Preparation method of microelectrode and in-situ electrochemical Raman spectrum pool

Abstract

The invention relates to a preparation method of a microelectrode and an in-situ electrochemical Raman spectrum pool, the in-situ electrochemical Raman spectrum pool comprises a base, a working electrode, an auxiliary electrode, a reference electrode and an electrode fixing table, the base is provided with an electrolytic tank and a limiting groove, the electrode fixing table is installed on the base, the electrode fixing table is provided with a plurality of limiting holes, and the working electrode and the auxiliary electrode are arranged on the base. The working electrode is mounted on the limiting groove, extends out of the corresponding limiting hole of the electrolytic tank and is exposed; and the working electrode comprises an electrode base and the microelectrode prepared by the preparation method of the microelectrode. According to the in-situ electrochemical Raman spectrum cell, the current collector and the micro-electric body are packaged in the microelectrode in the hose together, so that the exposed part of the current collector of the microelectrode is positioned outside the electrolyte of the electrolytic cell, and the exposed part of the micro-electric body of the microelectrode is positioned in the electrolyte of the electrolytic cell; therefore, the interference of the current collector on a microelectrode signal is effectively avoided; and the electrolytic tank without a bottom hole is formed, so that the electrolyte in the electrolytic tank is further prevented from leaking.

Description

Technical Field

[0001] The present application relates to the technical field of Raman spectroscopy detection, and in particular to a method for preparing a microelectrode and an in-situ electrochemical Raman spectroscopy cell. Background Art

[0002] In-situ electrochemical Raman spectroscopy is a technique that collects Raman signals from electrodes while conducting electrochemical tests, thereby achieving simultaneous monitoring of the electrochemical properties and structural changes of the electrodes. Since this technology involves the combined use of electrochemistry and Raman spectroscopy, a specially designed in-situ electrochemical Raman spectroscopy cell is required. Existing in-situ electrochemical Raman spectroscopy cells are unable to collect changes in Raman signals within a very short period of time after an electrochemical reaction occurs, and the very short period of time is usually on the order of nanoseconds or even microseconds. Currently, most in-situ electrochemical Raman cells on the market are designed based on conventional size electrodes, and the working electrode area is usually on the order of square centimeters. Therefore, existing in-situ electrochemical Raman spectroscopy cells can no longer meet the requirements of the microsecond level.

[0003] The main limitation of existing in situ electrochemical Raman spectroscopy on the electrochemical cell side is the charge and discharge effect of the electrode surface capacitance. The time constant of the electrode τ = R u C d Need to reach microseconds and below, where R u is the uncompensated resistance, which is related to the distance x from the working electrode to the reference electrode, the radius r0 of the working electrode, and the conductivity κ of the solution, and can be expressed by expression 1. d is the double-layer capacitance of the electrode surface, which can be expressed as: ; In the formula, is the interfacial capacitance per unit area, and the typical value for metal disk electrodes is 10~50μF / cm 2 , therefore, the electrode time constant τ can be expressed using expression 2, which means that when the roughness of the electrolyte and electrode surface is constant, the time constant is proportional to the size r0 of the working electrode. To reduce the time constant, it is necessary to reduce the electrode size, that is, to use a microelectrode. Typically, the effective size of a microelectrode is only 10~100μm, while the size of a conventional electrode is usually 0.1~1cm. Therefore, the structure of a microelectrode is usually different from that of a conventional electrode, and many designs suitable for conventional electrodes are not suitable for microelectrodes. It can be seen that time-resolved in situ electrochemical Raman requires a dedicated electrochemical cell compatible with microelectrodes.

[0004] Expression 1 is:

[0005]

[0006] Expression 2 is:

[0007]

[0008] Currently, there are electrolytic cells designed specifically for microelectrodes on the market, but there is still a lot of room for optimization overall. For example, there is an existing electrochemical device that can insert microelectrodes from the side, such as Fig.10 As shown. The electrochemical device design fixes the microelectrode through a pre-fixed electrode clamp so that it "lies flat" under the observation window, thereby avoiding leaving a hole at the bottom of the electrochemical cell, preventing leakage and facilitating movement. However, the electrochemical device scheme still uses a linear microelectrode. After being inserted horizontally into the electrolytic cell, only the side of the electrode can be observed, and the upper end surface of the microelectrode cannot be exposed, so the function is limited. At the same time, since the part of the microelectrode that contacts the electrode clamp is exposed to the solution, this may cause side reactions, thereby affecting the experimental results. Summary of the invention

[0009] The embodiments of the present application provide a method for preparing a microelectrode and an in-situ electrochemical Raman spectroscopy cell, which are used to solve the technical problem that the current collector of the working electrode of the existing microelectrode electrochemical testing device is exposed to the electrolyte and is prone to leakage, resulting in inaccurate detection results.

