Raman diffraction combined with in-situ characterization system and detection method

Abstract

The present invention discloses a Raman diffraction combined in-situ characterization system, including a rotating platform, a sample holder, an X-ray assembly, a first detector, and a Raman optical path assembly, wherein the sample holder is connected to a fixed plate at the center of the rotating platform, the X-ray assembly and the first detector are connected to the rotating plate of the rotating platform and form an X-ray diffraction optical path with the sample holder, the Raman optical path assembly is adjustable in a direction perpendicular to the X-ray diffraction optical path and is located above the sample holder, the Raman optical path assembly and the sample holder form a Raman optical path, and the X-ray diffraction optical path and the Raman optical path intersect at the sample holder. The present invention also discloses a detection method for the Raman diffraction combined in-situ characterization system. Beneficial effects of the present invention: Based on the combined system of X-ray light source and laser Raman, it is possible to realize synchronous testing of various research target systems under real working conditions, and to realize all-round structural evolution information such as material structure phase change and micromolecular vibration of the target research system under real working conditions.

Description

Technical Field

[0001] The invention relates to the technical field of spectrum characterization, and in particular to a Raman diffraction coupling system. Background Art

[0002] In the 100 years since Laue and others discovered the diffraction phenomenon of copper sulfate crystals in 1912, X-ray diffraction, an important detection method, has played a positive role in people's understanding and exploration of nature, especially in many fields such as condensed matter physics, materials science, life medicine, chemistry and chemical engineering, geology, mineralogy, environmental science, archaeology, and history.

[0003] XRD stands for X-ray Diffraction. It uses the diffraction phenomenon of X-rays in crystals to obtain the characteristics of X-ray signals after diffraction, and obtains diffraction patterns after processing. X-ray diffraction technology is used to identify the phases of substances in various fields, and to perform various qualitative and quantitative analyses; the crystallinity of substances is determined based on the diffraction pattern area of ​​the crystalline phase and the pattern area of ​​the amorphous phase. In short, X-ray diffraction technology has become the most basic and important means of structural testing.

[0004] At the same time, Raman spectroscopy uses the Raman scattering intensity and Raman shift correlation when the molecules of a substance generate Raman scattering under monochromatic light to analyze the vibration or rotation energy level of the sample molecules, thereby understanding the molecular structure. Traditionally, techniques such as powder X-ray diffraction (pXRD) and Raman spectroscopy have been used to study the crystal structure of materials. Using pXRD, the size of the coherent diffraction domains in the ab and c directions can be determined. These are considered to represent the average grain width LA and the average grain height LC of the fully crystalline region within the material. On the other hand, a Raman spectrometer is an instrument that can be used to study the molecular vibration and lattice vibration of a substance. It is based on the Raman scattering phenomenon and can provide information about the sample structure, chemical composition and physical properties by measuring the frequency shift and intensity of scattered light in the sample. Using Raman spectroscopy, the distance between crystal defects in the material can be determined. Crystal edges can also be regarded as defects. Therefore, if it is assumed that the material mainly consists of small grains, the distance between defects will be related to the grain width LA. Raman spectrometers usually consist of the following main parts: laser, optical system, sample chamber, detector, spectrometer system and other key components. Modern commercial Raman spectrometers usually use fiber coupling and grating dispersion technology to achieve high-sensitivity and high-resolution measurements. Raman spectrometers can be used in many applications, including materials science, chemical analysis, drug development, environmental monitoring and other fields. It has the advantages of non-invasiveness, no sample pretreatment, high sensitivity and high resolution, and can provide rich structural and composition information, helping scientists to gain a deeper understanding of the properties and reaction mechanisms of materials.

[0005] With the development and progress of modern science, researchers are constantly expanding the depth and breadth of basic research, and have gradually moved from the previous single model to the analysis and research of actual samples under various actual working conditions. Considering that under real working conditions, the properties and behaviors of substances are often affected by the joint action of multiple physical or chemical fields, a single characterization method is difficult to fully reflect the characteristics of materials. For example, XRD mainly targets crystalline samples with long-range structures, and amorphous and amorphous samples cannot obtain the corresponding structure. Similarly, Raman characterization mainly targets molecular structure changes, and it cannot provide effective information for various metal materials or other materials that do not have molecular vibrations. However, in a dynamic structural study, the morphological structure changes of substances are often continuous and variable, and the structure and morphology of the materials involved may change greatly. Taking the zeolite system in industrial catalysis as an example, due to the complexity of the zeolite formation process, it is obviously impossible to effectively obtain the complex transformation from amorphous to crystalline using a single Raman spectrometer or XRD characterization.

