In-situ Raman testing device and testing system

Abstract

The utility model provides an in-situ Raman testing device and a testing system, and relates to the technical field of electrochemistry and spectroscopy, and the in-situ Raman testing device provided by the utility model comprises a testing platform, a liquid inlet pipe, a liquid outlet pipe, a laser transmitter and a signal receiver, the transmitting end of the laser transmitter and the receiving end of the signal receiver are arranged opposite to the test platform; the test platform is provided with a solution cavity, a liquid inlet and a liquid outlet, the liquid inlet and the liquid outlet are communicated with the solution cavity, the liquid inlet pipe is communicated with the liquid inlet, the liquid outlet pipe is communicated with the liquid outlet, the liquid inlet pipe and the liquid outlet pipe are both used for being communicated with the flow battery, and the liquid inlet pipe or the liquid outlet pipe is provided with a detection solution conveying assembly; according to the in-situ Raman testing device provided by the utility model, the technical problem that in-situ Raman testing in related technologies is not provided with an internal electrolyte flow channel and a circulating device and cannot meet the operation requirement of a flow battery is solved.

Description

Technical Field

[0001] The utility model relates to the technical field of electrochemistry and spectroscopy, in particular to a Raman testing device and a testing system. Background Art

[0002] Raman spectroscopy has become one of the best characterization techniques for studying flow batteries due to its advantages such as non-destructiveness, fast analysis speed, high repeatability, qualitative and semi-quantitative analysis, etc. Raman spectroscopy can obtain information about most species in the electrolyte by detecting molecular vibrations. By analyzing the corresponding Raman signals to analyze the changes in the amount of solution-phase species, it is of great significance to reveal the reaction mechanism of active substances on the electrode.

[0003] Raman spectroscopy can be divided into in-situ Raman spectroscopy and ex-situ Raman spectroscopy. For liquid flow batteries, the ex-situ Raman spectroscopy sample preparation process requires taking out a portion of the electrolyte of the liquid flow battery for characterization measurement. This process is prone to cause electrolyte loss, irreversible oxidation of active substances, and pollution of the entire system. In addition, ex-situ Raman spectroscopy testing is not real-time and has a certain delay, which further affects the accuracy of the test. In contrast, in-situ Raman characterization technology is real-time and can collect real-time Raman signals during the normal charging and discharging process of the liquid flow battery to obtain the types and quantities of solution phase species at each moment, so as to explain the charging and discharging mechanism or attenuation mechanism of the liquid flow battery. Currently, the common in-situ Raman tests are button type and flange type, but both do not have internal electrolyte flow channels and circulation devices, and cannot meet the operation requirements of liquid flow batteries. Utility Model Content

[0004] The utility model aims to provide an in-situ Raman testing device and a testing system to alleviate the technical problem that the in-situ Raman testing in the related art does not have an internal electrolyte flow channel and a circulation device and cannot meet the operation requirements of the flow battery.

[0005] In a first aspect, the in-situ Raman testing device provided by the utility model comprises: a testing platform, a liquid inlet pipe, a liquid outlet pipe, a laser transmitter and a signal receiver, wherein the transmitting end of the laser transmitter and the receiving end of the signal receiver are both arranged relative to the testing platform;

[0006] The test platform has a solution cavity, and a liquid inlet and a liquid outlet connected to the solution cavity, the liquid inlet pipe is connected to the liquid inlet, the liquid outlet pipe is connected to the liquid outlet, the liquid inlet pipe and the liquid outlet pipe are both used to connect to the liquid flow battery, and the liquid inlet pipe or the liquid outlet pipe is provided with a detection solution delivery component.

[0007] Optionally, the test platform is made of glass.

[0008] Optionally, at least two ends of the liquid inlet pipe are made of elastic material;

[0009] And / or, at least two ends of the liquid outlet pipe are made of elastic material.

[0010] Optionally, the detection solution delivery component includes a detection delivery pump, which is disposed at the liquid inlet pipe or the liquid outlet pipe and is used to extract the solution in the liquid flow battery to the test platform.

[0011] Optionally, the in-situ Raman testing device further comprises a fixing mechanism, and the testing platform is mounted on the fixing mechanism.

[0012] Optionally, the in-situ Raman testing device further comprises a detachable connecting mechanism, the testing platform is arranged on the detachable connecting mechanism, and the detachable connecting mechanism is used to be connected to the liquid flow battery.

[0013] Optionally, the test platform is in an oblong shape, and along the length direction of the test platform, the liquid inlet is arranged at one end of the test platform, and the liquid outlet is arranged at the other end of the test platform.

