CN112485310B - Electrolytic cell device suitable for in-situ X-ray diffraction test - Google Patents
Electrolytic cell device suitable for in-situ X-ray diffraction test Download PDFInfo
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- CN112485310B CN112485310B CN202011132728.1A CN202011132728A CN112485310B CN 112485310 B CN112485310 B CN 112485310B CN 202011132728 A CN202011132728 A CN 202011132728A CN 112485310 B CN112485310 B CN 112485310B
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Abstract
The invention discloses an electrolytic cell device suitable for in-situ X-ray diffraction test.A reaction cell is arranged in a double-hole electrode holder; the reaction tank is divided into a test area and a working area; the test window film covers the test window; a working electrode support and a working platform for supporting and fixing a working electrode are arranged in the reaction tank; the leading-out end of the working electrode is provided with a clamping piece connected with a lead; the working electrode cover is buckled on the working area of the double-hole electrode seat; the double-hole electrode base is provided with a calibration platform, the upper surface of which is flush with the upper surfaces of the two side walls of the working area; the double-hole electrode holder is provided with two electrode through holes communicated with the reaction tank; the screw cap is screwed in the electrode through hole to fix the reference electrode or the counter electrode in the double-hole electrode holder; the defect of weak X-ray signals is avoided, the accuracy of the measuring result is high, the number of components is small, the structure is compact, the size is small, the assembly is convenient and fast, the cost is low, the universality is good, the device can be repeatedly used, and the dynamic change of the catalytic material under different electrochemical conditions can be effectively represented in real time.
Description
Technical Field
The invention relates to the field of X-ray diffraction (XRD) testing devices, in particular to an electrolytic cell reaction chamber suitable for in-situ XRD representation and a testing method thereof.
Background
In the electrochemical reaction, along with the catalytic reaction, the electrode material is often changed in structure, and the change is directly related to the activity and catalytic efficiency of the catalyst; however, the method is limited by the lack of the current material characterization technology and the lack of systematic understanding of the catalytic reaction mechanism, so that the research on aspects like Li battery, water decomposition, nitrogen fixation and the like cannot realize precise design and regulation of the required catalytic material; therefore, how to know the change of the catalyst components and the structure and how to observe the structure-activity relationship between the change and the catalytic performance of the catalyst components and the structure-activity relationship can help to promote the understanding of researchers on the catalytic reaction kinetics and provide theoretical knowledge for aspects of related research and development technologies.
X-ray diffraction (XRD) is an important characterization means for analyzing the microstructure and chemical composition of a material, and the XRD is used for analyzing the diffraction pattern of the material, so that information such as the components of the material, the structure or the form of atoms or molecules in the material and the like can be easily obtained; especially, currently, combining various characterization means with in situ techniques will help to dynamically study the changes in physical and chemical properties of materials under real-time reaction conditions; for example, an in-situ XRD electrolytic cell generated by combining X-ray diffraction with in-situ and electrochemical testing techniques is a very important analytical means in the current energy storage field, which can monitor the composition and structural changes of the material under in-situ electrochemical conditions in real time.
Although the combination of the XRD characterization means and the electrochemical testing technique can effectively resolve the reaction process of the catalytic reaction, XRD has a considerable difficulty in collecting the X-ray diffraction signal of the electrode material in the aqueous electrolyte solution. Because the penetration depth of laboratory XRD in a solid is only micrometer level, a working electrode is tested in an electrolyte, a sample immersed in an aqueous electrolyte solution is irradiated by XRD, X rays are absorbed by the aqueous electrolyte solution to be attenuated, the generated diffracted X ray signals are correspondingly attenuated and even lost, the dynamic change process of a catalytic material structure in the aqueous electrolyte solution is difficult to effectively test, the accuracy of a measurement result is low, and the characterization failure is even caused.
Therefore, there is still a need for improvement and development of the prior art.
Disclosure of Invention
In order to solve the technical problems, the invention provides the electrolytic cell reaction chamber suitable for in-situ X-ray diffraction tests, and the electrolytic cell reaction chamber has the advantages of high accuracy of measurement results, low cost and good universality.
