Electrochemistry-Raman-electric coil coupling integrated equipment

Abstract

The invention discloses electrochemical-Raman-electric coil coupling integrated equipment, and belongs to the crossing field of electrochemical analysis, spectrum detection and electromagnetic coupling technologies. According to the equipment, through modular design, the synergistic effect of electrochemistry, Raman spectrum and electromagnetic field is realized. After a sample to be tested is simply pretreated, a two-electrode testing system is used for electrochemical testing, and meanwhile, a Raman spectrum laser emission source tracks the component change in the sample passivation process. The magnetic field intensity control is realized through the variable-turn copper coil and the direct-current power supply, and the magnetic field intensity detector measures the magnetic field intensity in real time. The equipment can efficiently and accurately realize in-situ, real-time and quantitative detection on the surface of a sample to be detected, is simple to operate and low in cost, can simulate a variable-intensity magnetic field, has important significance on researching the influence of the magnetic field on a corrosion mechanism, and can be applied to research on a corrosion process, a corrosion mechanism and a corrosion rule in an electromagnetic environment.

Description

Technical Field

[0001] The present invention belongs to the cross-field of electrochemical analysis, spectral detection and electromagnetic coupling technology, and specifically relates to an electrochemical-Raman-electric coil coupling integrated equipment for high-sensitivity, in-situ integrated electrochemical testing, Raman spectral analysis and electromagnetic field simulation control functions. Background Art

[0002] Raman spectroscopy and electrochemical technology are widely used in energy storage, biomedicine and industrial corrosion protection due to their high sensitivity, molecular structure specificity and real-time dynamic monitoring capabilities, such as in-situ composition analysis of lithium-ion battery electrode materials, real-time tracking of biosensor interface reactions and dynamic evolution of metal surface passivation films. Raman spectroscopy accurately analyzes material composition and structural changes through molecular vibration information, while electrochemical technology can obtain kinetic parameters of electrode reactions such as current, potential, impedance, etc. in real time. The combination of the two can simultaneously realize the in-situ correlation of chemical information and electrochemical behavior, providing technical support for the multi-dimensional analysis of complex systems.

[0003] The electrochemical test uses a three-electrode system to monitor the electrochemical evolution of the coating. The working electrode is the coating sample, and the reference electrode and counter electrode are platinum wires, which are connected to the corrosion solution in the rubber gasket. The open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS) are measured in the frequency range from 10 5 Hz down to 10 -1 Hz, AC amplitude 5-10mV, obtain the impedance modulus |Z| and phase angle of the coating system with frequency changes, and the resulting impedance modulus |Z| will become the target function for evaluating corrosion. However, if we couple the magnetic field during the test, the impedance modulus will also change with the magnitude of the magnetic field loading and the speed of the magnetic field change. We can use the impedance modulus and Raman spectrum to determine whether the magnetic field has an impact on the corrosion process.

[0004] With the development of science and technology, in modern industrial environments, there are widespread electromagnetic field sources such as mobile phones and other communication equipment, laboratory instruments, electromagnetic shielding coatings, etc. The complex magnetic fields generated by them will significantly interfere with precision measurement equipment such as Raman equipment and electrochemical equipment that capture electrochemical information. Therefore, it is urgent to develop an electrochemical Raman integrated device that can couple the magnetic field environment to accurately analyze the impact of the magnetic field on the corrosion mechanism. This will not only help fill the current situation of less analysis of the impact of the magnetic field environment on the corrosion process and the lack of mechanism research, but also have great significance for some fields that are interfered by the magnetic field.

[0005] This patent develops an integrated "electrochemical-Raman-electric coil" coupling equipment, which provides an innovative research platform for corrosion mechanism analysis and long-term protection design in complex magnetic field environments through the precise correlation of electrochemical-Raman-magnetic field multi-dimensional data. Summary of the invention

[0006] The present invention provides an electrochemical-Raman-electric coil coupling integrated equipment, which realizes the synergistic effect of electrochemistry, Raman spectroscopy and electromagnetic field through modular design, fills the current research gap on the influence of electromagnetic field application on corrosion mechanism, and solves the problem of the influence of magnetic field on the sensitivity of Raman equipment and electrochemical equipment.