[0014] In a second aspect, the test system provided by the present invention comprises a liquid flow battery and the in-situ Raman test device described in the first aspect, wherein a liquid inlet pipe and a liquid outlet pipe in the in-situ Raman test device are respectively connected to the liquid flow battery.

[0015] Optionally, the liquid flow battery includes a battery body, a first liquid storage tank and a second liquid storage tank, the first liquid storage tank is connected to the battery body through a first pipeline, the second liquid storage tank is connected to the battery body through a second pipeline, the first pipeline is provided with a first liquid delivery component, and the second pipeline is provided with a second liquid delivery component;

[0016] The liquid inlet pipe and the liquid outlet pipe are both communicated with the first liquid storage tank or the second liquid storage tank.

[0017] Optionally, the first liquid delivery component includes a first delivery pump, and the first delivery pump is arranged in the first pipeline;

[0018] The second liquid delivery component includes a second delivery pump, and the second delivery pump is arranged in the second pipeline.

[0019] The utility model brings the following beneficial effects:

[0020] The detection solution delivery component allows the liquid in the flow battery to enter the solution cavity through the liquid inlet pipe and the liquid inlet, the light emitted by the laser transmitter irradiates the liquid passing through the solution cavity, the signal receiver collects the scattered signal of the light, and the solution in the solution cavity flows back to the flow battery through the liquid outlet and the liquid outlet pipe. The in-situ Raman test device provided by the utility model can be directly connected to the flow battery, and the liquid can be circulated in the flow battery and the solution cavity through the detection solution delivery component, thereby realizing real-time detection of solution phase species in the flow battery, which is helpful to explain the charging and discharging mechanism and failure mechanism of the flow battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the specific implementation methods of the utility model or the technical solutions in the related technologies, the drawings required for use in the specific implementation methods or the related technical descriptions will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the utility model. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0022] Figure 1 A schematic diagram of the structure of a test system provided by an embodiment of the utility model;

[0023] Figure 2 A schematic diagram of the structure of a test platform in an in-situ Raman test device provided by an embodiment of the utility model;

[0024] Figure 3 For polysulfide flow batteries at 10 mA cm -2 Constant current charge and discharge curves under current density;

[0025] Figure 4 In-situ Raman images of the flow battery during charge and discharge testing.

[0026] Icons: 100 - test platform; 110 - first connection end; 120 - second connection end; 200 - liquid inlet pipe; 210 - detection delivery pump; 300 - liquid outlet pipe; 400 - battery body; 500 - first liquid storage tank; 510 - first pipeline; 520 - first delivery pump; 600 - second liquid storage tank; 610 - second pipeline; 620 - second delivery pump. DETAILED DESCRIPTION

[0027] The technical solution of the utility model will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the utility model, not all of the embodiments. Based on the embodiments of the utility model, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the utility model.

[0028] In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicating the orientation or positional relationship, are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", and "third" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance.

[0029] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0030] like Figure 1 As shown, the in-situ Raman testing device provided by the embodiment of the utility model includes: a testing platform 100, a liquid inlet pipe 200, a liquid outlet pipe 300, a laser transmitter and a signal receiver, the transmitting end of the laser transmitter and the receiving end of the signal receiver are both arranged opposite to the testing platform 100; the testing platform 100 has a solution cavity, and a liquid inlet and a liquid outlet connected to the solution cavity, the liquid inlet pipe 200 is connected to the liquid inlet, and the liquid outlet pipe 300 is connected to the liquid outlet, the liquid inlet pipe 200 and the liquid outlet pipe 300 are both used to communicate with the liquid flow battery, and the liquid inlet pipe 200 or the liquid outlet pipe 300 is provided with a detection solution delivery component.

[0031] Specifically, the test platform 100 is a hollow structure and is made of a transparent material. A solution cavity is formed inside the test platform 100. The two ends of the test platform 100 are respectively provided with a first connection end 110 and a second connection end 120 protruding from the outer peripheral wall of the test platform 100. The first connection end 110 is provided with a liquid inlet connected to the solution cavity, and the second connection end 120 is provided with a liquid outlet connected to the solution cavity. One end of the liquid inlet pipe 200 is connected to the first connection end 110 and is connected to the liquid inlet. The other end of the liquid inlet pipe 200 is used to communicate with the liquid flow battery. One end of the liquid outlet pipe 300 is connected to the second connection end 120 and is connected to the liquid outlet. The other end of the liquid outlet pipe 300 is used to communicate with the liquid flow battery.