Meanwhile, the invention also provides a water system electrolyte testing method suitable for in-situ XRD characterization, which can effectively test the dynamic change process of the catalytic material structure in the water system electrolyte, and the testing process is simple and rapid.
The technical scheme of the invention is as follows: an electrolytic cell device suitable for in-situ X-ray diffraction tests comprises a double-hole electrode holder, a working electrode cover, a test window membrane, a membrane clamping plate, a reference electrode, a counter electrode and a threaded cap; wherein the content of the first and second substances,
the middle part of the double-hole electrode seat is provided with a reaction tank with the width exceeding the length of the X-ray slit; the reaction tank is divided into a test area and a working area, and the width of the test area exceeds the width of the X-ray slit;
the heights of the two side walls of the test area are lower than those of the two side walls of the working area, and the height difference can accommodate the thickness of a layer of test window film; a test window is arranged between two side walls of the test area, and is covered on the test window; the two membrane clamping plates are respectively positioned on two outer side walls of the double-hole electrode seat at the test window;
working electrode pillars with the same height as the top surfaces of the two side walls of the testing area extend upwards from the bottom surface of the reaction tank on the inner side walls far away from the working area in the testing area; a workbench with the same height as the top surface of the working electrode strut extends upwards from the bottom surface of the reaction tank on the inner side wall far away from the test area in the working area;
the working electrode cover is buckled on the working area of the double-hole electrode seat, the working electrode cover is provided with a liquid injection hole, and the working electrode cover faces one side of the testing area and extends downwards to form a blank holder capable of pressing a testing window film;
the leading-out end of the working electrode is provided with a clamping piece connected with a lead, and the clamping piece is positioned between the upper surface of the working electrode and the lower surface of the working electrode cover;
a calibration table is arranged on the upper part of the end face of the double-hole electrode seat close to the test area, and the upper surface of the calibration table is flush with the upper surfaces of the two side walls of the working area;
two electrode through holes communicated with the reaction tank are transversely arranged at intervals at one end, far away from the calibration table, of the double-hole electrode holder, an internal thread hole is further formed in the outer side end of each electrode through hole and used for screwing in a threaded cap to fix the reference electrode or the counter electrode in the double-hole electrode holder, and an electrode through hole matched with the reference electrode or the counter electrode and penetrating through the threaded cap is formed in the end face of the threaded cap along the axial lead of the threaded cap.
The electrolytic cell device suitable for the in-situ X-ray diffraction test is characterized in that: a baffle is arranged between the calibration table and the reaction tank, the height of the baffle is higher than the top surface of the calibration table, and the two end surfaces of the baffle exceed the width of the double-hole electrode holder.
The electrolytic cell device suitable for the in-situ X-ray diffraction test is characterized in that: the bottom of the two sides of the double-hole electrode seat at the test window is respectively extended downwards to form a lug, a threaded through hole is transversely formed in the lug along the width direction of the double-hole electrode seat, and a corresponding clamp plate screw through hole is formed in the corresponding position on the membrane clamp plate.
The electrolytic cell device suitable for the in-situ X-ray diffraction test is characterized in that: the test window film is an organic Kapton film.
The electrolytic cell device suitable for the in-situ X-ray diffraction test is characterized in that: o-shaped rubber rings are sleeved on the outer walls of the reference electrode and the counter electrode and used for preventing leakage of water system electrolyte.
The electrolytic cell device suitable for the in-situ X-ray diffraction test is characterized in that: the working electrode is carbon paper, graphite paper, a conductive glass sheet, a glassy carbon electrode sheet or a conductive metal foil coated with a catalyst material.
The electrolytic cell device suitable for the in-situ X-ray diffraction test is characterized in that: the double-hole electrode holder is made of a photosensitive resin 9400 material, nylon, PTFE, PEEK, PMMA or PLA material.
