Operando electrochemical cell for synchrotron-based x-ray scattering and absorption measurement

Abstract

The present invention relates to an electrochemical cell for X-ray scattering and absorption experiments that is configured to reduce bubbles in the electrolyte used for X-ray measurement and lower the scattering of X-rays to increase measurement accuracy, and configured to achieve high measurement efficiency even with low X-rays, thereby enabling further miniaturization and weight reduction.

Description

Technology Field

[0001] The present invention relates to a real-time electrochemical cell for synchrotron-based X-ray scattering and absorption experiments, and more specifically, to an electrochemical cell for X-ray scattering and absorption experiments in which, when configuring an electrolyte within an electrochemical cell through which X-rays must pass for synchrotron-based X-ray (hereinafter referred to as 'X-rays') measurement, the amount of electrolyte is optimized to minimize interference with X-rays and bubbles within the electrolyte are reduced, thereby minimizing the loss of X-ray intensity passing through the electrolyte and achieving high measurement efficiency, and enabling the cell to be miniaturized. Background Technology

[0003] Recently, cutting-edge technologies such as nanotechnology (NT) and biotechnology (BT) have been developing, and for these cutting-edge technologies, it is very important to analyze the state and function of materials configured in an operating state. Therefore, interest has increased in in-situ analysis techniques that can analyze materials without damaging the sample during or after the process.

[0004] In conventional light source analyzers, the sample measurement part was generally exposed to the atmosphere, and in the field of batteries that undergo electrochemical reactions involving oxidation and reduction reactions, such as secondary batteries, fuel cells, and solar cells, it was impossible to directly analyze changes in state unless special attachments were installed. Furthermore, since batteries are operated by assembling a positive electrode, an electrolyte, and a negative electrode, it was very difficult to directly observe the state of the electrodes operating under constant voltage, current, and resistance. Therefore, even if the battery was disassembled and the electrodes were examined, it could not be considered to reflect the operating state.

[0005] In this regard, the electrochemical reactions of such battery materials must be directly observed under conditions where actual voltage, current, and resistance are applied—that is, under operating conditions (in-situ; in-situation); furthermore, observing the electrode materials during actual charge and discharge operations without any additional changes in the battery is key to understanding the electrochemical action.

[0006] Accordingly, Korean Registered Patent No. 10-0802604 “Electrochemical In-Situ Cell for X-ray Absorption Spectrometer” is disclosed, which allows for the observation of electrochemical reactions of electrode materials, etc., in an in-situ state as described above.

[0007] The above “electrochemical in-situ cell for X-ray absorption spectrometer” is configured to provide an electrode inside, configure a flow path for an electrolyte to pass through the electrode, and pass X-rays through the electrolyte passing through the electrode to apply an electrical signal to the electrode material in an electrochemical atmosphere, thereby enabling direct observation of changes in the state of the electrode material, etc.

[0008] Here, since the electrolyte through which X-rays pass scatters or absorbs X-rays, thereby affecting the amount of X-ray transmission, ensuring that the amount of electrolyte at the X-ray transmission location is properly formed is a very important factor.

[0009] However, regarding the above “electrochemical in-drilling cell for X-ray absorption spectrometer,” there is little research on the appropriate amount of electrolyte filled in the space between the first window (13a) and the second window (13b) between the X-ray penetration location, that is, the X-ray injection and discharge path (16, 17).

[0010] In addition, the above “electrochemical in-drilling cell for X-ray absorption spectrometer” has a problem in that bubbles are generated due to residual gas or the influx of external air, and if these bubbles remain embedded in the electrolyte when X-rays pass through, they scatter the X-rays, thereby reducing the intensity of the incident X-rays.

[0011] Therefore, it is necessary to conduct research that can resolve the aforementioned problems in electrochemical drilling cells in order to observe real-time electrochemical reactions more accurately and successfully using X-rays or similar rays. The problem to be solved

[0013] The present invention has been devised to solve the aforementioned problems, and the objective of the present invention is to provide an electrochemical cell for X-ray scattering and absorption experiments that enables a catalytic reaction in the electrochemical cell while simultaneously minimizing interference with transmitted X-rays by forming an appropriate amount of electrolyte, thereby enabling the cell to exhibit high measurement accuracy and measurement efficiency.

[0014] In addition, another objective of the present invention is to provide an electrochemical cell for X-ray scattering and absorption experiments that can exhibit high measurement efficiency by reducing bubbles in the electrolyte and minimizing the loss of X-ray intensity passing through the electrolyte. means of solving the problem

[0016] To achieve the above objective, the present invention provides an electrochemical cell for X-ray scattering and absorption experiments, comprising: a first cell plate having an electrolyte inflow channel formed on one side through which an electrolyte is introduced and a first electrode is inserted, and an electrolyte outflow channel formed on the other side through which an electrolyte is discharged and a second electrode is inserted, and an electrolyte movement channel formed on one surface through which the electrolyte is connected to the electrolyte inflow channel and the electrolyte outflow channel through which the electrolyte is moved and an X-ray incident hole is provided for X-rays to be incident and transmitted through the electrolyte movement path; a second cell plate having an X-ray emission hole formed therein, which is positioned facing the electrolyte movement channel and has a sample sheet interposed between the electrolyte movement channel and the cell plate and emits X-rays that have passed through the X-ray incident hole, and a fixing means for tightly fixing the first cell plate and the second cell plate so as to hermetically seal the electrolyte movement channel, wherein the gap between the X-ray incident hole and the X-ray emission hole is 1.15 mm to 1.25 mm.