[0007] The in-situ electrochemical Raman system of the present invention comprises a sample to be tested (1), a solution container (2), a cover glass (3), an electrochemical workstation (4), a portable Raman spectrometer (5), a Raman laser emission source (6), a copper coil with a variable number of turns (7), a coil housing (8), a DC power supply (9), a magnetic field strength detector (10) and other components.

[0008] The present invention performs simple pretreatment such as grinding and polishing on the sample to be tested, and uses the sample to be tested (1) as the sample to be tested, and places a passivation liquid container (2) with a platinum wire / silver wire in the middle close to the sample to be tested (1). The top view of the solution container (2) adopts a circular ring structure, and the passivation solution is dripped into it, and then flattened with a cover glass (3) to prevent air from entering, solution contamination, and limit the Raman light scattering effect.

[0009] The electrochemical workstation (4) of the present invention adopts a two-electrode test system, a high-purity platinum wire / silver wire connects the counter electrode and the reference electrode, and the sample to be tested (1) serves as the working electrode. The optical lens of the portable Raman spectrometer (5) moves to the geometric center of the container (2) and focuses.

[0010] In the present invention, while the electrochemical workstation (3) is turned on to perform electrochemical potential scanning and other tests, the Raman spectrum laser emission source (6) performs tests at fixed intervals, thereby achieving in-situ tracking and recording of composition changes of the sample to be tested during the passivation process.

[0011] The Raman spectrometer (5) in the present invention adopts a portable Raman spectrometer, and uses a previously established correlation model between the Raman characteristic peak intensity and the concentration of the standard substance to be tested. The correlation model is a linear regularity model between the Raman characteristic peak intensities corresponding to the standard solutions with different concentration gradients. The Raman intensity measured in the external field is compared with the correlation model, and then the concentration of the substance ions in the passivation solution at this stage is inferred.

[0012] The invention adopts a copper coil (7) with a variable number of turns placed in a coil housing (8). A DC power supply (9) is connected to the copper coil (7). After power is turned on, the magnetic field strength is controlled by changing the number of coil turns. At the same time, a magnetic field strength detector (10) is used to measure the magnetic field strength in real time.

[0013] The present invention provides an "electrochemical-Raman-electric coil" coupling integrated device, which can record the electrochemical information and Raman information of the microscopic interface of the sample to be tested during the passivation process in real time in situ under an electromagnetic environment, and can be applied to the exploration of corrosion process, mechanism and law in an electromagnetic environment.

[0014] The present invention has the following beneficial effects:

[0015] (1) The present invention can efficiently and accurately realize in-situ, real-time, and quantitative detection of the surface of the sample to be tested.

[0016] (2) The present invention is easy to operate. The sample to be tested only needs to undergo simple pretreatment such as grinding and polishing. The size of the container can be designed according to the requirements by means such as 3D printing, thereby realizing in-situ tracing analysis of the passivation behavior of the sample at a low cost.

[0017] (3) The present invention can realize variable intensity magnetic field simulation and real-time magnetic field intensity measurement.

[0018] (4) The present invention converts sample surface information into solution composition information and impedance modulus, which can realize in-situ real-time electrochemical-Raman information tracking of the sample surface under a magnetic field environment, and is of great significance for studying the mechanism of corrosion affected by magnetic field. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 A three-dimensional diagram of the structure of the "electrochemical-Raman-electric coil" coupling integrated equipment in the present invention

[0020] Figure 2 The plan view of the "electrochemical-Raman-electric coil" coupling integrated equipment in the present invention (sample to be tested 1, solution container 2, cover glass 3, electrochemical workstation 4, portable Raman spectrometer 5, Raman laser emission source 6, variable turns copper coil 7, coil housing 8, DC power supply 9, magnetic field strength detector 10) DETAILED DESCRIPTION

[0021] In view of the existing problems, the present invention provides an "electrochemical-Raman-electric coil" coupling integrated equipment, which is further described below in conjunction with embodiments and drawings. The embodiments are provided to more clearly explain the embodiments of the present invention, but are not intended to limit the present invention.