[0006] Therefore, it is possible to consider combining multi-field coupling characterization techniques, such as X-ray diffraction and Raman characterization techniques, to comprehensively analyze the interactions between them, so as to obtain a more comprehensive and accurate description of material properties. In addition, combined research also requires rapid screening technology to test and evaluate changes in composition, structure and properties in the material library.

[0007] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art known to a person skilled in the art. Summary of the invention

[0008] The technical problem to be solved by the present invention is: how to solve the problem that a single characterization method is difficult to fully reflect the characteristics of a material.

[0009] The present invention solves the above technical problems through the following technical means:

[0010] A Raman diffraction combined in-situ characterization system comprises a rotating platform, a sample rack, an X-ray assembly, a first detector, and a Raman optical path assembly, wherein the sample rack is connected to a fixed plate at the center of the rotating platform, the X-ray assembly and the first detector are connected to the rotating plate of the rotating platform and form an X-ray diffraction optical path with the sample rack, the Raman optical path assembly is adjustable in a direction perpendicular to the X-ray diffraction optical path and is located above the sample rack, the Raman optical path assembly and the sample rack form a Raman optical path, and the X-ray diffraction optical path and the Raman optical path intersect at the sample rack.

[0011] The sample holder, X-ray assembly, first detector and Raman optical path assembly of the present invention are integrated on a rotating platform, and the X-ray diffraction pattern and Raman spectrum from the same sample or sample area can be measured simultaneously or sequentially. Therefore, the optical path of the present invention is composed of an X-ray diffraction optical path and a Raman optical path; in order to match the simultaneity of the two detection modes in the whole system, the system separately designs a Raman optical path. Compared with the existing commercial Raman optical path, the Raman optical path structure design in the present invention is simple and efficient. Based on the diffraction, scattering and other technical means of the laboratory X-ray light source, the present invention can achieve the second-level time resolution capability of general samples in conventional laboratories, and at the same time has enough physical space to adapt to a variety of in-situ reaction test devices under different environmental conditions. At the same time, matching the combined system of laser Raman, it can realize the synchronous testing of various research target systems under real working conditions. Realizing the full range of structural evolution information such as material structure phase change and micromolecular vibration of the target research system under real working conditions provides great help for further understanding of scientific problems in the reaction process.

[0012] Preferably, it also includes a first movable component that can enable the X-ray component to move horizontally along the direction of the X-ray diffraction light path, the X-ray component includes an X-ray machine and an X-optical mirror, the bottom of the X-ray machine is connected to the top of the first movable component, the X-optical mirror is connected to the transmitting end of the X-ray machine, and the bottom of the first movable component is connected to the rotating plate of the rotating platform.

[0013] Preferably, it also includes a second movable component capable of enabling the first detector to move horizontally along the direction of the X-ray diffraction light path, the bottom of the first detector is connected to the top of the second movable component, and the bottom of the second movable component is connected to the rotating plate of the rotating platform.

[0014] The present invention enables the X-ray component and the first detector to move along the X-ray diffraction optical path through the first moving component and the second moving component, realizes signal collection in different modes, and expands the resolution and detection range of XRD.

[0015] Preferably, the sample rack includes a rack body, a first window, a second window, and a third window. The bottom of the rack body is fixedly connected to the rotating platform. The top of the rack body is provided with a horizontal channel and a vertical channel vertically connected to the horizontal channel. The two ends of the horizontal channel are respectively connected to the second window and the third window, and the top of the vertical channel is connected to the first window.

[0016] Preferably, the first window is made of laser-transparent material, and the second window and the third window are made of X-ray-transparent material; the size of the first window and the second window is greater than or equal to 1 mm, the size of the third window is 1-6 mm, and the opening angle of the third window is greater than 60 degrees.

[0017] The independent design of the sample holder can ensure both the parallel transmission of X-rays and the vertical incidence of the Raman optical path. Similar optical path designs can also be extended to different in-situ reactor structure designs.

[0018] Preferably, the light source target material of the X-ray assembly is one of a Cu target, a Mo target and an Ag target.

[0019] The Cu target is for low-energy samples, the Mo target is for medium-energy samples, and the Ag target is for high-energy samples. They can not only meet the sample penetration requirements of various in-situ testing devices, but also achieve non-destructive testing requirements in various in-situ testing environments.