[0017] In a preferred embodiment, the electrolyte transfer channel may include a first transfer channel connected to the electrolyte inflow channel; a second transfer channel connected to the electrolyte outflow channel; and a bubble reduction channel between the first transfer channel and the second transfer channel, configured to reduce bubbles in the electrolyte introduced into the first transfer channel and transfer them to the second transfer channel.

[0018] In a preferred embodiment, the electrochemical cell for the X-ray scattering and absorption experiment may have a second moving channel positioned higher than the first moving channel.

[0019] In a preferred embodiment, the bubble reduction channel may include one or more rising channels configured to allow the electrolyte to rise and move in a height direction.

[0020] In a preferred embodiment, the rising path may be a single vertical path where the distance between the first moving path and the second moving path can form the shortest distance.

[0021] In a preferred embodiment, the bubble reduction channel may have a width wider than the respective channel widths of the first and second moving channels.

[0022] In a preferred embodiment, the X-ray emission hole may be formed in the shape of a narrow halo, with the diameter expanding as it extends toward the direction of X-ray emission. Effects of the invention

[0024] The present invention has the following excellent effects.

[0025] First, according to the electrochemical cell for X-ray scattering and absorption experiments of the present invention, the electrolyte transport channel for transporting the electrolyte forms a depth of 0.65 mm to 0.75 mm, which has been proven by experiments to produce a high measurement effect even with low X-ray irradiation, thereby enabling the electrochemical cell for X-ray scattering and absorption experiments to be more miniaturized.

[0026] In addition, according to the electrochemical cell for X-ray scattering and absorption experiments of the present invention, the electrolyte transport channel that moves the electrolyte raises the electrolyte in the opposite direction of gravity or provides a space that relieves the pressure of the electrolyte, thereby reducing bubbles, so that the X-rays passing through the electrolyte can form a low scattering degree.

[0027] In addition, according to the electrochemical cell for X-ray scattering and absorption experiments of the present invention, the X-ray emission hole that emits X-rays is formed in the shape of a near-narrow circle with a diameter that expands as it moves toward the emission direction, so that the X-rays can be appropriately dispersed and diffracted and incident on an X-ray measuring device.

[0028] Based on their operation, the electrochemical cell for X-ray scattering and absorption experiments of the present invention has the advantage of very high measurement accuracy. Brief explanation of the drawing

[0030] FIG. 1 is a diagram illustrating the use of an electrochemical cell for X-ray scattering and absorption experiments of the present invention. FIG. 2 is an exploded perspective view of an electrochemical cell for X-ray scattering and absorption experiments of the present invention. Figure 3 is a drawing of Figure 2 viewed from the opposite side. FIG. 4 is a cross-sectional perspective view of an electrochemical cell for X-ray scattering and absorption experiments of the present invention. FIG. 5 is a front view of a first cell plate, which is a component of an electrochemical cell for X-ray scattering and absorption experiments of the present invention. FIGS. 6a to 6e are drawings showing various structures in which the bubble reduction channel of the first cell plate can reduce bubbles through the rising channel. FIGS. 7A and 7B are drawings showing various structures capable of reducing bubbles, in which the bubble reduction channel of the first cell plate is formed with a wider width than other channels. Figure 8a shows the X-ray measurement results when a flow rate of 0.02 ml / min is applied during a stability test of an electrochemical cell for X-ray scattering and absorption experiments, and Figure 8b shows the X-ray measurement results when a flow rate of 0.01 ml / min is applied. Figure 9 shows the operating results of an electrochemical cell for X-ray scattering and absorption experiments in electrochemical catalytic reaction experiments of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Specific details for implementing the invention

[0031] The terms used in this invention have been selected to be as widely used as possible; however, in specific cases, terms have been arbitrarily selected by the applicant. In such cases, the meaning should be understood by considering the meaning described or used in the detailed description of the invention, rather than merely the name of the term.

[0032] Hereinafter, the technical configuration of the present invention will be described in detail with reference to preferred embodiments illustrated in the attached drawings.

[0033] However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Throughout the specification, the same reference numerals indicate the same components.

[0034] FIG. 1 is a diagram illustrating the principle of use of an electrochemical cell for X-ray scattering and absorption experiments of the present invention.