An aqueous electrolyte testing method suitable for in-situ X-ray diffraction characterization, using an electrolytic cell device suitable for in-situ X-ray diffraction testing as described in any one of the above, and comprising the following assembly steps before performing in-situ XRD testing on a working electrode:
A. preparing a catalyst material into slurry, coating the slurry on a working electrode, and drying;
B. hydraulic tapes are uniformly wound on the outer walls of the reference electrode and the counter electrode, or O-shaped rubber rings are sleeved on the outer walls of the reference electrode and the counter electrode, and are respectively arranged in the electrode through holes of the double-hole electrode holder, and the reference electrode and the counter electrode are screwed down after being sleeved with threaded caps;
C. placing a working electrode on a working electrode support and a worktable in a reaction tank, and making one end loaded with a catalyst face the working electrode support;
D. covering a test window film above a test area of the reaction tank, and screwing two clamping plate screws to enable film clamping plates on two sides of the double-hole electrode holder to respectively clamp the test window film and ensure that the surface of the test window film is smooth and has no wrinkles;
E. placing the clamping piece at the leading-out end of the working electrode, covering the working electrode cover, and screwing the two cover plate screws to press the edge pressing of the working electrode cover against the testing window film; the working electrode and the external electrochemical workstation electrode are mutually connected by adopting a flexible electrode;
F. filling aqueous electrolyte into the reaction tank through a liquid filling hole on the working electrode cover to ensure that the aqueous electrolyte completely submerges the working electrode;
G. and connecting the calibration table of the double-hole electrode holder to a test table of the X-ray diffractometer, and respectively connecting the working electrode, the reference electrode and the counter electrode into corresponding circuits of the X-ray diffractometer through respective binding posts.
The electrolytic cell reaction chamber suitable for the in-situ X-ray diffraction test and the water system electrolyte test method suitable for the in-situ XRD representation, provided by the invention, have the advantages that the defect of weak X-ray signals is avoided, the accuracy of the measurement result is high, the number of components is small, the structure is compact, the size is small, the assembly is convenient and fast, the cost is low, the universality is good, the method can be repeatedly used, the continuous in-situ XRD test can be carried out on the same working electrode, the method is particularly suitable for the structure representation of the catalyst in the water system electrolyte, the dynamic change of the catalytic material under different electrochemical conditions can be effectively represented in real time, the components and the structural change of the material under the in-situ electrochemical conditions can be further monitored in real time, the crystal form, the structure and the component change information of the catalyst material in the electrocatalysis process are known, and the blank of the water system condition reaction chamber in the field of electrochemical instruments in China is filled.
Drawings
The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way; the shapes, the proportional sizes, and the like of the respective members in the drawings are merely schematic for aiding the understanding of the present invention, and do not specifically limit the shapes, the proportional sizes, and the like of the respective members of the present invention; those skilled in the art, having the benefit of the teachings of this invention, may choose from the various possible shapes and proportional sizes to implement the invention as a matter of case.
FIG. 1 is a perspective view of an embodiment of an electrolytic cell apparatus suitable for in situ X-ray diffraction testing in accordance with the present invention;
FIG. 2 is a top view block diagram of FIG. 1 of the present invention;
FIG. 3 is a cross-sectional view of the A-A step of FIG. 2 according to the present invention;
FIG. 4 is a perspective view of an electrode holder for use in an embodiment of an electrolytic cell apparatus suitable for in situ X-ray diffraction testing in accordance with the present invention;
the various reference numbers in the figures are summarized: the device comprises a double-hole electrode seat 100, an electrode through hole 101, an internal thread hole 103, a reaction cell 110, a test area 111, a side wall 111a (of the test area 111), a working area 112, a side wall 112a (of the working area 112), a working electrode support 113, a working table 114, a calibration table 120, a baffle 130, a lug 140, a threaded through hole 141, a working electrode cover 200, a liquid injection hole 201, a cover plate screw through hole 202, a pressing edge 203, a test window film 300, a film clamping plate 400, a clamping plate screw through hole 401, a threaded cap 500, an electrode perforation 501 and an O-shaped rubber ring 600.