[0022] Specific implementation method 1: This implementation method is an integrated equipment of "electrochemical-Raman-electric coil" coupling, which is implemented according to the following steps:

[0023] The metal sample to be tested is ground and polished to serve as the sample to be tested (1). A container (2) with a platinum wire / silver wire in the middle is placed tightly against the sample to be tested (1), the solution is dripped into the container (2), and then it is flattened with a cover glass (3). The electrochemical workstation (4) adopts a two-electrode test system, with high-purity platinum wire / silver wire connecting the counter electrode and the reference electrode, and the sample to be tested serving as the working electrode. The optical lens of the portable Raman spectrometer (5) is moved to the geometric center of the rubber ring and focused. The DC power supply (9) and the magnetic field strength detector (10) are turned on, and it is observed that the magnetic field measured by the magnetic field strength detector (10) is stable.

[0024] Turn on the Raman spectroscopy laser emission source (6) to collect information. The Raman spectroscopy laser emission source (6) uses a static / dynamic scanning mode at fixed intervals to test the composition information of the passivation solution, so as to realize in-situ tracking and recording of the composition changes of the sample to be tested (1) during the passivation process. Prepare standard mixed solutions of different concentrations, and establish a correlation model between the Raman characteristic peak intensity and concentration of the standard. Compare the Raman intensity of the sample to be tested measured by the Raman spectroscopy laser emission source (6) with the standard intensity concentration model, and infer the concentration of the substance in the passivation solution at this stage.

[0025] The electrochemical workstation (4) is turned on for electrochemical potentiodynamic scanning and firstly the open circuit potential (OCP) is measured, and the sample is left to stand for about 1 hour until it is stable. Then the electrochemical impedance spectroscopy (EIS) measurement is performed regularly (e.g., once every 1 hour), with a frequency range of 10 5 Hz down to 10 -1 Hz, AC amplitude 5 ~ 10mV, in order to obtain the impedance modulus |Z| and phase angle of the coating system changing with frequency. The impedance modulus |Z| generated will become the objective function for evaluating corrosion.

[0026] After the electrochemical workstation (4) and the portable Raman spectrometer (5) complete the test, the number of turns of the variable-turn copper coil (7) is changed, and the magnetic field strength detector (10) is observed until the magnetic field reaches the required stable magnetic field strength, and the measurement work of the electrochemical workstation (4) and the portable Raman spectrometer (5) is repeated to obtain a new set of Raman concentrations and impedance modulus values ​​of the sample to be tested. Repeated operations obtain sufficient experimental data to explore the mechanism of magnetic field affecting corrosion.

Claims

1. An electrochemical-Raman-electrical coil coupling integrated equipment, characterized in that The in-situ electrochemical Raman system includes components such as a sample to be tested, a solution container, a cover glass, an electrochemical workstation, a portable Raman spectrometer, a Raman laser emission source, a copper coil with a variable number of turns, a coil housing, a DC power supply, and a magnetic field strength detector.

2. The electrochemical-Raman-electrical coil coupling integrated equipment according to claim 1, characterized in that The solution container can be designed and manufactured in shape according to demand through 3D printing and other technologies, or existing products such as gaskets can be used.

3. The electrochemical-Raman-electrical coil coupling integrated equipment according to claim 1, characterized in that The height of the passivation liquid container is 0.1-5 mm, preferably 0.5 mm.

4. An electrochemical-Raman-electrical coil coupling integrated equipment, characterized in that The solution container is provided with a metal electrode in the middle which is in direct contact with the solution.

5. The solution container according to claim 4, characterized in that The metal electrode penetrating the solution container may be a platinum wire / silver wire electrode, or may be a saturated calomel electrode, a standard hydrogen electrode, a carbon rod or other electrode materials.

6. The electrochemical-Raman-electrical coil coupling integrated equipment according to claim 1, characterized in that The number of turns of the variable turns copper coil can be adjusted to change the magnetic field strength, and the stability can be verified by a magnetic field strength tester.

7. The variable turns copper coil according to claim 4 is characterized in that: The variable turns copper coil has a turn adjustment range of 10 to 200 turns, and a magnetic field intensity control range of 0.1 to 5T.

8. The variable turns copper coil according to claim 4 is characterized in that: It can be connected to a 220 DC power supply, or it can be connected to an AC power supply through a rectifier.

Images