[0035] Referring to FIG. 1, the electrochemical cell (1000) for X-ray scattering and absorption experiments of the present invention (hereinafter referred to as the ‘real-time electrochemical cell’) is configured to transmit X-rays by being installed between an X-ray emitting device (100) that emits X-rays and an X-ray absorbing device (200) that absorbs X-rays emitted from the X-ray emitting device (100), and is configured to enable various catalytic electrochemical reaction experiments using the transmitted X-rays.

[0036] Here, the X-ray emitting device (100) may be, for example, a synchrotron accelerator, but is not limited thereto, and any device of various types capable of emitting X-rays may be used, and the X-ray absorbing device (200) may be configured to absorb X-rays that have passed through the real-time electrochemical cell (1000) and measure the X-ray value, etc.

[0037] The real-time electrochemical cell (1000) of the present invention is configured to observe the catalytic electrochemical reaction state in real time under conditions where actual voltage is applied and operation is performed, i.e., in-situ conditions, and includes at least two electrodes (1115, 1125) for causing an electrochemical reaction, and may be configured so that the electrolyte moves through all of the included electrodes (1115, 1125).

[0038] In addition, the real-time electrochemical cell (1000) of the present invention may be configured such that a sample sheet (1500) containing a catalytic material is inserted into an electrolyte that moves through electrodes (1115, 1125), and X-rays emitted from an X-ray emitting device (100) pass through the sample sheet (1500) and are absorbed by an X-ray absorption device (200), thereby allowing real-time observation of the catalytic electrochemical reaction occurring between the electrodes, the electrolyte, the catalytic material, and the X-rays.

[0039] For example, physical / chemical changes of the catalytic material occurring on the electrode surface during an electrochemical reaction, the electronic state of the catalytic material under voltage application conditions, such as the X-ray absorption fine structure (XAFS), and changes in physical properties such as the size and crystal structure of the catalytic material, such as small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and X-ray diffraction (XRD), can be observed in real time.

[0040] Their observations are highly useful as they can be applied to most experiments demonstrating electrochemical catalytic reactions, such as hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER).

[0041] FIG. 2 is an exploded perspective view of an electrochemical cell for X-ray scattering and absorption experiments of the present invention, FIG. 3 is a view of FIG. 2 from the opposite side, and FIG. 4 is a cross-sectional perspective view of an electrochemical cell for X-ray scattering and absorption experiments of the present invention.

[0042] Referring to FIGS. 2 to 4, the real-time electrochemical cell (1000) of the present invention, which is utilized as described above, may first be configured to include a first cell plate (1100), a second cell plate (1200), and a fixing means (1300).

[0043] Specifically, the first cell plate (1100) is not limited but preferably is a plate made of Teflon or PEEK material, and an electrolyte inflow channel (1110) is formed on one side to allow the electrolyte to flow in and the first electrode (1115) to be inserted, and an electrolyte outflow channel (1120) is formed on the other side to allow the electrolyte to flow out and the second electrode (1125) to be inserted.

[0044] Here, preferably, the first electrode (1115) may be a reference electrode and the second electrode (1125) may be a counter electrode, but is not limited to these, and any electrode capable of inducing an electrochemical reaction may be used. Examples include a working electrode.

[0045] Additionally, the first electrode (1115) and the second electrode (1125) may be configured to be easily detachable from the first cell plate (1100) so that they can be replaced with other electrodes. This allows for the replacement and use of a wider variety of electrodes depending on the experimental purpose or situation.

[0046] The electrolyte inflow channel (1110) into which the first electrode (1115) is inserted forms a length from one side of the first cell plate (1100) to the electrolyte transfer channel (1130) to be described later, and the electrolyte outflow channel (1120) into which the second electrode (1125) is inserted forms a length from the electrolyte transfer channel (1130) to the other side of the first cell plate (1100).

[0047] At this time, as will be described later, the electrolyte flow path (1130) may be formed on one surface of the first cell plate (1100). Here, the term "one surface of the first cell plate (1100)" refers to the front or rear side of the first cell plate (1100) where the electrolyte inflow path (1110) or the electrolyte outflow path (1120) is not formed.

[0048] That is, when the real-time electrochemical cell (1000) of the present invention is viewed in a planar cross-section, the electrolyte inflow channel (1110) and the electrolyte outflow channel (1120) have an L-shaped form that is bent from the side of the first cell plate (1100) toward the front or rear and extends to the electrolyte movement channel (1130).

[0049] Additionally, the electrolyte inlet channel (1110) and the electrolyte outlet channel (1120) may form the same height, but preferably, the height of the electrolyte outlet channel (1120) may be formed higher than that of the electrolyte inlet channel (1110). This is a structure resulting from the connected electrolyte transfer channel (1130) being formed high to reduce bubbles, and this will be explained in more detail in the section on the electrolyte transfer channel (1130).