Detailed Description
The embodiments and examples of the present invention will be described in detail below with reference to the accompanying drawings, and the described embodiments are only for the purpose of illustrating the present invention and are not intended to limit the embodiments of the present invention.
As shown in fig. 1 to 4, an electrolytic cell device (/ reaction chamber) suitable for in situ X-ray diffraction testing (/ characterization) according to the present invention comprises a dual-well electrode holder 100, a working electrode (not shown), a working electrode cover 200, a test window membrane 300, a membrane clamp 400, a reference electrode (not shown), a counter electrode (not shown), and a screw cap 500; wherein the content of the first and second substances,
a reaction cell 110 with the width exceeding the length of the X-ray slit is arranged downwards on the top surface of the middle part of the double-hole electrode holder 100 and is used for containing aqueous electrolyte; the reaction cell 110 is divided into a test area 111 and a working area 112 along the length direction of the double-hole electrode holder 100, and the width of the test area 111 exceeds the width of the X-ray slit;
the height of the two side walls 111a of the testing area 111 is lower than that of the two side walls 112a of the working area 112, and the height difference can accommodate the thickness of a layer of testing window film 300; a test window is arranged between two side walls 111a of the test area 111;
a test window film 300 is overlaid on the test window; the two film clamping plates 400 are respectively positioned on two outer side walls of the double-hole electrode holder 100 at the test window and are used for clamping two (front and back) surfaces of the test window film 300 from two opposite directions;
a working electrode support 113 extending upward from the bottom of the reaction cell 110 on the inner side wall of the test region 111 away from the working region 112 and having a height equal to the top surface of the two side walls 111a of the test region 111 for supporting one end of a working electrode (not shown) loaded with a catalyst;
a worktable 114 which extends upwards from the bottom of the reaction cell 110 and has the same height as the top surface of the working electrode support 113 is arranged on the inner side wall of the working area 112 far away from the test area 111 and is used for fixing the leading-out end of a working electrode (not shown);
the working electrode cover 200 is buckled on the working area 112 of the double-hole electrode holder 100, the size of the working electrode cover 200 is matched with that of the working area 112, and the working electrode cover 200 is provided with a liquid injection hole 201 for injecting aqueous electrolyte into the reaction tank 110 through the liquid injection hole 201; the working electrode cover 200 is extended downwards to form a pressing edge 203 capable of pressing the test window film 300 towards one side of the test area 111, and is used for matching with the top surfaces of the two side walls of the test area 111 to press the top surface of the test window film 300 from top to bottom;
the leading-out end of the working electrode is provided with a clamping piece (not shown) connected with a lead wire, and the clamping piece is used for leading out the working electrode to the corresponding binding post; and the clip is positioned between the upper surface of the working electrode and the lower surface of the working electrode cover 200;
the upper part of the end face of the double-hole electrode holder 100 close to the test area 111 is provided with a calibration table 120 which is used for being connected with a test table of an X-ray diffractometer; the upper surface of the calibration stage 120 is flush with the upper surfaces of the two side walls 112a of the working area 112, so that the focal plane of the X-ray overlaps with the surface of the working electrode loaded with the catalyst, thereby ensuring the reference plane of the in-situ XRD test, and the focal point of the incident X-ray falls at the center of the catalyst-loaded area;
two electrode through holes 101 communicated with the reaction tank 110 are transversely arranged at intervals at one end of the double-hole electrode holder 100, which is far away from the calibration table 120, and are used for respectively loading a reference electrode and a counter electrode, and the rear ends of the reference electrode and the counter electrode are respectively connected with a lead wire for leading the reference electrode or the counter electrode out to a corresponding binding post; the outer side end of each electrode through hole 101 is also provided with an internal threaded hole 103 for screwing a threaded cap 500 to fix the reference electrode or the counter electrode in the double-hole electrode holder 100, and simultaneously, the overflow of the aqueous electrolyte from the electrode through hole 101 is prevented in a threaded sealing manner; the end face of the screw cap 500 is provided along the axial line thereof with an electrode through hole 501 for passing a reference electrode or a counter electrode, and a lead for leading out the reference electrode or the counter electrode.
