell according to any one of claims 1-9; The light emitter is disposed on one side of the base of the electrochemical in-situ cell, and the light emitter is configured to emit external light to the sample in the electrochemical in-situ cell through the first through hole of the electrochemical in-situ cell; The scanner of the spectral imaging microscope is located on one side of the upper cover of the electrochemical in-situ cell. The scanner is configured to control the probe to approach the sample surface and scan the sample surface through the probe. The microscope acquires information about the absorption of external light by the sample during the chemical reaction process; the absorption of external light by the sample during the chemical reaction process is configured to detect the sample.

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