[0050] Meanwhile, the electrolyte inlet path (1110) and the electrolyte outlet path (1120) are connected to a flexible hose or a rigid pipe that forms a length outside the first cell plate (1100), and either the electrolyte inlet path (1110) or the electrolyte outlet path (1120) is equipped with a power supply means (not shown), such as a pump, to provide power for moving the electrolyte, thereby enabling the movement of the electrolyte from the electrolyte inlet path (1110) through the electrolyte movement path (1130) to the electrolyte outlet path (1120).

[0051] At this time, the power supply means generates back pressure or suction pressure depending on the position to move the electrolyte, and through this movement, bubbles generated from the first electrode (1115) or the second electrode (1125), etc. due to the electrochemical reaction can be continuously discharged to prevent them from remaining in the electrolyte, and X-rays passing through the electrolyte can be prevented from scattering due to the bubbles.

[0052] The electrolyte flow path (1130) is formed to be exposed on one surface of the first cell plate (1100), and the flow path can be formed in the form of a groove that forms a depth inwardly from one surface of the first cell plate (1100). That is, when viewing only one surface of the first cell plate (1100), the electrolyte flow path (1130) is visible.

[0053] Here, a sample sheet (1500) containing a catalyst material is positioned in an electrolyte transfer channel (1130) exposed on one surface of the first cell plate (1100) through which the electrolyte moves, and as the moving electrolyte passes in close contact with the sample sheet (1500), the electrolyte and the catalyst required for the electrochemical reaction come into contact.

[0054] As will be described later, the electrolyte transfer channel (1130) is covered by the second cell plate (1200) to form an airtight seal so that the electrolyte comes into contact only with the sample sheet (1500) and does not leak to the outside. Furthermore, one or more O-rings (1175) are provided on the outer radius of the electrolyte transfer channel (1130) to further prevent leakage of the electrolyte, and the second cell plate (1200) covers and seals the electrolyte transfer channel (1130) and the O-ring (1175) together to prevent leakage of the electrolyte.

[0055] Preferably, the O-ring (1175) provided on the outer radius of the electrolyte flow path (1130) may be provided to be fitted into the O-ring groove (1170) shown in FIG. 3 or FIG. 4, and for this purpose, the O-ring groove (1170) may be provided in a ring shape by forming a length along the circumferential perimeter on the outer side of the electrolyte flow path (1130) within the first cell plate (1100).

[0056] The electrolyte transfer channel (1130) may be configured to include a first transfer channel (1131), a second transfer channel (1132), and a bubble reduction channel (1133), and these will be described in more detail with reference to FIGS. 5 to 7b.

[0057] Meanwhile, the electrolyte transfer channel (1130) may be provided with an X-ray incident hole (1140) that penetrates in the thickness direction of the first cell plate (1100), and the X-ray emitted from the X-ray emitting device (100) may be configured to pass through the electrolyte moving along the X-ray incident hole (1140).

[0058] At this time, the X-ray incident hole (1140) can be sealed with a first film (1160) so that the electrolyte moving along the electrolyte flow path (1130) does not leak into the X-ray incident hole (1140). The first film (1160) can be configured to be inserted into the first cell plate (1100) through a film insert (1150) mounted on the first cell plate (1100) to seal the X-ray incident hole (1140).

[0059] Specifically, the first film (1160) may be a polyimide film that transmits X-rays and is non-conductive and chemically resistant, but is not necessarily limited to a polyimide film; any film that transmits X-rays and exhibits properties such as non-conductivity and chemical resistance may be used.

[0060] The film insert (1150) is mounted on the opposite side of the first cell plate (1100) in which the electrolyte flow path (1130) is formed, and may be configured to include an insertion part (1151) and a fastening part (1152).

[0061] Here, the insertion part (1151) is configured to form a diameter larger than the diameter of the X-ray incident hole (1140) so as to be inserted into the first cell plate (1100), and a first film (1160) is attached to the end so that when the insertion part (1151) is inserted into the first cell plate (1100), the first film (1160) can be configured to seal the X-ray incident hole (1140).

[0062] At this time, it is preferable that the insertion part (1151) extends from the insertion opening of the first cell plate (1100) into which the insertion part (1151) is inserted to the inner surface where the X-ray incident hole (1140) is formed, so that the first film (1160) is in close contact with and sealed to the X-ray incident hole (1140).

[0063] Additionally, the fastening portion (1152) may be formed with a larger diameter than the insertion portion (1151) so as to face the first cell plate (1100) when the first cell plate (1100) is inserted into the insertion portion (1151), and may be configured to be fastened to the first cell plate (1100) in a facing state.

[0064] The fixation of the film insert (1150) to the first cell plate (1100) through the fastening part (1152) allows for easy fixing and release, making it easy to repair or replace the first film (1160).

[0065] Meanwhile, it is preferable that the film insert (1150) has an X-ray incident hole (1140) of the same diameter as the X-ray incident hole (1140) so that the X-ray transmission path to the X-ray incident hole (1140) is not blocked. That is, the X-ray incident hole (1140) formed in the electrolyte transfer channel (1130) can be extended to the film insert (1150).