[0032] The laser transmitter is used to provide monochromatic light, and the light emitted by the laser transmitter is irradiated to the solution passing through the solution chamber. The signal receiver can be a CCD (charge-coupled device) camera or other photoelectric conversion device for detecting and analyzing spectral signals.

[0033] The detection solution delivery component allows the liquid in the flow battery to enter the solution cavity through the liquid inlet pipe 200 and the liquid inlet, the light emitted by the laser transmitter irradiates the liquid passing through the solution cavity, the signal receiver collects the scattered light signal, and the solution in the solution cavity flows back to the flow battery through the liquid outlet and the liquid outlet pipe 300. The original Raman test device provided by the embodiment of the utility model can be directly connected to the flow battery, and the liquid is circulated in the flow battery and the solution cavity through the detection solution delivery component, thereby realizing real-time detection of solution phase species in the flow battery, which is helpful to explain the charge and discharge mechanism and failure mechanism of the flow battery.

[0034] The test platform 100 is made of glass. Specifically, the test platform 100 can be made of quartz glass, borosilicate glass or sapphire, which is a glass that absorbs a specific wavelength band of incident light during the test. In this embodiment, the test platform 100 is made of quartz glass, and the quartz glass absorbs a specific wavelength band of incident light during the test. -1 Up to 800cm -1 The test platform 100 made of quartz glass has high light transmittance and has no reaction with the electrolyte, thereby improving the accuracy of detection.

[0035] In an embodiment of the utility model, at least two ends of the liquid inlet pipe 200 are made of elastic material; or, at least two ends of the liquid outlet pipe 300 are made of elastic material, or, at least two ends of the liquid inlet pipe 200 and at least two ends of the liquid outlet pipe 300 are both made of elastic material.

[0036] Specifically, as an embodiment, the liquid inlet pipe 200 is made of rubber material as a whole, one end of the liquid inlet pipe 200 made of rubber is sleeved on the first connection end 110, and the other end is sleeved on the interface for liquid discharge of the liquid flow battery; as another embodiment, the middle part of the liquid inlet pipe 200 is made of glass, and both ends of the liquid inlet pipe 200 are made of rubber material, and the two ends made of rubber are respectively sleeved on the two ends of the middle part made of glass, and the ends of the two ends away from the middle part are respectively connected to the first connection end 110 and the interface for liquid discharge of the liquid flow battery. The liquid inlet pipe 200 made of rubber has a certain elasticity and can be more tightly connected to the first connection end 110 and the interface for liquid discharge of the liquid flow battery, thereby improving the sealing of the connection between the liquid inlet pipe 200, the first connection end 110 and the liquid flow battery, and preventing solution leakage.

[0037] As an embodiment, the liquid outlet pipe 300 is made of rubber material as a whole, one end of the liquid outlet pipe 300 made of rubber is sleeved on the second connection end 120, and the other end is sleeved on the interface for liquid inlet of the liquid flow battery; as another embodiment, the middle part of the liquid outlet pipe 300 is made of glass, and both ends of the liquid outlet pipe 300 are made of rubber material, and the two ends made of rubber are respectively sleeved on the two ends of the middle part made of glass, and the ends of the two ends away from the middle part are respectively connected to the second connection end 120 and the interface for liquid inlet of the liquid flow battery. The liquid outlet pipe 300 made of rubber has a certain elasticity and can be more tightly connected to the second connection end 120 and the interface for liquid inlet of the liquid flow battery, thereby improving the sealing of the connection between the liquid outlet pipe 300, the second connection end 120 and the liquid flow battery, and preventing solution leakage.

[0038] like Figure 1 As shown, the detection solution delivery assembly includes a detection delivery pump 210 , which is disposed on the liquid inlet pipe 200 or the liquid outlet pipe 300 and is used to extract the solution in the liquid flow battery to the test platform 100 .

[0039] Specifically, the detection delivery pump 210 is arranged on the liquid inlet pipe 200. Under the action of the detection delivery pump 210, the solution in the liquid flow battery enters the detection platform through the liquid inlet pipe 200, and then flows back to the liquid flow battery through the liquid outlet pipe 300, thereby realizing the circulation of the solution between the liquid flow battery and the detection platform, realizing the detection of the solution while enabling the liquid flow battery to work normally.

[0040] As a way of installing the test platform 100, the in-situ Raman test device also includes a fixing mechanism, and the test platform 100 is installed on the fixing mechanism. Specifically, the fixing mechanism includes a fixing seat, and the test platform 100 can be connected to the fixing seat through a card slot. The fixing seat supports the test platform 100, improves the stability of the test platform 100, and enables the signal receiver to collect accurate and stable Raman signals.