[0010] In order to achieve the above objectives, the embodiments of the present application provide the following technical solutions:

[0011] In one aspect, a method for preparing a microelectrode is provided, comprising the following steps:

[0012] Obtaining materials for preparing microelectrodes, the materials comprising thick copper wire, thin copper wire, a hose, conductive silver glue, sealant and sandpaper;

[0013] The thick copper wire and the thin copper wire are fixedly connected with each other using the conductive silver glue to obtain an electrode wire;

[0014] The thin copper wire of the electrode lead is placed in the hose and fixed by the sealant to obtain an initial microelectrode with the thick copper wire exposed for a first distance;

[0015] The sandpaper is used to grind the exposed thick copper wire of the initial microelectrode to obtain a bendable microelectrode.

[0016] Preferably, the diameter of the thick copper wire is 0.3 mm, and the length of the thick copper wire is 10 cm; and / or, the diameter of the thin copper wire is 25 μm, and the length of the thin copper wire is 3 cm; and / or, the inner diameter of the hose is 0.4 mm, and the length of the hose is 10 cm; and / or, the sealant is made of epoxy resin; and / or, the hose is a polytetrafluoroethylene hose.

[0017] On the other hand, an in-situ electrochemical Raman spectroscopy cell is provided, comprising a base, a working electrode, an auxiliary electrode, a reference electrode and an electrode fixing platform, wherein the base is provided with an electrolytic cell and a limiting groove for installing the working electrode, the electrode fixing platform is installed on the base, and a plurality of limiting holes for fixing the working electrode, the auxiliary electrode and the reference electrode are provided on the electrode fixing platform, the working electrode is installed on the limiting groove and extends out and is exposed through the limiting hole corresponding to the electrolytic cell, and the working electrode comprises an electrode base matching the limiting groove and a microelectrode prepared by the above-mentioned microelectrode preparation method and arranged on the electrode base.

[0018] Preferably, the electrode base is provided with a connection hole for matching and installing the microelectrode; and / or, the electrode base is provided with a limiting boss for fixed installation, and the working electrode also includes an electrode pressure cover covering the limiting boss and fixing the working electrode in the limiting groove.

[0019] Preferably, the in-situ electrochemical Raman spectroscopy cell comprises an observation mechanism with adjustable focal length, the electrolytic cell is provided with a mounting limit groove for threaded connection with the observation mechanism, and the mounting limit groove is provided with a first internal thread.

[0020] Preferably, the observation mechanism includes a first fixing element, an observation element and a second fixing element, the inner wall surface of the first fixing element is provided with a second internal thread, and the outer wall surface of the second fixing element is provided with a second external thread matching the second internal thread threaded connection, and the observation element is arranged between the first fixing element and the second fixing element; the outer wall surface of the first fixing element is provided with a first external thread matching the first internal thread in the installation limit groove, and the axial distance between the observation element and the observed substance placed in the electrolytic cell is adjusted by adjusting the screwing length of the first external thread and the first internal thread threaded connection.

[0021] Preferably, a sealing gasket for fixing the observation element is provided between the observation element and the second fixing element; and / or slots for assembly and disassembly are provided on the first fixing element and the second fixing element.

[0022] Preferably, the in-situ electrochemical Raman spectroscopy cell comprises a weight element for keeping the center of gravity of the electrolytic cell always at the center of the base, and a slot for installing the weight element is provided on the base.

[0023] Preferably, the auxiliary electrode is an electrode made of platinum wire or carbon rod; and / or, the reference electrode is an electrode made of Hg / HgO, Ag / AgCl or Hg / Hg2SO4.

[0024] Preferably, the in-situ electrochemical Raman spectroscopy cell includes a gland for fixing the electrode and the pipeline on the electrode fixing platform, and the electrode fixing platform is also provided with a first mounting hole, a second mounting hole and several pipeline through holes; correspondingly, the gland is provided with through holes matching the limiting hole, the second mounting hole and several pipeline through holes.

[0025] The microelectrode preparation method and in-situ electrochemical Raman spectroscopy cell, the in-situ electrochemical Raman spectroscopy cell, comprises a base, a working electrode, an auxiliary electrode, a reference electrode and an electrode fixing platform, the base is provided with an electrolytic cell and a limiting groove for installing the working electrode, the electrode fixing platform is installed on the base, the electrode fixing platform is provided with a plurality of limiting holes for fixing the working electrode, the auxiliary electrode and the reference electrode, the working electrode is installed on the limiting groove and extends out through the limiting hole corresponding to the electrolytic cell to be exposed, the working electrode comprises an electrode base matched with the limiting groove and a microelectrode prepared by the above-mentioned microelectrode preparation method and arranged on the electrode base. It can be seen from the above technical scheme that the embodiments of the present application have the following advantages: the in-situ electrochemical Raman spectroscopy cell, by encapsulating the current collector and the microelectrode together in a hose, can allow the exposed part of the current collector of the microelectrode to be located outside the electrolyte of the electrolytic cell, while the exposed part of the microelectrode of the microelectrode is located within the electrolyte of the electrolytic cell, thereby effectively avoiding the interference of the current collector on the microelectrode signal; by providing an electrolytic cell without a bottom hole, leakage of the electrolyte in the electrolytic cell is further avoided, thereby solving the technical problem that the current collector of the working electrode in the existing microelectrode electrochemical testing device is exposed to the electrolyte and is prone to leakage, resulting in inaccurate detection results.