[0066] The X-ray incident hole (1140) formed in the electrolyte flow path (1130) is designated as the first X-ray incident hole (1141), extending from the fastening part (1152) of the film insert (1150) to the insertion part (1151), and the X-ray incident hole (1140) extending with the same diameter as the first X-ray incident hole (1141) is designated as the second X-ray incident hole (1142) to distinguish them.

[0067] The second cell plate (1200) is not limited to, but preferably is a plate made of Teflon or PEEK material, is positioned facing the electrolyte flow path (1130), and can be fixed in close contact with the first cell plate (1100) by the fixing means (1300) described later.

[0068] Here, the second cell plate (1200), which is fixed in close contact with the first cell plate (1100) by a fixing means (1300), can seal the electrolyte flow path (1130) exposed on one surface of the first cell plate (1100).

[0069] At this time, a sample sheet (1500) containing a catalyst material is positioned in front of the electrolyte transfer channel (1130) before the first cell plate (1100) and the second cell plate (1200) are fixed in close contact with each other by the fixing means (1300), and can be interposed in the gap between the electrolyte transfer channel (1130) and the second cell plate (1200) when the first cell plate (1100) and the second cell plate (1200) are fixed in close contact by the fixing means (1300).

[0070] A sample sheet (1500) interposed between the gap between the electrolyte transfer channel (1130) and the second cell plate (1200) comes into contact with the electrolyte when the electrolyte is moved to the electrolyte transfer channel (1130) by a power supply means, and when X-rays penetrate the electrolyte along with the operation of the first electrode (1115) and the second electrode (1125), an electrochemical reaction occurs, allowing the catalytic reaction described above to be observed.

[0071] Additionally, the second cell plate (1200) may be connected to the X-ray incident hole (1140) to form an X-ray emission hole (1240) that emits X-rays passing through the X-ray incident hole (1140) to the outside. At this time, the X-ray emission hole (1240) is formed in the shape of a near-narrow-circle light whose diameter expands toward the direction of X-ray emission, thereby providing optimal performance for X-ray diffraction and dispersion.

[0072] Meanwhile, the X-ray emission hole (1240) of the second cell plate (1200) that seals the electrolyte flow path (1130) preferably forms a gap of 1.15 mm to 1.25 mm with the X-ray incidence hole (1140) of the first cell plate (1100). The reference point is the end point of the X-ray incidence hole (1140) and the start point of the X-ray emission hole (1240).

[0073] If the distance between the X-ray incident hole (1140) and the X-ray exit hole (1240) is less than 1.15 mm, the amount of electrolyte formed between them is small and the catalytic reaction may be insignificant, and if it exceeds 1.25 mm, the amount of electrolyte moving through the electrolyte passage (1130) is large and it may be difficult to measure X-rays due to scattering of X-rays.

[0074] Of course, if the distance between the X-ray incident hole (1140) and the X-ray exit hole (1240) exceeds 1.25 mm, measurement can be performed with X-rays of higher sensitivity, but in that case, it is difficult to miniaturize and lighten the real-time electrochemical cell (1000) of the present invention.

[0075] For this reason, when the distance between the X-ray incident hole (1140) and the X-ray exit hole (1240) is 1.15 mm to 1.25 mm, the amount of electrolyte is optimized to minimize interference with the X-ray and minimize loss of X-ray intensity, thereby achieving high measurement efficiency with less X-ray and making the real-time electrochemical cell (1000) smaller and lighter.

[0076] Meanwhile, the second cell plate (1200) sealing the electrolyte transfer channel (1130) at this time can form a gap of 0.65 mm to 0.75 mm with the electrolyte transfer channel (1130). That is, the depth (D) of the electrolyte transfer channel can form a gap of 0.65 mm to 0.75 mm.

[0077] Meanwhile, as described above, an O-ring groove (1170) is formed in the first cell plate (1100), and an O-ring (1175) is fitted into the O-ring groove (1170). When the second cell plate (1200) is fixed in close contact with the first cell plate (1100) by the fixing means (1300), the O-ring (1175) is also fixed in close contact, thereby further preventing leakage of the electrolyte.

[0078] Additionally, a second film (1260) may be attached to one surface of the second cell plate (1200) so that the electrolyte moving along the electrolyte flow path (1130) does not leak into the X-ray emission hole (1240).

[0079] Here, one surface of the second cell plate (1200) to which the second film (1260) is attached is not limited, but preferably can be attached to the surface facing the first cell plate (1100).

[0080] Additionally, the second film (1260) may be a polyimide film that is non-conductive and chemically resistant while allowing X-rays to pass through, but is not necessarily limited to a polyimide film; any film that allows X-rays to pass through and exhibits properties such as non-conductivity and chemical resistance may be used.

[0081] In addition, the second cell plate (1200) may be formed so that a sheet support (1270) protrudes from the top. Here, the sheet support (1270) supports one side of a sample sheet (1500) interposed between the first cell plate (1100) and the second cell plate (1200) to ensure that an electrochemical reaction occurs more reliably.

