Sample stage for in-situ electrochemical X-ray diffraction analysis
阅读说明：本技术 一种用于原位电化学x射线衍射分析的样品台 (Sample stage for in-situ electrochemical X-ray diffraction analysis ) 是由 邹健莉 王军 曹鲁杰 于 2019-04-14 设计创作，主要内容包括：本发明专利公布了一种用于原位电化学X射线衍射分析的样品台,属于材料测试及研究领域,本装置可以对金属离子电池电极材料在二电极及三电极电化学充放电过程中进行原位X射线衍射分析,对材料的晶体结构,化学变化,所受应力进行跟踪分析,适用于目前常用的X射线衍射分析仪器,通过正极固定片和半圆形视窗的设计来实现任意角度的X射线衍射分析,本装置有利于最大限度的收集光学信号,为研究电极材料的性能提供信息,具有安装拆卸方便,适于在长期循环过程中的原位观测等优点。(The invention discloses a sample stage for in-situ electrochemical X-ray diffraction analysis, which belongs to the field of material testing and research, can perform in-situ X-ray diffraction analysis on a metal ion battery electrode material in the two-electrode and three-electrode electrochemical charging and discharging processes, performs tracking analysis on the crystal structure, chemical change and stress of the material, is suitable for the X-ray diffraction analysis instrument commonly used at present, and realizes the X-ray diffraction analysis at any angle through the design of an anode fixing piece and a semicircular window.)
1. A sample stage for in situ electrochemical X-ray diffraction analysis, comprising: the sample table main body (01) is matched with a sample rod of a commercial X-ray diffractometer, a main external structure of the sample table is formed by a semicircular window (02), an anode connecting port (03), a cathode connecting port (04) and a reference electrode connecting port (05), X-rays penetrate through the semicircular window (02) to enter materials to be tested below two small semicircular anode fixing pieces (06) and then are diffracted out of the semicircular window (02), low-angle X-rays can be blocked by an X-ray baffle plate (08) to improve the sensitivity of a detector, the anode fixing piece (06) and the X-ray baffle plate (08) are simultaneously fixed by an anode piece fixing screw (07), an electrode material placing platform with adjustable height is arranged in the sample table main body (01) to place a cathode and a reference electrode, and all parts of the sample table are sealed by a sealing ring or a sealing gasket, the semicircular window (02) is provided with a closed space, so that the electrochemical reaction can be carried out in a specific atmosphere environment.
2. The sample stage of claim 1, wherein: the negative pole post (9), division board (10), reference electrode post (11) three electrode material place the platform as an organic whole are contained in foretell sample platform main part (01), negative pole material and reference electrode can be placed respectively on negative pole post (9) and reference electrode post (11), place diaphragm and anodal material on negative pole material and the reference electrode, electrode material place the platform highly can adjust through the rotation of negative pole post fixation nut (13), the surface height of the electrode material studied flushes with sample platform main part (01) outer edge, can carry out the X-ray diffraction experiment that is greater than 0 degree and is less than 45 degrees angles.
3. The sample stage of claim 1, wherein: the positive electrode fixing piece (06) is composed of two small semi-circles, is placed in parallel with a gap in the middle, the distance of the gap is determined by the size of the positive electrode slice, and at least allows X-rays to pass through, and the structure can allow X-rays with any angle to enter to study the electrode material.
4. The sample stage of claim 1, wherein: the X-ray baffle plate (08) can connect two positive fixing pieces (06) together, the lower end of the X-ray baffle plate is in a knife edge shape, the height of the X-ray baffle plate can be infinitely close to a tested sample, and simultaneously diffracted X-rays can be allowed to pass through and can be blocked from X-rays which may directly hit a detector.
5. A sample stage for in situ electrochemical X-ray diffraction analysis according to claims 1 and 4, wherein: the size and shape of the external outline of the sample stage main body (01) are adjusted according to the X-ray powder diffractometer used, so that the sample stage main body is suitable for instruments of different models.
6. The sample stage of claim 1, wherein: the negative pole column fixing nut (13) adopts an internal thread design, is used for fixing the negative pole connecting port (04) and the negative pole column (09) by screwing threads, and simultaneously exerts pressure on the positive pole, the negative pole and the diaphragm assembled in the sample stage to play a role in compressing the positive pole, the negative pole and the diaphragm.
7. The sample stage of claim 1, wherein: the positive electrode connecting port (03), the negative electrode connecting port (04) and the reference electrode connecting port (05) are respectively provided with a groove which is specially designed, and the groove can be directly connected with the crocodile clip to prevent the crocodile clip from falling off.
8. The sample stage of claim 1, wherein: the contact part of the negative pole connecting port (04) and the negative pole column (09) is provided with a semicircular bulge design for reducing friction, and when the negative pole column fixing nut (13) is screwed, the negative pole column (09) does not rotate along with the negative pole connecting port (04).