[0020] Preferably, the Raman optical path component includes a laser generator, an optical coupling lens group, a light source, an objective lens, a second detector, and a spectrometer; the light source generates visible light which sequentially passes through the optical coupling lens group and the objective lens to reach the sample surface, and then is reflected to the second detector; the laser generator generates laser light which passes through the objective lens to reach the sample surface, excites the Raman signal of the sample, and then returns to the spectrometer.

[0021] Preferably, the optical coupling mirror group consists of three reflective optical mirrors, the laser generator is arranged in a vertical direction to the objective lens, the first reflective optical mirror is located between the laser generator and the objective lens, the second reflective optical mirror is located directly below the first reflective optical mirror, the third reflective optical mirror is located on one side of the second reflective optical mirror, the second detector is located on one side of the first reflective optical mirror, and the spectrometer is located on the other side of the third reflective optical mirror; the laser emitted by the laser generator passes through the first reflective optical mirror, the second reflective optical mirror, and the objective lens to the sample to excite the Raman signal of the sample, and the Raman signal reflected back by the sample passes through the second reflective optical mirror and the third reflective optical mirror to the spectrometer; the light emitted by the light source passes along the third reflective optical mirror, the second reflective optical mirror, and the objective lens to the sample, and the light signal reflected back by the sample passes through the second reflective optical mirror and the third reflective optical mirror to the second detector.

[0022] The detection method of the Raman diffraction combined in-situ characterization system adopts the above-mentioned Raman diffraction combined in-situ characterization system, and comprises the following steps: placing the sample on the sample holder, adjusting the rotating plate of the rotating platform so that the X-ray assembly and the first detector form a horizontal X-ray diffraction optical path with the sample holder, and the Raman optical path assembly and the sample holder form a vertical Raman optical path, and the Raman optical path and the X-ray diffraction optical path are vertically crossed on the sample; turning on the X-ray assembly, the first detector, and the Raman optical path assembly, and acquiring the XRD signal and the Raman signal at the same position of the sample.

[0023] The present invention can realize more ultrafast reaction in-situ observation and multi-field multi-modal in-situ test conditions through the in-situ Raman / X-ray diffraction combined characterization system, and can also realize online monitoring and recording of material structure change information in the reaction process of new energy battery system, electrochemical reaction system and other multi-phase reaction system on a time scale of seconds. Through the combination of multi-field and multi-modal instruments, the ability to reveal the material structure and reaction process in multi-phase reactions in a wider range of time and space and other multi-scale aspects is realized. Such as X-ray absorption spectrum, X-ray small angle scattering, etc., to obtain the structural information of materials under different high temperature environments.

[0024] Preferably, the X-ray assembly has two working modes, including a transmission mode and a reflection mode; in the transmission mode, the X-ray assembly has two working modes, including a transmission mode and a reflection mode; in the transmission mode, the X-ray assembly moves to a suitable distance from the sample holder through the first movable assembly, and after the X-rays are emitted by the X-ray assembly through the sample, the first detector collects the signal, and the position and angle of the first detector and the sample holder are adjusted to detect the signals at different distances and angles; in the reflection mode, the X-ray assembly and the first detector are moved to a distance equal to the sample holder through the first movable assembly and the second movable assembly, and the X-ray assembly and the first detector are synchronously rotated by the rotating plate of the rotating platform to realize signal collection at different angles.

[0025] Preferably, the light source of the X-ray assembly includes a linear light source and a point light source, the linear light source is used for the reflection mode, and the point light source is used for the transmission mode; the first detector is one of a zero-dimensional detector, a one-dimensional detector, and a two-dimensional detector, the zero-dimensional detector is used for the reflection mode, and the one-dimensional detector and the two-dimensional detector are compatible with the reflection mode and the transmission mode.

[0026] The advantages of the present invention are:

[0027] (1) The sample holder, X-ray assembly, first detector, and Raman optical path assembly of the present invention are integrated on a rotating platform, and the X-ray diffraction pattern and Raman spectrum from the same sample or sample area can be measured simultaneously or sequentially. Therefore, the optical path of the present invention is composed of an X-ray diffraction optical path and a Raman optical path; in order to match the simultaneity of the two detection modes in the entire system, the system of the present invention separately designs a Raman optical path. Compared with the existing commercial Raman optical path, the Raman optical path structure design in the present invention is simple and efficient. Based on the diffraction, scattering and other technical means of the laboratory X-ray light source, the present invention can achieve the second-level time resolution capability of general samples in conventional laboratories, and at the same time has sufficient physical space to adapt to a variety of in-situ reaction test devices under different environmental conditions; at the same time, matched with the laser Raman combined system, it can realize the synchronous testing of various research target systems under real working conditions. The realization of all-round structural evolution information such as material structure phase change and micromolecular vibration of the target research system under real working conditions provides great help for further in-depth understanding of scientific problems in the reaction process;