[0041] As another embodiment, the in-situ Raman test device further includes a detachable connection mechanism, and the test platform 100 is disposed on the detachable connection mechanism, and the detachable connection mechanism is used to connect to the flow battery. Specifically, the detachable connection mechanism includes a mounting seat, and the test platform 100 can be mounted on the mounting seat by a snap-on method, and the mounting seat can be detachably mounted on the flow battery by bolts. The test platform 100 is detachably mounted on the flow battery through the mounting seat, so that it is convenient to move with the flow battery.

[0042] like Figure 2As shown, the test platform 100 is in an oblong shape, and along the length direction of the test platform 100, the liquid inlet is arranged at one end of the test platform 100, and the liquid outlet is arranged at the other end of the test platform 100. Specifically, along the length direction of the test platform 100, one end of the test platform 100 is provided with a first connection end 110, the liquid inlet is arranged at the first connection end 110, and the other end of the test platform 100 is provided with a second connection end 120, and the liquid outlet is arranged at the second connection end 120. The laser emitter is opposite to the outer peripheral wall of the test platform 100, and the test platform 100 is set in an oblong shape, so that the laser emitter can irradiate the solution flowing through the test platform 100.

[0043] The test system provided by the embodiment of the utility model comprises a liquid flow battery and the above-mentioned in-situ Raman test device, and the liquid inlet pipe 200 and the liquid outlet pipe 300 in the in-situ Raman test device are respectively connected to the liquid flow battery.

[0044] Specifically, the liquid flow battery includes a battery body 400, a first liquid storage tank 500 and a second liquid storage tank 600. The first liquid storage tank 500 is connected to the battery body 400 through a first pipeline 510, and the second liquid storage tank 600 is connected to the battery body 400 through a second pipeline 610. The first pipeline 510 is provided with a first liquid delivery component, and the second pipeline 610 is provided with a second liquid delivery component; the liquid inlet pipe 200 and the liquid outlet pipe 300 are both connected to the first liquid storage tank 500 or the second liquid storage tank 600.

[0045] Specifically, the first liquid storage tank 500 is connected to the positive electrode of the battery body 400 through the first pipeline 510, and the first liquid delivery assembly allows the solution to circulate between the first liquid storage tank 500 and the positive electrode of the battery body 400; the second liquid storage tank 600 is connected to the negative electrode of the battery body 400 through the second pipeline 610, and the second liquid delivery assembly allows the solution to circulate between the second liquid storage tank 600 and the negative electrode of the battery body 400. The in-situ Raman test device can be connected to the first liquid storage tank 500 through the liquid inlet pipe 200 and the liquid outlet pipe 300, and the solution is circulated between the first liquid storage tank 500 and the detection platform through the detection delivery pump 210, or the in-situ Raman test device can be connected to the second liquid storage tank 600 through the liquid inlet pipe 200 and the liquid outlet pipe 300, and the solution is circulated between the second liquid storage tank 600 and the detection platform through the detection delivery pump 210.

[0046] The first liquid delivery assembly includes a first delivery pump 520, which is disposed in the first pipeline 510; the second liquid delivery assembly includes a second delivery pump 620, which is disposed in the second pipeline 610. Figure 1As shown, the first delivery pump 520 is disposed on the first pipeline 510 and communicated with the first pipeline 510, and the second delivery pump 620 is disposed on the second pipeline 610 and communicated with the second pipeline 610. The first delivery pump 520 circulates the solution between the first liquid storage tank 500 and the positive electrode of the battery body 400, and the second delivery pump 620 circulates the solution between the second liquid storage tank 600 and the negative electrode of the battery body 400, so as to realize the normal operation of the battery body 400.

[0047] The following is a specific description using the example of the detection platform being connected to the second liquid storage tank 600.