[0026] The microelectrode prepared by the microelectrode preparation method is bendable, so that the microelectrode can be introduced in a bent manner from above the electrolytic cell of the chemical Raman spectroscopy cell and the observation end surface of the microelectrode is exposed upward, thereby solving the problem of matching the electrolytic cell and the microelectrode of the existing chemical Raman spectroscopy cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0028] Figure 1 A flowchart of the steps of the method for preparing the microelectrode described in the embodiment of the present application;

[0029] Figure 2 This is a schematic diagram of the structure of the in-situ electrochemical Raman spectroscopy cell described in the embodiments of the present application;

[0030] Figure 3This is a schematic diagram of the decomposition structure of the in-situ electrochemical Raman spectroscopy cell described in the embodiments of the present application;

[0031] Figure 4 This is a schematic diagram of the structure of the working electrode in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application;

[0032] Figure 5 This is a schematic diagram of the structure of the electrode cover 4 in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application;

[0033] Figure 6 This is a schematic diagram of the structure of the base in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application;

[0034] Figure 7 This is a schematic diagram of the structure of the first fixed element in the in-situ electrochemical Raman spectroscopy cell described in an embodiment of the present application;

[0035] Figure 8 This is a schematic diagram of the structure of the pressure cover in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application;

[0036] Fig. 9 This is a schematic diagram of the structure of the electrode fixing platform in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application;

[0037] Fig.10 This is an implementation effect diagram of the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application;

[0038] Fig.11 Schematic diagram of the structure of an existing electrochemical device into which a microelectrode can be inserted from the side. DETAILED DESCRIPTION

[0039] In order to make the purpose, features, and advantages of the invention of this application more obvious and easy to understand, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the drawings in the embodiments of this application. Obviously, the embodiments described below are only part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0040] In the description of the embodiments of the present application, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the embodiments of the present application, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0041] In the embodiments of the present application, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral one; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the embodiments of the present application can be understood according to the specific circumstances.

[0042] The embodiments of the present application provide a method for preparing a microelectrode and an in-situ electrochemical Raman spectroscopy cell, which solve the technical problem that the current collector of the working electrode of the existing microelectrode electrochemical testing device is exposed to the electrolyte and is prone to leakage, resulting in inaccurate detection results.

[0043] Embodiment 1:

[0044] Figure 1 This is a flow chart of the steps of the method for preparing the microelectrode described in an embodiment of the present application.

[0045] like Figure 1 As shown, the present application embodiment provides a method for preparing a microelectrode, comprising the following steps:

[0046] S1. Obtain materials for preparing microelectrodes, including thick copper wire, thin copper wire, hose, conductive silver glue, sealant and sandpaper.

[0047] It should be noted that in step S1, the material for preparing the microelectrode is obtained to provide the material for preparing the microelectrode. In the present embodiment, the thick copper wire can be a copper wire with a diameter of 0.3 mm and a length of 10 cm. The thin copper wire can be a copper wire with a diameter of 25 μm and a length of 3 cm. The hose can be a tube with an inner diameter of 0.4 mm and a length of 10 cm. The sealant can be made of epoxy resin. The hose can be a polytetrafluoroethylene hose. Among them, the sandpaper includes sandpaper of several different mesh sizes. The mesh size can be 100 mesh to 12000 mesh.

[0048] S2. Use conductive silver glue to fix the thick copper wire and the thin copper wire to obtain an electrode wire.

[0049] It should be noted that in step S2, the electrode wire is made. In this embodiment, a thin copper wire with a diameter of 25 μm is connected to a thick copper wire with a diameter of 0.3 mm using conductive silver glue to ensure that the two copper wires are electrically connected and that the thin copper wire is exposed to at least 2 cm of the electrode wire. The electrode wire is a copper wire with a front end of 25 μm diameter and a rear end of 0.3 mm diameter. The front end will serve as the micro-electric body of the electrode wire, and the rear end will serve as the current collector of the electrode wire.

[0050] S3. Place the thin copper wire of the electrode lead in a soft tube and fix it with a sealant to obtain an initial microelectrode with the thick copper wire of the first distance exposed.

[0051] It should be noted that in step S3, the electrode wire produced in step S2 is placed in the hose. In this embodiment, after the conductive silver glue in the electrode wire is dried, the front end of the electrode wire is inserted into the hose, so that the rear end of the electrode wire is exposed for a first distance for connecting the electrode clamp, and the front end of the electrode wire is encapsulated in the hose, and then a sealant made of epoxy resin is poured into the hose for potting. After the glue is dried, the thin copper wire with a diameter of 25 μm is completely fixed in the hose. Among them, the first distance is at most 9 cm.