[0028] (2) The present invention enables the X-ray assembly and the first detector to move along the X-ray diffraction optical path through the first moving assembly and the second moving assembly, thereby realizing signal collection in different modes and expanding the resolution and detection range of XRD;

[0029] (3) The sample holder is designed independently, which can ensure both parallel transmission of X-rays and vertical incidence of Raman light paths. Similar light path designs can also be extended to different in-situ reactor structure designs.

[0030] (4) Cu target is for low-energy samples, Mo target is for medium-energy samples, and Ag target is for high-energy samples. They can not only meet the sample penetration requirements of various in-situ test devices, but also realize the non-destructive testing requirements in various in-situ test environments;

[0031] (5) The present invention can realize more ultrafast reaction in-situ observation and multi-field multi-modal in-situ test conditions through the in-situ Raman / X-ray diffraction combined characterization system, and can also realize online monitoring and recording of material structure change information in the reaction process of new energy battery system, electrochemical reaction system and other multi-phase reaction system on a time scale of seconds. Through the combination of multi-field and multi-modal instruments, the ability to reveal the material structure and reaction process in multi-phase reactions in a wider range of time and space is achieved. Such as X-ray absorption spectrum, X-ray small angle scattering, etc., to obtain the structural information of materials under different high temperature environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a schematic structural diagram of a Raman diffraction combined in-situ characterization system according to an embodiment of the present invention;

[0033] Figure 2 1 is a schematic structural diagram of a Raman diffraction combined in-situ characterization system (with a hidden rotating platform) according to an embodiment of the present invention;

[0034] Figure 3 2 is a schematic diagram of the transmission mode operation of the Raman diffraction combined in-situ characterization system according to an embodiment of the present invention;

[0035] Figure 4 2 is a schematic diagram of the reflection mode operation of the Raman diffraction combined in-situ characterization system according to an embodiment of the present invention;

[0036] Figure 5 is a schematic diagram of the working of the sample holder according to an embodiment of the present invention;

[0037] Figure 6 is a schematic diagram of a Raman optical path component according to an embodiment of the present invention;

[0038] Numbers in the figure:

[0039] 1. Rotating platform; 2. Sample holder; 21. First window; 22. Second window; 23. Third window; 3. X-ray assembly; 31. X-ray machine; 32. X-ray optical mirror; 4. First detector; 5. Raman optical path assembly; 51. Laser generator; 52. Light source; 53. Objective lens; 54. Second detector; 55. Spectrometer; 56. First transflective optical mirror; 57. Second transflective optical mirror; 58. Third transflective optical mirror; 6. First moving assembly; 7. Second moving assembly. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Embodiment 1:

[0042] like Figure 1 , Figure 2As shown, the Raman diffraction combined in-situ characterization system includes a rotating platform 1, a sample rack 2, an X-ray assembly 3, a first detector 4, and a Raman optical path assembly 5. The sample rack 2 is connected to a fixed plate at the center of the rotating platform 1, the X-ray assembly 3 and the first detector 4 are connected to the rotating plate of the rotating platform 1 and form an X-ray diffraction optical path with the sample rack 2, and the Raman optical path assembly 5 can be adjusted along the direction perpendicular to the X-ray diffraction optical path and is located above the sample rack 2. The Raman optical path assembly 5 forms a Raman optical path with the sample rack 2, and the X-ray diffraction optical path and the Raman optical path intersect at the sample rack 2. Among them, the bottom of the X-ray assembly 3 is connected to the first movable assembly 6, which can realize the X-ray assembly 3 to approach and move away from the sample rack 2 along the X-ray diffraction optical path. The bottom of the first detector 4 is connected to the second movable assembly 7, which can realize the first detector 4 to approach and move away from the sample rack 2 along the X-ray diffraction optical path.

[0043] The rotating platform 1 can adopt the existing technology, but the middle part of the rotating platform 1 is fixed to ensure that the sample holder 2 is fixed at its center position and remains motionless. The first movable component 6 and the second movable component 7 are connected to the rotating plate of the rotating platform 1. The rotating plate of the rotating platform 1 can rotate around the central axis, so that the first movable component 6 and the X-ray component 3, as well as the second movable component 7 and the first detector 4, can rotate around the sample holder 2.