[0082] Additionally, the sheet support (1270) can also be used as a reference point to easily determine the mounting direction of the real-time electrochemical cell (1000) of the present invention. Here, the sheet support (1270) may be provided in an L-shape bent in one direction as shown in the drawing to make it easier to determine the mounting direction.

[0083] The fixing means (1300) for closely fixing the first cell plate (1100) and the second cell plate (1200) is not limited in shape, and any shape that closely fixes the first cell plate (1100) and the second cell plate (1200) is sufficient.

[0084] However, referring to the drawings of the present invention illustrating a preferred form, the fixing means (1300) may be composed of a first fixing plate (1310) and a second fixing plate (1320) formed on the outer sides of the second cell plate (1200) of the first cell plate (1100) based on the view of the present invention from the side.

[0085] Specifically, on one of the first fixing plate (1310) and the second fixing plate (1320), a fixing pin (1330) that protrudes toward the other fixing plate may be formed at a position symmetrical to each other with respect to the center of the plate.

[0086] That is, a fixing pin (1330) may be formed on the upper and lower sides or the left and right sides of one of the first fixing plate (1310) and the second fixing plate (1320). Here, in the present invention, four pins are exemplified, with two on each side, but it is sufficient to provide only two fixing pins (1330).

[0087] A fixing pin (1330) protruding from one fixing plate toward another fixing plate can be inserted into another fixing plate by penetrating the first fixing plate (1310) and the second fixing plate (1320) in sequential or reverse order.

[0088] To this end, the first cell plate (1100) and the second cell plate (1200) form a fixing pin through hole (1332) through which a fixing pin (1330) passes, and a fixing pin insertion hole (1334) can be formed in the fixing plate among the first fixing plate (1310) and the second fixing plate (1320) where the fixing pin (1330) is not provided.

[0089] Additionally, the first fixed plate (1310) and the second fixed plate (1320) may be configured to be fastened with fastening bolts (not shown). That is, the fastening bolts may be fastened from the first fixed plate (1310) to the second fixed plate (1320) by penetrating the first cell plate (1100) and the second cell plate (1200), or fastened from the second fixed plate (1320) to the first fixed plate (1310) by penetrating the first cell plate (1100) and the second cell plate (1200).

[0090] To this end, continuous bolt insertion holes (1340) can be formed from the first fixed plate (1310) to the first cell plate (1100), the second cell plate, and the second fixed plate (1320). The positions of the bolt insertion holes (1340) are not limited, but at least two may be provided at positions symmetrical with respect to the center of each plate, and preferably, they may all be provided at the vertices of the plates so that four fastening bolts can be fastened.

[0091] The fixing method using the above fixing pin (1330) and fastening bolt may be provided with only one of the two, but it is more preferable to form both.

[0092] Meanwhile, the first fixed plate (1310) and the second fixed plate (1320) may be configured with a step offset hole (1350) to offset the step difference and to bring the first cell plate (1100) and the second cell plate (1200) closer together without interference from the step difference, in the event that a step difference occurs when the first cell plate (1100) is protruded by the fastening part (1152) of the film insert (1150) as shown in the drawing, or when a step difference occurs when the second cell plate (1200) is protruded by the X-ray emission hole (1240).

[0093] The step offset hole (1350) is configured to allow the fastening part (1152), which is a protruding part, or the X-ray emission hole (1240) to be inserted and fitted, thereby offsetting the step, so that the first fixing plate (1310) and the second fixing plate (1320) can be closely fixed to the first cell plate (1100) and the second cell plate (1200) at a closer distance, and leakage of the electrolyte can be prevented more reliably. In addition, the surface of the real-time electrochemical cell (1000) of the present invention may be smoothed to improve aesthetics.

[0094] Meanwhile, in addition to the configuration including the first fixing plate (1310) and the second fixing plate (1320), any form of fixing means (1300) that closely fixes the first cell plate (1100) and the second cell plate (1200) as described above is sufficient.

[0095] That is, the fixing means (1300) may be an uneven surface and an uneven groove configured in a different form on the first cell plate (1100) and the second cell plate (1200), although not shown in the drawing, to directly connect the first cell plate (1100) and the second cell plate (1200).

[0096] In other words, one of the first cell plate (1100) and the second cell plate (1200) may have an uneven surface formed that protrudes to the other cell plate, and the other may have an uneven groove into which the uneven surface is inserted, so that the first cell plate (1100) and the second cell plate (1200) may be formed to be directly coupled.

[0097] Meanwhile, the present invention is characterized in that, in the real-time electrochemical cell (1000) configured as described above, the electrolyte flow path (1130) is configured to reduce bubbles. This will be examined in more detail with reference to FIGS. 5 to 7b.