[0052] S4. Use sandpaper to grind the exposed thick copper wire of the initial microelectrode to obtain a bendable microelectrode.

[0053] It should be noted that, in order to facilitate the connection of the microelectrode, in step S4, the exposed thick copper wire of the initial microelectrode prepared in step S3 is polished in sequence from coarse to fine using sandpaper until the end face of the 25 μm diameter thin copper wire in the hose is exposed and polished; then the polished copper wire is wiped with ethanol and the conductivity is tested to obtain a microelectrode with a diameter of 25 μm and good flexibility.

[0054] In the embodiment of the present application, the microelectrode prepared by the microelectrode preparation method is to encapsulate the current collector and the microelectric body together in a hose, which cleverly solves the problem of current collector exposure. The exposed part of the current collector is located outside the electrolyte, while the exposed part of the microelectric body is located inside the electrolyte, thereby effectively avoiding the interference of the current collector on the microelectrode signal.

[0055] It should be noted that the main reason why the current microelectrodes are not well adapted is that the microelectrodes are linear. The microelectrodes prepared by the microelectrode preparation method are bendable, which makes it possible to introduce the microelectrode in a bent manner from above the electrolytic cell of the chemical Raman spectroscopy cell and expose the observation end face of the microelectrode upward, thereby solving the problem of adaptation between the electrolytic cell and the microelectrode of the existing chemical Raman spectroscopy cell.

[0056] Embodiment 2:

[0057] Figure 2 Schematic diagram of the structure of the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application, Figure 3 This is a schematic diagram of the decomposed structure of the in-situ electrochemical Raman spectroscopy cell described in an embodiment of the present application.

[0058] like Figure 2 and Figure 3As shown, an embodiment of the present application provides an in-situ electrochemical Raman spectroscopy cell, including a base 1, a working electrode 3, an auxiliary electrode 8, a reference electrode 7 and an electrode fixing platform 13. The base 1 is provided with an electrolytic cell 1-11 and a limiting groove 1-2 for installing the working electrode 3. The electrode fixing platform 13 is installed on the base 1. The electrode fixing platform 13 is provided with a plurality of limiting holes for fixing the working electrode 3, the auxiliary electrode 8 and the reference electrode 7. The working electrode 3 is installed on the limiting groove 1-2 and extends out and is exposed through the limiting hole 13-4 corresponding to the electrolytic cell 1-11. The working electrode 3 includes an electrode base 3-4 matching the limiting groove 1-2 and a microelectrode prepared by the above-mentioned microelectrode preparation method and arranged on the electrode base 3-4.

[0059] It should be noted that the content of the preparation method of the microelectrode has been described in Example 1 and will not be repeated in this example. The auxiliary electrode 8 and the reference electrode 7 are arranged in the electrolytic cell 1-11 through the corresponding limiting holes 13-6 and the limiting holes 13-9. In this embodiment, the in-situ electrochemical Raman spectroscopy cell is provided with an electrolytic cell 1-11 with no holes at the bottom on the base 1, and several limiting holes for limiting the electrodes are provided through the electrode fixing platform 13 located above the base 1, so that all holes are above the liquid level of the electrolytic cell 1-11, fundamentally preventing the liquid in the electrolytic cell 1-11 from leaking, thereby solving the problem of electrolytic cell leakage in the existing electrochemical Raman spectroscopy cell. Among them, the in-situ electrochemical Raman spectroscopy cell adopts Example 1 to manufacture a microelectrode in which the current collector and the microelectric body are encapsulated in a hose, so that the exposed part of the current collector of the microelectrode is located outside the electrolyte of the electrolytic cell 1-11, while the exposed part of the microelectric body of the microelectrode is located inside the electrolyte of the electrolytic cell 1-11, thereby effectively avoiding the interference of the current collector on the microelectrode signal.

[0060] In the embodiment of the present application, the auxiliary electrode 8 can be an electrode made of platinum wire or carbon rod. The reference electrode 7 can be an electrode made of Hg / HgO, Ag / AgCl or Hg / Hg2SO4.

[0061] It should be noted that after the electrolyte is injected into the electrolytic cell 1-11, the electrolyte, the working electrode 3, the auxiliary electrode 8 and the reference electrode 7 in the electrolytic cell 1-11 constitute a three-electrode system of an in-situ electrochemical Raman spectroscopic cell, so that the in-situ electrochemical Raman spectroscopic cell can obtain the electrochemical signal and Raman signal transmitted by the microelectrode in the working electrode 3 when powered on, and obtain the electrochemical Raman spectrum based on the electrochemical signal and the Raman signal, so as to obtain test data for studying the change of material structure with potential through the in-situ electrochemical Raman spectroscopic cell.