[0048] Before conducting in-situ Raman testing experiments on the charge and discharge of polysulfide flow batteries, the Raman signal of a certain concentration of Na2S2 solution is tested to determine the position of the Raman peak corresponding to the ions to be monitored. Figure 4 Curve A in the middle shows that S2 2－ The Raman peak corresponding to the ion is at 451 cm －1 . Figure 3 For polysulfide flow batteries at 10 mA cm －2 The constant current charge and discharge curves under current density. The positive electrode of the battery is 0.5M Na4Fe(CN)6 solution, and the negative electrode is 0.5M Na2S2 solution. Figure 3 The test results show that the capacity of the polysulfide flow battery is 80 mAh (charging time is 7200 s), which is close to the theoretical capacity (calculated based on the positive electrode active material), indicating that the device is operating normally. Figure 4 This is the in-situ Raman image of the above-mentioned flow battery during charging and discharging test. The test was carried out using a laser confocal Raman spectrometer with a laser wavelength of 532nm, a laser power of 40mW, and a single spectrum acquisition time of 30s. Figure 3 The A curve in the middle corresponds to the initial state of the negative electrode electrolyte, which is the Raman curve at 451cm －1 Nearby is S2 2－ When the charge is close to 100% SOC, its Raman curve corresponds to the B curve, 451cm －1 The peak of polysulfide at 451 cm-1 decreases sharply. During the discharge process, the Raman curves at 50% SOC discharge and 100% SOC discharge correspond to curve C and curve D, respectively. －1 The peak of polysulfide at the position gradually increases, which proves that during the charging process, S2 2－ ions are continuously reduced to S 2－ , and its corresponding Raman signal gradually weakens. During the discharge process, S 2－ Constantly oxidized to S2 2－ , resulting in S2 2－ The corresponding Raman signal is continuously enhanced. In situ Raman characterization is achieved by real-time detection of S2 2－The change of Raman signal, reaction S2 2－ The specific changes in concentration during the charging and discharging process help to reveal the reaction mechanism of the flow battery, thus proving the effectiveness of this in situ Raman test.

[0049] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the utility model, rather than to limit it. Although the utility model has been described in detail with reference to the aforementioned embodiments, ordinary technicians in this field should understand that they can still modify the technical solutions recorded in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the utility model.

Claims

1. An in-situ Raman testing device, characterized in that: include: A test platform (100), a liquid inlet pipe (200), a liquid outlet pipe (300), a laser transmitter and a signal receiver, wherein the transmitting end of the laser transmitter and the receiving end of the signal receiver are both arranged opposite to the test platform (100); The test platform (100) has a solution cavity, and a liquid inlet and a liquid outlet connected to the solution cavity; the liquid inlet pipe (200) is connected to the liquid inlet, and the liquid outlet pipe (300) is connected to the liquid outlet; the liquid inlet pipe (200) and the liquid outlet pipe (300) are both used to communicate with a liquid flow battery, and the liquid inlet pipe (200) or the liquid outlet pipe (300) is provided with a detection solution delivery component.

2. The in-situ Raman testing device according to claim 1, characterized in that: The test platform (100) is made of glass.

3. The in-situ Raman testing device according to claim 1, characterized in that: At least two ends of the liquid inlet pipe (200) are made of elastic material; And / or, at least two end portions of the liquid outlet pipe (300) are made of elastic material.

4. The in-situ Raman testing device according to claim 1, characterized in that: The detection solution delivery component comprises a detection delivery pump (210), which is arranged on the liquid inlet pipe (200) or the liquid outlet pipe (300) and is used to extract the solution in the liquid flow battery to the test platform (100).

5. The in-situ Raman testing device according to claim 1, characterized in that: The in-situ Raman testing device further comprises a fixing mechanism, and the testing platform (100) is installed on the fixing mechanism.

6. The in-situ Raman testing device according to claim 1, characterized in that: The in-situ Raman testing device further comprises a detachable connecting mechanism, the testing platform (100) is arranged on the detachable connecting mechanism, and the detachable connecting mechanism is used to be connected to the liquid flow battery.

7. The in-situ Raman testing device according to claim 1, characterized in that: The test platform (100) is in an oblong shape; along the length direction of the test platform (100), the liquid inlet is arranged at one end of the test platform (100), and the liquid outlet is arranged at the other end of the test platform (100).

8. A testing system, characterized in that: It comprises a liquid flow battery and the in-situ Raman testing device according to any one of claims 1 to 7, wherein a liquid inlet pipe (200) and a liquid outlet pipe (300) in the in-situ Raman testing device are respectively connected to the liquid flow battery.

9. The test system according to claim 8, characterized in that: The liquid flow battery comprises a battery body (400), a first liquid storage tank (500) and a second liquid storage tank (600), wherein the first liquid storage tank (500) is connected to the battery body (400) via a first pipeline (510), and the second liquid storage tank (600) is connected to the battery body (400) via a second pipeline (610), the first pipeline (510) is provided with a first liquid delivery component, and the second pipeline (610) is provided with a second liquid delivery component; The liquid inlet pipe (200) and the liquid outlet pipe (300) are both in communication with the first liquid storage tank (500) or the second liquid storage tank (600).

10. The test system according to claim 9, characterized in that: The first liquid delivery component comprises a first delivery pump (520), and the first delivery pump (520) is arranged in the first pipeline (510); The second liquid delivery component comprises a second delivery pump (620), and the second delivery pump (620) is arranged in the second pipeline (610).

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