[0044] The first movable component 6 and the second movable component 7 can adopt a combination of a slider and a slide rail in the prior art. In this embodiment, the first movable component 6 and the second movable component 7 enable the X-ray component 3 and the first detector 4 to move along the X-ray diffraction optical path, realize signal collection in different modes, and expand the resolution and detection range of XRD.

[0045] This embodiment gives priority to the design requirements of the X-ray diffraction optical path, designs the entire X-ray diffraction optical path in the xy plane, and realizes various XRD test conditions by rotating the X-ray component 3 and the first detector 4 in the xy plane. At the same time, this embodiment realizes the in-situ Raman test function of the sample by placing the Raman optical path component 5 just above the sample holder 2 (in the z-axis direction).

[0046] The X-ray assembly 3 includes an X-ray machine 31 and an X-ray optical mirror 32. The bottom of the X-ray machine 31 is connected to the top of the first movable assembly 6, the X-ray optical mirror 32 is connected to the emission end of the X-ray machine 31, and the bottom of the first movable assembly 6 is connected to the rotating plate of the rotating platform 1. Specifically, the X-ray optical mirror 32 is fixed to the exit position of the X-ray machine 31 by mechanical fixing methods such as bolts and clamping, and is used for monochromatization and focusing of X-rays. The entire X-ray machine 31 can be fixed to the slider at the top of the first movable assembly 6 by bolts or clamping, and the slide rail at the bottom of the first movable assembly 6 is fixed to the rotating plate of the rotating platform 1 by bolts or the like. The slider and the slide rail can realize radial sliding along the rotating platform 1 with high precision.

[0047] In this embodiment, the X-ray assembly 3 and the first detector 4 have two working modes, including a transmission mode and a reflection mode. In the transmission mode, Figure 3 As shown, after the X-ray machine 31 moves to a suitable distance from the sample holder 2 through the first moving assembly 6, the X-ray is emitted by the X-ray machine 31, and reaches the first detector 4 after passing through the sample. In order to further expand the resolution and detection range of XRD, the radial movement of the second moving assembly 7 under the first detector 4 and the circumferential rotation of the rotating platform 1 can be used to achieve this; in the reflection mode, as shown Figure 4 As shown, the X-ray machine 31 and the first detector 4 are first moved to a distance equal to the sample holder 2 through the first moving assembly 6 and the second moving assembly 7, and then the X-ray machine 31 and the first detector 4 are synchronously rotated by the rotating platform 1 to realize the XRD angle measurement and signal collection.

[0048] The selection of the X-ray light source 52 mainly involves the shape of the light source 52 and the target material used. The light source shape includes two types: linear light source and point light source. The linear light source is mainly designed for the X-ray machine 31 and the first detector 4 to rotate synchronously (reflection type); the point light source is mainly designed for the X-ray machine 31 and the first detector 4 to move linearly (transmission type). The light source target material can be replaced and selected according to the different X-ray absorption capabilities of the sample to be tested, including three types: Cu target, Mo target and Ag target. The Cu target is for low-energy samples, the Mo target is for medium-energy samples, and the Ag target is for high-energy samples. Taking ordinary dynamic in-situ experiments as an example, a medium-energy Mo target (E~17keV) can be selected, which can not only meet the sample penetration requirements of various in-situ test devices, but also achieve non-destructive testing requirements in various in-situ test environments.

[0049] The first detector 4 is a signal collector for collecting X-ray scattering and diffraction signals, and can adopt different types of detectors such as zero-dimensional (0D), one-dimensional (1D) or two-dimensional (2D). Among them, the 0D detector is mainly used for reflective optical path use, and the 1D and 2D detectors are compatible with reflective and transmissive optical path structures.

[0050] like Figure 5 As shown, the sample rack 2 includes a rack body, a first window 21, a second window 22, and a third window 23. The bottom of the rack body is fixedly connected to the rotating platform 1. The top of the rack body is provided with a horizontal channel and a vertical channel vertically connected to the horizontal channel. The horizontal channel and the vertical channel form an inverted T-shaped structure. The two ends of the horizontal channel are respectively connected to the second window 22 and the third window 23, and the top of the vertical channel is connected to the first window 21.