[0062] In an embodiment of the present application, the in-situ electrochemical Raman spectroscopy cell fixes the working electrode 3 at the center of the electrolytic cell 1-11 through the limiting groove 1-2, and the auxiliary electrode 8 and the reference electrode 7 are respectively arranged in the electrolytic cell 1-11 through the limiting holes of the electrode fixing platform 13, so that the working electrode 3, the auxiliary electrode 8, and the reference electrode 7 can all work independently, so that the working electrode 3 can be replaced according to user needs, thereby improving the practicality of the in-situ electrochemical Raman spectroscopy cell.

[0063] The present application provides an in-situ electrochemical Raman spectroscopy cell, comprising a base, a working electrode, an auxiliary electrode, a reference electrode and an electrode fixing platform, wherein an electrolytic cell and a limiting groove for installing the working electrode are provided on the base, the electrode fixing platform is installed on the base, a plurality of limiting holes for fixing the working electrode, the auxiliary electrode and the reference electrode are provided on the electrode fixing platform, the working electrode is installed on the limiting groove and extends out through the limiting hole corresponding to the electrolytic cell to be exposed, and the working electrode comprises an electrode base matching the limiting groove and a microelectrode prepared by the above-mentioned microelectrode preparation method and arranged on the electrode base. The in-situ electrochemical Raman spectroscopy cell can make the exposed part of the current collector of the microelectrode be located outside the electrolyte of the electrolytic cell, while the exposed part of the microelectrode of the microelectrode is located inside the electrolyte of the electrolytic cell, by encapsulating the microelectrode with the current collector and the microelectrode in a hose, thereby effectively avoiding the interference of the current collector on the microelectrode signal; by providing an electrolytic cell without a bottom hole, leakage of the electrolyte in the electrolytic cell is further avoided, solving the technical problem of the existing microelectrode electrochemical testing device in which the current collector of the working electrode is exposed to the electrolyte and is prone to leakage, resulting in inaccurate detection results.

[0064] Figure 4 Schematic diagram of the structure of the working electrode in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application. Figure 4 In the figure, 3-1 indicates a microelectrode.

[0065] like Figure 3 and Figure 4 As shown, in one embodiment of the present application, a connection hole 3-2 for matching and installing the microelectrode is provided on the electrode base 3-4; and / or, a limiting boss 3-3 for fixed installation is provided on the electrode base 3-4, and the working electrode 3 also includes an electrode pressure cover 4 that covers the limiting boss 3-3 and fixes the working electrode 3 in the limiting groove 1-2.

[0066] Figure 5 Schematic diagram of the structure of the electrode cover 4 in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application.

[0067] like Figure 3 and Figure 5As shown, in the embodiment of the present application, a connection hole column matching with the limiting protrusion 3-3 is provided in the electrode gland 4. In order to facilitate fixing the working electrode 3 to the electrode gland 4 of the limiting groove 1-2, a third external thread 4-1 is provided on the outer wall of the connection hole column. The end face 4-2 of the connection hole column is smooth.

[0068] Figure 6 This is a schematic diagram of the structure of the base in the in-situ electrochemical Raman spectroscopy cell described in an embodiment of the present application.

[0069] like Figure 3 and Figure 6 As shown, in one embodiment of the present application, the in-situ electrochemical Raman spectroscopy cell includes a weight element 2 for keeping the center of gravity of the electrolytic cell 1-11 always at the center of the base 1, and a slot 1-1 for installing the weight element 2 is provided on the corresponding base 1.

[0070] It should be noted that the weight element 2 may be a weight block. In this embodiment, the weight element 2 is placed in the slot 1-1 of 1 to balance the entire in-situ electrochemical Raman spectroscopy cell, keep the center of gravity of the base 1 at the center, and prevent the in-situ electrochemical Raman spectroscopy cell from flipping and falling during use.

[0071] In the embodiments of the present application, Figure 6 As shown, the inner wall surface of the limit groove 1-2 is provided with a third internal thread 1-3 matching the third external thread 4-2. In order to facilitate the installation of the electrode fixing platform 13, a plurality of mounting holes are provided on the corresponding base 1. In this embodiment, four mounting holes are provided on the base 1, and the four mounting holes are respectively Figure 6 The numbers are 1-5, 1-6, 1-8 and 1-9. Each mounting hole can be a screw hole.

[0072] It should be noted that in order to prevent the electrolyte in the electrolytic cell 1-11 from being filled and overflowing, a liquid outlet 1-7 is provided on the base 1.

[0073] Figure 7 This is a schematic diagram of the structure of the first fixed element in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application. Figure 7 In the figure, 16-2 represents a step slot for placing the observation element 17.