[0098] FIG. 5 is a front view of a first cell plate, which is a component of an electrochemical cell for X-ray scattering and absorption experiments of the present invention; FIG. 6a to 6e are drawings showing various structures in which the bubble reduction channel of the first cell plate can reduce bubbles through an upward channel; and FIG. 7a and 7b are drawings showing various structures in which the bubble reduction channel of the first cell plate is formed with a wider width than other channels to reduce bubbles.

[0099] Referring to FIGS. 5 to 7b, the electrolyte transfer channel (1130) may be configured to include a first transfer channel (1131), a second transfer channel (1132), and a bubble reduction channel (1133).

[0100] Specifically, the first moving channel (1131) is a channel connected to the electrolyte inflow channel (1110) and can preferably form a length in the horizontal direction. Additionally, the second moving channel (1132) is a channel connected to the electrolyte outflow channel (1120) and can preferably form a length in the horizontal direction.

[0101] The bubble reduction channel (1133) is a channel connecting the first movement channel (1131) and the second movement channel (1132) between the first movement channel (1131) and the second movement channel (1132), and can be formed with a structure that reduces bubbles in the electrolyte. That is, the electrolyte introduced into the first movement channel (1131) can be transferred to the second movement channel (1132) in a state where bubbles are reduced through the structure of the bubble reduction channel (1133) while passing through the bubble reduction channel (1133).

[0102] The above bubble reduction channel (1133) may be configured to include one or more rising channels (1135) configured to allow the electrolyte to rise and move in a height direction.

[0103] That is, the bubble reduction channel (1133) may be in the form of one rising channel (1135) or a vertical channel (1135a) as shown in FIG. 5, or one rising channel (1135) or a sloped channel (1135b) as shown in FIG. 6a, or two rising channels (1135) or vertical channels (1135a) as shown in FIG. 6b and FIG. 6c.

[0104] Here, preferably, the second moving channel (1132) may be positioned higher than the first moving channel (1131), because when the second moving channel (1132) is positioned higher than the first moving channel (1131), it must include at least one rising channel (1135).

[0105] However, as shown in FIG. 6d or FIG. 6e, the first moving channel (1131) and the second moving channel (1132) may be the same in height, and in this case, the bubble reduction channel (1133) may be configured to include one or more rising channels (1135) in the same way.

[0106] Since the above-mentioned upward flow path (1135) structurally moves the electrolyte in the opposite direction of gravity (upward direction) that resists gravity, the electrolyte delivered from the first moving flow path (1131) at equal pressure rises from the bottom to the top of the upward flow path (1135), and the heavier electrolyte has the property of tending to descend under the influence of gravity, while the bubbles in the lighter electrolyte have the property of tending to rise, so the bubbles can be discharged more quickly and reduced.

[0107] Here, it is most preferable that the rising path (1135) forms a single vertical path (1135a) such that the distance between the first moving path (1131) and the second moving path (1132) forms the shortest distance, as in the embodiment shown in FIG. 5 of the present invention, thereby minimizing interference factors for the movement of the electrolyte.

[0108] Meanwhile, the bubble reduction channel (1133) may be formed in a shape that forms a wider width (C) than the respective channel widths (A, B) of the first and second moving channels (1131, 1132). This applies to both cases where the second moving channel (1132) is formed higher than the first moving channel (1131), as shown in FIG. 7a, and where the first moving channel (1131) and the second moving channel (1132) are formed at the same height, as shown in FIG. 7b.

[0109] As shown in FIGS. 7a and 7b, if the width (C) of the bubble reduction channel (1133) is wider than the widths (A, B) of the first moving channel (1131) and the second moving channel (1132), the pressure of the electrolyte introduced through the first moving channel (1131) is lowered at an instantaneous rate, and the bubbles in the electrolyte rise and escape, thereby reducing the bubbles in the electrolyte.

[0110] In particular, as shown in FIG. 7b, when the second moving channel (1132) is formed at a higher height than the first moving channel (1131), and the bubble reduction channel (1133) is formed with a width (A, B) wider than the width of the first moving channel (1131) and the second moving channel (1132), the effect of doubled bubble reduction can also be achieved.

[0112] [Verification of Stability and Operation of Electrochemical Cell for X-ray Scattering and Absorption Experiments]

[0113] Experiments were conducted to verify the stability and operation of the real-time electrochemical cell (1000) of the present invention as described above. For the experiments to verify the stability and operation, a prototype of the real-time electrochemical cell (1000) as described above was fabricated, and X-rays of various sensitivities were measured while varying the flow rate.

[0114] Here, the prototype of the real-time electrochemical cell (1000) is manufactured with a gap of 1.2 mm between the X-ray incident hole (1140) and the X-ray exit hole (1240) (here, the depth (D) of the electrolyte transfer channel (1130) is 0.7 mm), and the shape of the electrolyte transfer channel (1130) is such that the second transfer channel (1132), located in the direction of electrolyte outflow, is positioned higher than the first transfer channel (1131), located in the direction of electrolyte inflow.