[0051] The first window 21 is suitable for laser transmission, and the first window 21 is made of laser-transmitting material, and highly transparent quartz or sapphire material can be selected; the size of the first window 21 is greater than or equal to 1 mm; the second window 22 and the third window 23 are made of materials with high X-ray penetration ability, such as metal beryllium, graphite carbon or polymer film, the size of the second window 22 is greater than or equal to 1 mm, the size of the third window 23 is 1-6 mm, and the opening angle of the third window 23 is greater than 60 degrees.

[0052] The sample holder 2 is independently designed to ensure both parallel transmission of X-rays and vertical incidence of the Raman optical path. Similar optical path designs can also be extended to different in-situ reactor structure designs.

[0053] like Figure 6 As shown, the Raman optical path component 5 includes a laser generator 51, an optical coupling mirror group, a light source 52, an objective lens 53, a second detector 54, and a spectrometer 55; wherein the optical coupling mirror group is composed of three transflective optical mirrors, specifically, a first transflective optical mirror 56, a second transflective optical mirror 57, and a third transflective optical mirror 58.

[0054] The laser generator 51 is arranged perpendicular to the objective lens 53, the first transflective optical mirror 56 is located between the laser generator 51 and the objective lens 53, the second transflective optical mirror 57 is located directly below the first transflective optical mirror 56, the third transflective optical mirror 58 is located on the right side of the second transflective optical mirror 57, the second detector 54 is located on the right side of the first transflective optical mirror 56, the spectrometer 55 is located on the right side of the third transflective optical mirror 58, and the light source 52 is located above the third transflective optical mirror 58.

[0055] The laser generator 51 is the emission source in the Raman detection system. In this structure, a semiconductor laser or an all-solid-state laser can be selected, and its excitation wavelength is selected according to the sample to be measured, such as 532nm, 375nm or 793nm and other different wave number bands to adapt to different application scenarios.

[0056] The light source 52 is an LED lamp, which is mainly used to provide light source illumination and assist imaging, and a light source in the visible light band is selected.

[0057] The objective lens 53 is mainly used for optical imaging and focusing and collimation of Raman light. Objective lenses 53 of different magnifications, such as 4X, 10X, 20X, 50X and 100X, can be selected to adapt to different application scenarios.

[0058] The second detector 54 is a CMOS detector, which is mainly used for optical imaging.

[0059] The spectrometer 55 is used to analyze the Raman signal, and the Raman signal collector is placed above the optical path to collect the Raman signal generated after the laser excites the sample.

[0060] At the same time, the Raman optical path component 5 is integrated in the housing and can move up and down in the vertical direction through displacement components such as a screw rod and a cylinder.

[0061] The laser light emitted by the laser generator 51 ( Figure 6 The Raman signal of the sample is excited by the first transflective optical mirror 56, the second transflective optical mirror 57, and the objective lens 53, and the Raman signal reflected by the sample ( Figure 6 The light emitted by the light source 52 ( Figure 6 The light reflected by the sample ( Figure 6 The signal (solid line) passes through the second transflective optical mirror 57 and the third transflective optical mirror 58 to the second detector 54.

[0062] The working principle is: the light source 52 generates visible light, passes through the optical coupling lens group and the objective lens 53, reaches the sample surface through the dotted arrow line, and its optical signal returns to the second detector 54 through the solid arrow to achieve optical imaging, and is focused after being adjusted up and down by the displacement component. Then, the laser generator 51 passes through the thick solid line through the objective lens 53 to reach the sample, excites the Raman signal of the sample, and then returns to the spectrometer 55 through the dotted arrow to collect and analyze the Raman signal.

[0063] The entire Raman optical path is placed on a vertical plane of the Z axis perpendicular to the horizontal plane where the X-ray diffraction optical path is located, and intersects with the sample point from top to bottom. Among them, the laser generator 51, the optical coupling lens group, the light source 52, the objective lens 53 and the second detector are all on this vertical plane and can be moved up and down.

[0064] In this embodiment, the sample holder 2, the X-ray assembly 3, the first detector 4, and the Raman optical path assembly 5 are integrated on a rotating platform 1, and the X-ray diffraction pattern and the Raman spectrum from the same sample or sample area can be measured simultaneously or sequentially. Therefore, the optical path of the present invention is composed of an X-ray diffraction optical path and a Raman optical path. In order to match the simultaneity of the two detection modes in the entire system, the system is separately designed with a Raman optical path. Compared with the existing commercial Raman optical path, the Raman optical path structure design in this embodiment is simple and efficient.