[0074] like Figure 3 , Figure 6 and Figure 7As shown, in one embodiment of the present application, the in-situ electrochemical Raman spectroscopy cell includes an observation mechanism with adjustable focal length, and an installation limit groove 1-4 for threaded connection with the observation mechanism is provided on the electrolytic cell 1-11, and a first internal thread is provided on the installation limit groove 1-4. The observation mechanism includes a first fixing element 16, an observation element 17 and a second fixing element 19, the inner wall surface of the first fixing element 16 is provided with a second internal thread 16-3, and the outer wall surface of the corresponding second fixing element 19 is provided with a second external thread matching the second internal thread thread connection, and the observation element 17 is arranged between the first fixing element 16 and the second fixing element 19; the outer wall surface of the first fixing element 16 is provided with a first external thread 16-1 matching the first internal thread in the installation limit groove 1-4, and the axial distance between the observation element 17 and the observed substance placed in the electrolytic cell 1-11 is adjusted by adjusting the screwing length of the first external thread 16-1 and the first internal thread thread connection.

[0075] It should be noted that the first fixing element 16 and the second fixing element 19 can be selected as a pressure ring. The observation element 17 can be selected as a glass observation piece with a thickness of 0.17 mm. The in-situ electrochemical Raman spectroscopy cell greatly reduces the distance from the working electrode 3 to the observation microscope through the 0.17 mm thick observation piece, so that the objective lens with a short working distance can be used, thereby improving the Raman signal collection efficiency.

[0076] In an embodiment of the present application, a sealing gasket 18 for fixing the observation element 17 is provided between the observation element 17 and the second fixing element 16; and / or, a slot 16-4 for disassembly and assembly is provided on the first fixing element 16 and the second fixing element 19.

[0077] It should be noted that the sealing gasket 18 can be a flat gasket made of silicone. The working principle of the observation mechanism is to first place the circular observation element 17 on the inner hole of the first fixed element 16, then place the sealing gasket 18 made of large-diameter silicone on the surface of the observation element 17, and then connect the second external thread of the second fixed element 19 with the second internal thread in the first fixed element 16 so that the observation element 17 is compressed, sealed and fixed. Afterwards, the axial distance is adjusted by connecting the first external thread 16-1 of the first fixed element 16 with the internal thread of the mounting limit groove 1-4 of the base 1, so that the focal length between the spectral microscope lens and the observed substance can be adjusted through the in-situ electrochemical Raman spectroscopy cell, thereby obtaining clear imaging and more detailed spectral information.

[0078] Figure 8 This is a schematic diagram of the structure of the cover in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application. Fig. 9 This is a schematic diagram of the structure of the electrode fixing platform in the in-situ electrochemical Raman spectroscopy cell described in the embodiment of the present application.

[0079] like Figure 2 , Figure 3 , Figure 8 and Fig. 9 As shown, in one embodiment of the present application, the in-situ electrochemical Raman spectroscopy cell includes a gland 12 for fixing electrodes and pipes on an electrode fixing platform 13, and the electrode fixing platform 13 is also provided with a first mounting hole, a second mounting hole and several pipe through holes; the corresponding gland 12 is provided with through holes matching the limiting hole, the second mounting hole and several pipe through holes.

[0080] It should be noted that if Figure 8 and Fig. 9 As shown, corresponding to the four mounting holes of the base 1, the fixed electrode fixing platform 13 is also provided with four first mounting holes, which are numbered 13-1, 13-2, 13-11 and 13-12 respectively. The fixed electrode fixing platform 13 is also provided with two second mounting holes, which are numbered 13-3 and 13-10; the gland 12 is correspondingly provided with two through holes matching the second mounting holes, which are numbered 12-1 and 12-8. There are three pipeline through holes on the fixed electrode fixing platform 13, which are the air intake through hole 13-5, the liquid intake through hole 13-7 and the exhaust through hole 13-8 respectively, and the gland 12 is correspondingly provided with three through holes matching the pipeline through holes, which are numbered 12-6, 12-4 and 12-3. Among them, the through holes 12-7, 12-5 and 12-2 correspond to the limit holes 13-4, 13-6 and 13-9 respectively.

[0081] like Figure 2 and Figure 3 As shown, in an embodiment of the present application, the in-situ electrochemical Raman spectroscopy cell includes a liquid inlet pipe 9, an exhaust pipe 11 and an air inlet pipe 10, and the liquid inlet pipe 9, the exhaust pipe 11 and the air inlet pipe 10 are all arranged on the pipe through hole of the electrode fixing platform 13 through a fastener 15 with a central through hole.