[0115] Additionally, the bubble reduction channel (1133) connecting the first moving channel (1131) and the second moving channel (1132) is formed as a single vertical channel such that the distance between the first moving channel (1131) and the second moving channel (1132) can form the shortest distance. The result is as shown in FIGS. 8 and 9.

[0116] Figure 8a shows the X-ray measurement results when a flow rate of 0.02 ml / min is applied during a stability test of an electrochemical cell for X-ray scattering and absorption experiments, Figure 8b shows the X-ray measurement results when a flow rate of 0.01 ml / min is applied, and Figure 9 shows the operation results of an electrochemical cell for X-ray scattering and absorption experiments in electrochemical catalytic reaction experiments of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER).

[0117] Referring to FIG. 8, the real-time electrochemical cell (1000) of the present invention was confirmed to have X-ray measurement stability at various flow rates such as 0.01 ml / min and 0.02 ml / min, and referring to FIG. 9, the real-time electrochemical cell (1000) of the present invention was confirmed to operate in various electrochemical catalytic reaction experiments such as hydrogen evolution reaction (HER) and oxygen evolution reaction (OER).

[0118] This is judged to be the result of the smooth reduction of bubbles, which are an interfering factor in X-ray measurement, within the electrolyte flow path (1130).

[0120] As described above, the present invention has been illustrated and explained with reference to preferred embodiments, but it is not limited to the aforementioned embodiments, and various changes and modifications may be made by those skilled in the art within the scope of the invention without departing from the spirit of the invention. Explanation of the symbols

[0122] 100: X-ray emitter 200: X-ray absorption device 1000: Electrochemical cell for X-ray scattering and absorption experiments 1100 : First cell plate 1110: Electrolyte inflow path 1115: First electrode 1120 : Electrolyte outflow path 1125 : Second electrode 1130 : Electrolyte flow path 1131 : 1st Mobile Euro 1132 : 2nd Mobile Euro 1133 : Bubble reduction Euro 1135 : Rising Euro 1135a : Vertical Euro 1135b : Slope Euro 1140 : X-ray entrance hole 1141: 1st X-ray Intrusion Hall 1142: Second X-ray Intrusion Hole 1150 : Film insert 1151 : Insert 1152 : Connecting part 1160: First film 1170 : O-ring groove 1175 : O-ring 1200 : Second cell plate 1240 : X-ray Exit Hall 1260: Second Film 1270 : Seat support piece 1300 : Fixing means 1310: First fixed plate 1320 : Second fixed plate 1330 : Fixing pin 1332 : Fixing pin through hole 1334 : Fixing pin insertion hole 1340 : Bolt insertion hole 1350 : Step offset hole 1500 : Sample sheet

Claims

Claim 1 A first cell plate having an electrolyte inlet channel formed on one side through which an electrolyte is introduced and a first electrode is inserted, and an electrolyte outlet channel formed on the other side through which an electrolyte is discharged and a second electrode is inserted, and an electrolyte movement channel formed on one surface through which an X-ray incident hole is provided for the electrolyte to be incident and transmitted through the electrolyte movement path connected to the electrolyte inlet channel and the electrolyte outlet channel, wherein the electrolyte is moved; a second cell plate having an X-ray emission hole formed therein for emitting X-rays transmitted through the X-ray incident hole, wherein a sample sheet is interposed between the electrolyte movement channel and the second cell plate in a position facing the electrolyte movement channel, and the second cell plate having an X-ray emission hole formed therein for emitting X-rays transmitted through the X-ray incident hole, and a fixing means for tightly fixing the first cell plate and the second cell plate so as to hermetically seal the electrolyte movement channel, wherein the gap between the X-ray incident hole and the X-ray emission hole is 1.20 mm to 1.25 mm, and the electrolyte movement channel comprises: a first movement channel connected to the electrolyte inlet channel and having a length in the horizontal direction; and a channel connected to the electrolyte outlet channel and having a length in the horizontal direction A real-time electrochemical cell for synchrotron-based X-ray scattering and absorption experiments, comprising a second moving channel formed therein and a bubble reduction channel configured between the first moving channel and the second moving channel to reduce bubbles in the electrolyte introduced into the first moving channel and transfer them to the second moving channel, wherein the second moving channel is provided at a higher position than the first moving channel, and the bubble reduction channel includes one or more rising channels configured to allow the electrolyte to rise and move in the height direction, wherein the bubble reduction channel forms a width wider than the respective channel widths of the first and second moving channels, and wherein the depth of the electrolyte moving channel forms a gap of 0.65 mm to 0.75 mm. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 A real-time electrochemical cell for synchrotron-based X-ray scattering and absorption experiments according to claim 1, wherein the rising path is a single vertical path such that the distance between the first moving path and the second moving path can form the shortest distance. Claim 6 delete Claim 7 A real-time electrochemical cell for synchrotron-based X-ray scattering and absorption experiments according to claim 1, characterized in that the X-ray emission hole is formed in the shape of a near-narrow halo, with the diameter expanding as it extends in the direction of X-ray emission.

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