Technical Field
The invention relates to the field of experimental equipment capable of carrying out in-situ X-ray diffraction analysis on a material under an electrochemical condition, in particular to experimental equipment for carrying out in-situ X-ray diffraction analysis on a metal ion battery electrode material under a charging and discharging condition.
Background
In order to improve the performance and service life of the battery, researchers need to perform detailed analysis and research on the changes of the electrode material in the charging and discharging processes, and through X-ray diffraction analysis, the information such as the crystal form change of the electrode material, the generation of new substances, the particle size change of the material, the stress change involved in the charging and discharging processes and the like can be obtained, so that the method is an effective and practical research means. At present, for the X-ray diffraction analysis of an electrode material, an ex-situ method is mainly adopted, namely, a battery material is charged and discharged to a certain degree, then the charging and discharging control is cut off, after the battery is opened, the electrode material is taken out, and the X-ray diffraction analysis is carried out on the electrode material directly or after cleaning and drying. The device that can carry out the normal position experiment can improve above-mentioned non-normal position test often can not accurately reflect the problem of electrode material actual conditions, though the device that can be used for carrying out the normal position experiment has aroused extensive concern, but still there are some inadequacies, chinese utility model patent that the grant official publication is CN 207541001U discloses "a lithium air battery normal position X ray diffraction testing arrangement", the utility model relates to a device is because gas feed and export are located the testing arrangement both sides, the integrated device is not applicable to and puts in the X ray diffractometer of present comparatively commonly used, and because positive grade mainboard and negative pole mainboard do not leave the interface of external electrochemistry workstation, bring a great deal of difficulty for the test of reality. The invention patent with the grant publication number of CN 102435625B discloses an X-ray diffraction in-situ test method and a sample holder, wherein a part of the device is composed of a polymer film, the sealing mode of the device is used for preventing the device from being reused, only two-electrode tests can be carried out, and the device is greatly influenced by the environment during measurement. In conclusion, the device which can accurately regulate and control the electrochemical reaction by the three-electrode method and perform the in-situ electrochemical X-ray diffraction analysis on the basis is still absent. In order to make up for the defects of the existing testing method and enable the in-situ X-ray diffraction analysis means to become a favorable tool for researching electrochemical reaction and new energy batteries, the patent provides a sample table device capable of carrying out two-electrode and three-electrode electrochemical tests, and the device can be used for carrying out in-situ X-ray diffraction experiments under electrochemical conditions (the incident angle is between 0 and 45 degrees). The design of the sample table has universality, the appearance of the sample table can be conveniently changed so as to be suitable for different X-ray diffraction instruments, and meanwhile, the sample table is simple and convenient to assemble, good in repeated measurement stability and capable of being repeatedly used for a long time.
Disclosure of Invention
As described above, aiming at the problem that the current in-situ electrochemical X-ray diffraction analysis lacks a proper sample stage, the present invention provides a sample stage for in-situ electrochemical X-ray diffraction analysis, which can perform an in-situ X-ray diffraction analysis experiment in a two-electrode or three-electrode electrochemical reaction without modifying a diffractometer, wherein the incident angle can be any angle interval between 0 and 45 degrees, and in order to achieve the above purpose, the present invention adopts the following technical scheme: the sample table can be directly placed in a diffractometer by matching the design of parameters such as the size, the thickness and the like of the appearance of the sample table main body (01) with a sample rod of a commercial X-ray diffractometer; the main external structure of the sample table is formed by a sample table main body (01), a semicircular window (02), an anode connecting port (03), a cathode connecting port (04) and a reference electrode connecting port (05), and is sealed by an O-shaped sealing ring and a sealing gasket, X-rays penetrate through the semicircular window (02) to enter a material to be tested below two small semicircular anode fixing pieces (06), then the X-rays are diffracted out of the semicircular window (02) and received by a detector of a diffractometer, and the low-angle X-rays can be blocked by an X-ray baffle plate (08) to improve the sensitivity of the detector; the semicircular window (02) is made of glass or PET, and the two materials have high X-ray transmittance and are stable to common organic solvents; the positive plate fixing screw (07) fixes the positive fixing plate (06) and the X-ray baffle plate (08) at the same time, the positive plate fixing screw (07), the positive fixing plate (06) and the X-ray baffle plate (08) are made of stainless steel materials, and the X-ray baffle plate (08) simultaneously plays a role in connecting the two positive fixing plates; an electrode material placing platform with adjustable height is arranged in the sample table main body (01) to place a negative electrode and a reference electrode, a semicircular window (02) is internally provided with a closed space, so that electrochemical reaction can be carried out in a specific atmosphere environment, and all parts of the sample table are sealed by a sealing ring or a sealing gasket.
The negative pole post (9) is contained in the sample platform main body (01), the partition plate (10) and the electrode material placing platform integrated with the reference electrode post (11), the negative pole material and the reference electrode can be placed on the negative pole post (9) and the reference electrode post (11) respectively, the diaphragm and the positive pole material are placed on the negative pole material and the reference electrode in sequence, the height of the electrode material placing platform can be adjusted through the rotation of the negative pole post fixing nut (13), the outer surface height of the electrode material to be researched is flush with the outer edge of the sample platform main body (01), and the X-ray diffraction experiment with the angle larger than 0 degree and smaller than 45 degrees can be carried out.