[0082] It should be noted that the fastener 15 can be selected as a screw with a central through hole. The intake pipe 10 and the exhaust pipe 11 are respectively inserted into the central through hole position of the fastener 15 on the gland 12 and penetrated into the electrolytic cell 1-11 to realize the intake and exhaust functions. The screw 14 is screwed into the internal threads of the second mounting hole 13-10 and the second mounting hole 13-3 through the through hole 12-1 and through 12-8; and then the fastener 15 is screwed into the internal threads of the exhaust through hole 13-8 and the intake through hole 13-5 through the through hole 12-3 and through hole 12-6 to realize the fixation of the gland 12 and the electrode fixing platform 13. The reference electrode 7, the auxiliary electrode 8 and the liquid inlet pipe 9 are respectively inserted into the through hole 12-2, the through hole 12-7 and the through hole 12-4 on the gland 12, and then the reference electrode 7 and the auxiliary electrode 8 are covered with an O-shaped sealing ring 5, and the liquid inlet pipe 9 is covered with a silicone sealing flat gasket 6, so that the gland 12 fixes the components on the electrode fixing platform 13. In other embodiments, if the electrolytic cell of the in-situ electrochemical Raman spectroscopy cell does not require gas to enter, the fastener 15 can be replaced by a screw 14 without a central through hole.

[0083] In the embodiment of the present application, the working electrode 3 is first placed on the base 1, and the electrode base 3-4 is coaxially matched with the limiting groove 1-2 so that its radial direction is fixed, and then the third external thread 4-1 of the gland 4 is threadedly connected with the third internal thread 1-3 of the limiting groove 1-2, so that the end face 4-2 of the connecting hole column contacts and presses the connecting hole 3-2, so as to achieve axial fixation of the working electrode 3. Finally, the microelectrode 3-1 is covered with a silicone sealing flat gasket 6, and is fixed through the limiting hole 13-6 of the electrode fixing platform 13 and the through hole 12-5 of the gland 12 in turn, and then extended out for easy connection.

[0084] In the embodiments of the present application, the in-situ electrochemical Raman spectroscopy cell adopts a bendable microelectrode and a fully enclosed base, avoiding opening from the bottom of the base, and completely solving the leakage problem; at the same time, the bottom of the base remains flat, which is conducive to its free movement on the microscope displacement stage, making the experiment more convenient, and the bendable microelectrode can solve the problem of electrolytic cell and microelectrode adaptation; the use of ultra-thin observation elements can greatly reduce the impact of refractive index changes on Raman signal acquisition. The in-situ electrochemical Raman spectroscopy cell can replace the working electrode according to demand, so that the in-situ electrochemical Raman spectroscopy cell can realize the functions of microelectrode and normal electrode in-situ Raman spectroelectrochemistry. The in-situ electrochemical Raman spectroscopy cell ensures the inlet and outlet of liquid through the liquid inlet pipe, and the inlet and outlet pipes can also be used to introduce suitable gas above or below the liquid surface of the electrolyte in the electrolytic cell to create a specific gas atmosphere, which is convenient for research.

[0085] Fig.10 This is a diagram showing the implementation effect of the in-situ electrochemical Raman spectroscopy cell described in an embodiment of the present application.

[0086] In the embodiments of the present application, Fig.10 As shown in the figure, the overall implementation effect diagram of the in-situ electrochemical Raman spectroscopy cell shows the layout of the entire device. The entire in-situ electrochemical Raman spectroscopy cell is under a microscope, and the Raman signal changes on the surface of the microelectrode are observed and collected through a microscope through a 0.17mm transparent observation element (such as a window). The bendable microelectrode is inserted from the top of the electrolytic cell, and the connecting end (such as the end) of the microelectrode faces upward after bending. Acidic, alkaline or neutral electrolyte can be injected into the electrolytic cell. After the auxiliary electrode and the reference electrode are inserted, the power is turned on to start collecting electrochemical signals.

[0087] It should be pointed out in particular that Fig.10 The 3D printed model shown in the figure is made of different materials than the final version. The final version of the shell will be made of corrosion-resistant materials such as PEEK or PTFE and processed by lathe. The size specifications of the auxiliary electrode and reference electrode used can be flexibly adjusted according to the hole size of the corresponding limit hole.

[0088] Those skilled in the art can clearly understand that, for the convenience and brevity of description, the specific working processes of the systems, devices and units described above can refer to the corresponding processes in the aforementioned method embodiments and will not be repeated here.

[0089] In the several embodiments provided in the present application, it should be understood that the disclosed systems, devices and methods can be implemented in other ways. For example, the device embodiments described above are only schematic. For example, the division of the units is only a logical function division. There may be other division methods in actual implementation, such as multiple units or components can be combined or integrated into another system, or some features can be ignored or not executed. Another point is that the mutual coupling or direct coupling or communication connection shown or discussed can be an indirect coupling or communication connection through some interfaces, devices or units, which can be electrical, mechanical or other forms.

[0090] The units described as separate components may or may not be physically separated, and the components shown as units may or may not be physical units, that is, they may be located in one place or distributed on multiple network units. Some or all of the units may be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0091] In addition, each functional unit in each embodiment of the present application may be integrated into one processing unit, or each unit may exist physically separately, or two or more units may be integrated into one unit. The above-mentioned integrated unit may be implemented in the form of hardware or in the form of software functional units.