[0065] This embodiment is based on laboratory X-ray diffraction, scattering and other technical means, which can achieve the second-level time resolution capability of general samples in conventional laboratories, and at the same time has sufficient physical space to adapt to a variety of in-situ reaction test devices under different environmental conditions. At the same time, matched with the laser Raman combined system, it can realize the synchronous testing of various research target systems under real working conditions. Realizing the comprehensive structural evolution information of the target research system under real working conditions, such as material structure phase change, micromolecular vibration, etc., provides great help for further understanding of scientific problems in the reaction process.

[0066] Embodiment 2:

[0067] The present embodiment discloses a detection method of a Raman diffraction combined in-situ characterization system, which adopts the Raman diffraction combined in-situ characterization system in the above-mentioned embodiment 1, and includes the following steps: placing a sample on a sample holder 2, and adjusting the sample to the intersection of the XRD and Raman optical paths; using a first movable component 6 and a second movable component 7 to form a horizontal X-ray diffraction optical path with the sample holder by an X-ray component 3 and a first detector 4; moving the Raman optical path component 5 up and down, so that the Raman optical path component 5 can effectively focus on the surface of the sample to be tested, forming a vertical Raman optical path with the sample holder, and the Raman optical path and the X-ray diffraction optical path are vertically crossed on the sample; turning on the X-ray component 3, the first detector 4, and the Raman optical path component 5, and acquiring an XRD signal and a Raman signal at the same position of the sample.

[0068] In this embodiment, the X-ray assembly 3 has two working modes, including a transmission mode and a reflection mode. In the transmission mode, Figure 3 As shown, after the X-ray machine 31 moves to a suitable distance from the sample holder 2 through the first movable component 6, the X-ray is emitted by the X-ray machine 31, and reaches the first detector 4 after passing through the sample. In order to further expand the resolution and detection range of XRD, it can be achieved through the radial movement of the second movable component 7 under the first detector 4 and the circumferential rotation of the rotating platform 1; in the reflection mode, the X-ray machine 31 and the first detector 4 are first moved to a distance equal to the sample holder 2 through the first movable component 6 and the second movable component 7, and then the X-ray machine 31 and the first detector 4 are synchronously rotated by the rotating platform 1 to realize the angle measurement and signal acquisition of XRD.

[0069] The X-ray light source 52 and the target material are selected as needed. The shapes of the light source 52 include linear light sources and point light sources. The linear light source is mainly designed for the X-ray machine 31 and the first detector 4 to rotate synchronously (reflection type); the point light source is mainly designed for the X-ray machine 31 and the first detector 4 to move linearly (transmission type). The light source target material can be replaced and selected according to the different X-ray absorption capabilities of the sample to be tested, including three types: Cu target, Mo target and Ag target. The Cu target is for low-energy samples, the Mo target is for medium-energy samples, and the Ag target is for high-energy samples. Taking ordinary dynamic in-situ experiments as an example, a medium-energy Mo target (E~17keV) can be selected, which can not only meet the sample penetration requirements of various in-situ test devices, but also achieve non-destructive testing requirements in various in-situ test environments.

[0070] The first detector 4 is a signal collector for collecting X-ray scattering and diffraction signals, and can adopt different types of detectors such as zero-dimensional (0D), one-dimensional (1D) or two-dimensional (2D). Among them, the 0D detector is mainly used for reflective optical path use, and the 1D and 2D detectors are compatible with reflective and transmissive optical path structures.

[0071] This embodiment can realize more ultrafast reaction in-situ observation and multi-field multi-modal in-situ test conditions through the in-situ Raman / X-ray diffraction combined characterization system, and can also realize online monitoring and recording of material structure change information in the reaction process of new energy battery system, electrochemical reaction system and other multi-phase reaction system on a time scale of seconds. Through the combination of multi-field and multi-modal instruments, the ability to reveal the material structure and reaction process in multi-phase reactions in a wider range of time and space and other multi-scale aspects is achieved. Such as X-ray absorption spectrum, X-ray small angle scattering, etc., to obtain the structural information of materials under different high temperature environments.