The positive electrode fixing piece (06) is composed of two small semi-circles, is placed in parallel, has a gap in the middle, and the distance of the gap is determined by the size of the positive electrode piece.
The X-ray baffle plate (08) can connect two positive fixing pieces (06) together, the lower end of the X-ray baffle plate is in a knife edge shape, the height of the X-ray baffle plate can be infinitely close to a sample to be detected, diffracted X-rays can be allowed to pass through the X-ray baffle plate, and the X-rays which may directly hit a detector can be blocked.
The sample table main body (01) is prepared from engineering plastics PEEK or PPS; the size and shape of the external profile are adjusted according to the X-ray powder diffractometer used so as to be suitable for different models of instruments.
The negative pole column fixing nut (13) adopts an internal thread design, is used for fixing the negative pole connecting port (04) and the negative pole column (09) by screwing threads, and simultaneously exerts pressure on the positive pole, the negative pole and the diaphragm assembled in the sample stage to play a role in compressing the positive pole, the negative pole and the diaphragm.
The positive electrode connecting port (03), the negative electrode connecting port (04) and the reference electrode connecting port (05) are respectively provided with a groove which is specially designed, and the groove can be directly connected with the crocodile clip to prevent the crocodile clip from falling off.
The contact part of the negative pole connecting port (04) and the negative pole column (09) is provided with a semicircular bulge design for reducing friction, and when the negative pole column fixing nut (13) is screwed, the negative pole column (09) does not rotate along with the negative pole connecting port (04).
The invention has the beneficial effects that the sample stage for X-ray diffraction test is provided, the sample stage can be used for carrying out two-electrode or three-electrode electrochemical regulation and control test on a material to be researched in a closed space and simultaneously collecting X-ray diffraction signals, the electrode material is arranged at the position which is parallel to the outer edge of the sample stage, the diffractometer detector can be allowed to collect the signals with the incident angle of 0-45 degrees, and the sample stage is simple to assemble and maintain and can be repeatedly used.
Drawings
The invention is further described with reference to the following figures and examples.
FIG. 1 is a front view of the overall appearance of a sample stage.
FIG. 2 is a front view of the main body of the sample stage.
Fig. 3 is a schematic perspective view (top view) of the sample stage body.
Fig. 4 is a perspective view (bottom view) of the main body of the sample stage.
FIG. 5 is a front view of the internal structure of the sample stage.
FIG. 6 is a perspective view of the internal structure of the sample stage.
FIG. 7 is a schematic top view of the internal structure of the sample stage.
FIG. 8 is a schematic perspective view of the internal reference electrode and negative electrode structure of the sample stage.
FIG. 9 is a front view of the structure of the reference electrode and the negative electrode inside the sample stage.
FIG. 10 is a perspective view of an X-ray baffle.
FIG. 11 is a perspective view of a semicircular window and a window key.
In the figure, 01, a sample table main body, 02, a semicircular window, 03, a positive electrode connecting port, 04, a negative electrode connecting port, 05, a reference electrode connecting port, 06, a positive electrode fixing piece, 07, a positive electrode piece fixing screw, 08. X-ray baffle plates, 09, a negative electrode column, 10, a separation plate, 11, a reference electrode column, 12, a reference electrode connecting column, 13, a negative electrode column fixing nut, 14, a sealing ring groove, 15, a window spoon, 16, a negative electrode column sealing ring groove and 17 are test material placing spaces.
Detailed Description
[ example 1 ]
As shown in fig. 1, the external main body of the sample stage according to the present invention is composed of a main body 01 of the sample stage and a semicircular window 02, wherein a positive electrode connection port 03, a negative electrode connection port 04 and a reference electrode connection port 05 are provided below the main body 01 (fig. 2, 3 and 4) of the sample stage for connecting with an additionally equipped alligator clip, and the alligator clip is connected with an external electrochemical workstation for precisely controlling current and voltage. The middle platform of the sample stage main body 01 (figure 2) is provided with threads (not shown in the figure) which are matched with the threads in the semicircular window 02, and the semicircular window 02 is sealed by the sealing ring sample stage main body 01 arranged in the sealing ring groove 14. The semicircular window 02 is made of transparent materials such as glass or PEI (polyetherimide) and the like so as to facilitate the entrance and exit of X-rays.
As shown in fig. 5 and 6, which are schematic views of the inside of the sample stage, the positive electrode fixing pieces 06 are fixed to the sample stage main body 01 by positive electrode
When the electrode material storage platform is used, the electrode material storage platform consisting of the negative pole column 09, the
- 上一篇：一种医用注射器针头装配设备
- 下一篇：一种适用于手持式X荧光光谱仪的样品成像系统