[0092] If the integrated unit is implemented in the form of a software functional unit and sold or used as an independent product, it can be stored in a computer-readable storage medium. Based on this understanding, the technical solution of the present application is essentially or the part that contributes to the prior art or all or part of the technical solution can be embodied in the form of a software product. The computer software product is stored in a storage medium, including several instructions for a computer device (which can be a personal computer, server, or network device, etc.) to perform all or part of the steps of the method described in each embodiment of the present application. The aforementioned storage medium includes: U disk, mobile hard disk, read-only memory (ROM), random access memory (RAM), disk or optical disk, etc., various media that can store program codes.

[0093] As described above, the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a microelectrode, characterized in that: The following steps are involved: obtaining materials for preparing microelectrodes, the materials comprising thick copper wire, thin copper wire, a hose, conductive silver glue, sealant and sandpaper; The thick copper wire and the thin copper wire are fixedly connected with each other using the conductive silver glue to obtain an electrode wire; The thin copper wire of the electrode lead is placed in the hose and fixed by the sealant to obtain an initial microelectrode with the thick copper wire exposed for a first distance; The sandpaper is used to grind the exposed thick copper wire of the initial microelectrode to obtain a bendable microelectrode.

2. The method for preparing a microelectrode according to claim 1, characterized in that: The diameter of the thick copper wire is 0.3 mm, and the length of the thick copper wire is 10 cm; and / or, the diameter of the thin copper wire is 25 μm, and the length of the thin copper wire is 3 cm; and / or, the inner diameter of the hose is 0.4 mm, and the length of the hose is 10 cm; and / or, the sealant is made of epoxy resin; and / or, the hose is a polytetrafluoroethylene hose.

3. An in-situ electrochemical Raman spectroscopy cell, characterized in that: It includes a base, a working electrode, an auxiliary electrode, a reference electrode and an electrode fixing platform, the base is provided with an electrolytic cell and a limiting groove for installing the working electrode, the electrode fixing platform is installed on the base, and the electrode fixing platform is provided with a plurality of limiting holes for fixing the working electrode, the auxiliary electrode and the reference electrode, the working electrode is installed on the limiting groove and extends out through the limiting hole corresponding to the electrolytic cell to be exposed, and the working electrode includes an electrode base matching the limiting groove and a microelectrode prepared by the microelectrode preparation method as described in claim 1 or 2 and arranged on the electrode base.

4. The in-situ electrochemical Raman spectroscopy cell according to claim 3, characterized in that: The electrode base is provided with a connection hole for matching and installing the microelectrode; and / or, the electrode base is provided with a limiting boss for fixed installation, and the working electrode also includes an electrode pressure cover covering the limiting boss and fixing the working electrode in the limiting groove.

5. The in-situ electrochemical Raman spectroscopy cell according to claim 3, characterized in that: It comprises an observation mechanism with adjustable focal length, the electrolytic cell is provided with a mounting limit groove for threaded connection with the observation mechanism, and the mounting limit groove is provided with a first internal thread.

6. The in-situ electrochemical Raman spectroscopy cell according to claim 5, characterized in that: The observation mechanism includes a first fixing element, an observation element and a second fixing element. The inner wall surface of the first fixing element is provided with a second internal thread, and the outer wall surface of the second fixing element is provided with a second external thread matching the second internal thread threaded connection. The observation element is arranged between the first fixing element and the second fixing element; the outer wall surface of the first fixing element is provided with a first external thread matching the first internal thread in the installation limit groove, and the axial distance between the observation element and the observed substance placed in the electrolytic cell is adjusted by adjusting the screwing length of the first external thread and the first internal thread threaded connection.

7. The in-situ electrochemical Raman spectroscopy cell according to claim 6, characterized in that: A sealing gasket for fixing the observation element is arranged between the observation element and the second fixing element; and / or slots for disassembly and assembly are provided on the first fixing element and the second fixing element.

8. The in-situ electrochemical Raman spectroscopy cell according to any one of claims 3 to 7, characterized in that: It comprises a weight balancing element for keeping the center of gravity of the electrolytic cell always at the center of the base, and a slot for installing the weight balancing element is provided on the base.

9. The in-situ electrochemical Raman spectroscopy cell according to any one of claims 3 to 7, characterized in that: The auxiliary electrode is an electrode made of platinum wire or carbon rod; and / or the reference electrode is an electrode made of Hg / HgO, Ag / AgCl or Hg / Hg2SO4.

10. The in-situ electrochemical Raman spectroscopy cell according to any one of claims 3 to 7, characterized in that: It comprises a gland for fixing the electrode and the pipeline on the electrode fixing platform, and the electrode fixing platform is also provided with a first mounting hole, a second mounting hole and several pipeline through holes; correspondingly, the gland is provided with through holes matching the limiting hole, the second mounting hole and several pipeline through holes.

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