[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A detection method using Raman diffraction combined with an in-situ characterization system, characterized in that: A Raman diffraction combined in-situ characterization system is used for detection. The Raman diffraction combined in-situ characterization system includes a rotating platform, a sample holder, an X-ray assembly, a first detector, and a Raman optical path assembly. The sample holder is connected to a fixed plate at the center of the rotating platform. The X-ray assembly and the first detector are connected to the rotating plate of the rotating platform and form an X-ray diffraction optical path with the sample holder. The Raman optical path assembly can be adjusted in a direction perpendicular to the X-ray diffraction optical path and is located above the sample holder. The Raman optical path assembly and the sample holder form a Raman optical path, and the X-ray diffraction optical path and the Raman optical path intersect at the sample holder. The sample holder includes a frame body, a first window, a second window, and a third window. The bottom of the frame body is fixedly connected to the rotating platform. The top of the frame body is provided with a horizontal channel and a vertical channel vertically connected to the horizontal channel. The two ends of the horizontal channel are respectively connected to the second window and the third window, and the top of the vertical channel is connected to the first window. The method comprises the following steps: placing a sample on a sample holder, adjusting a rotating plate of a rotating platform so that an X-ray assembly, a first detector and the sample holder form a horizontal X-ray diffraction optical path, and a Raman optical path assembly and the sample holder form a vertical Raman optical path, so that the Raman optical path and the X-ray diffraction optical path are vertically intersected on the sample; turning on the X-ray assembly, the first detector and the Raman optical path assembly, and acquiring an XRD signal and a Raman signal at the same position of the sample; The X-ray assembly has two working modes, including a transmission mode and a reflection mode; in the transmission mode, the X-ray assembly moves to a suitable distance from the sample holder through the first moving assembly, and after the X-ray is emitted by the X-ray assembly through the sample, the signal is collected by the first detector, and the position and angle of the first detector and the sample holder are adjusted to detect the signal at different distances and angles; in the reflection mode, the X-ray assembly and the first detector are moved to a distance equal to the sample holder through the first moving assembly and the second moving assembly, and the X-ray assembly and the first detector are synchronously rotated by the rotating plate of the rotating platform to realize signal collection at different angles; The first window is made of laser-transmitting material, and the second window and the third window are made of X-ray-transmitting material; the size of the first window and the second window is greater than or equal to 1 mm, the size of the third window is 1-6 mm, and the opening angle of the third window is greater than 60 degrees; The Raman optical path assembly includes a laser generator, an optical coupling lens group, a light source, an objective lens, a second detector, and a spectrometer; the light source generates visible light that sequentially passes through the optical coupling lens group and the objective lens to reach the sample surface, and then is reflected to the second detector; the laser generator generates laser light that passes through the objective lens to reach the sample surface, excites the Raman signal of the sample, and then returns to the spectrometer; The optical coupling mirror group consists of three reflective optical mirrors. The laser generator is arranged in a vertical direction to the objective lens. The first reflective optical mirror is located between the laser generator and the objective lens. The second reflective optical mirror is located directly below the first reflective optical mirror. The third reflective optical mirror is located on one side of the second reflective optical mirror. The second detector is located on one side of the first reflective optical mirror. The spectrometer is located on the other side of the third reflective optical mirror. The laser emitted by the laser generator passes through the first reflective optical mirror, the second reflective optical mirror and the objective lens to the sample to excite the Raman signal of the sample. The Raman signal reflected back by the sample passes through the second reflective optical mirror and the third reflective optical mirror to the spectrometer. The light emitted by the light source passes along the third reflective optical mirror, the second reflective optical mirror and the objective lens to the sample. The light signal reflected back by the sample passes through the second reflective optical mirror and the third reflective optical mirror to the second detector.

2. The detection method of the Raman diffraction combined with in-situ characterization system according to claim 1, characterized in that: It also includes a first movable component that can enable the X-ray component to move horizontally along the direction of the X-ray diffraction light path. The X-ray component includes an X-ray machine and an X-optical mirror. The bottom of the X-ray machine is connected to the top of the first movable component, the X-optical mirror is connected to the transmitting end of the X-ray machine, and the bottom of the first movable component is connected to the rotating plate of the rotating platform.

3. The detection method of the Raman diffraction combined with in-situ characterization system according to claim 1, characterized in that: It also includes a second movable component that can enable the first detector to move horizontally along the direction of the X-ray diffraction light path, the bottom of the first detector is connected to the top of the second movable component, and the bottom of the second movable component is connected to the rotating plate of the rotating platform.

4. The detection method of the Raman diffraction combined with in-situ characterization system according to claim 1, characterized in that: The light source of the X-ray component includes a linear light source and a point light source, the linear light source is used in the reflection mode, and the point light source is used in the transmission mode; the first detector is one of a zero-dimensional detector, a one-dimensional detector, and a two-dimensional detector, the zero-dimensional detector is used in the reflection mode, and the one-dimensional detector and the two-dimensional detector are compatible with the reflection mode and the transmission mode.

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