Furthermore, hydraulic tapes (such as raw material tapes) are wound on the outer walls of the reference electrode and the counter electrode, or O-shaped rubber rings 600 are sleeved on the outer walls of the reference electrode and the counter electrode, so as to prevent the leakage of the aqueous electrolyte; when the reference electrode and the counter electrode are installed and fixed in the double-hole electrode holder 100, the wound hydraulic tapes are only positioned at the electrode through hole 101 section and the electrode through hole 501 section to prevent the water system electrolyte from seeping out of the electrode through hole 101, the internal thread hole 103 and the electrode through hole 501; the fitted O-ring 600 is located at the bottom of the female screw hole 103 to prevent the aqueous electrolyte from leaking out of the female screw hole 103 and the electrode through-hole 501.
Further, a baffle 130 is disposed between the calibration stage 120 and the reaction cell 110 for blocking the aqueous electrolyte, so as to avoid the aqueous electrolyte from overflowing due to improper operation and causing contact, contamination and erosion of the sample stage device (not shown); the height of the baffle 130 is higher than the top surface of the calibration stage 120, and both end surfaces of the baffle 130 exceed the width of the dual-hole electrode holder 100.
Specifically, the bottom of the two sides of the dual-hole electrode holder 100 at the test window respectively extends downwards to form a lug 140, a threaded through hole 141 is transversely formed in the lug 140 along the width direction of the dual-hole electrode holder 100, and a corresponding clamp plate screw through hole 401 is formed in the corresponding position on the membrane clamp plate 400, so that the membrane clamp plate 400 is fastened on the outer side wall of the dual-hole electrode holder 100 by using a clamp plate screw, and the test window membrane 300 is clamped from two opposite directions (front and back).
Specifically, two threaded blind holes are formed in the upper end face of the workbench 114 in the reaction tank 110 at intervals, and two cover plate screw through holes 202 are formed in the working electrode cover 200 at intervals, so that the working electrode cover 200 is fastened to the top of the double-hole electrode holder 100 by using cover plate screws, and then the clamping clips and the leading-out ends of the working electrodes are clamped.
In the embodiment of the invention of the electrolytic cell device (/ reaction chamber) suitable for in-situ X-ray diffraction test (/ characterization), the dual-hole electrode holder 100 can be made of materials such as photosensitive resin 9400 material, PTFE, nylon, PEEK, PMMA or PLA for aqueous electrolytes with different phs, such as acidity, neutrality and alkalinity; for example, the dual-hole electrode holder 100 can be made of acid-base-resistant resin, nylon or PTFE material; for the acidic water-quality electrolyte, the photosensitive resin 9400 material is preferably adopted to manufacture the double-hole electrode holder 100; for alkaline aqueous electrolytes, the dual-hole electrode holder 100 is preferably made of nylon or PTFE.
Specifically, the working electrode support 113 and the working platform 114 in the reaction cell 110, and the calibration platform 120 and the baffle 130 on the dual-hole electrode holder 100 can be made of the same material as the dual-hole electrode holder 100, and are preferably integrally connected with the dual-hole electrode holder 100; the cross-sectional shape of the working electrode support 113 is preferably trapezoidal as illustrated, with the shorter side of the trapezoid facing the table 114, and the cross-sectional shape of the working electrode support 113 may also be semicircular, triangular, diamond-shaped, or rectangular; the table 114 is rectangular in cross-sectional shape.
Specifically, the working electrode cap 200 may also be made of the same material as the dual-hole electrode holder 100; the two cover plate screws are preferably plastic screws made of PTFE materials, but stainless steel screws can also be adopted; and the specification of the two cover plate screws is preferably M3 type screws.
Specifically, the two film clamping plates 400 can be made of PLA, PMMA, PTFE or nylon material, preferably PLA material; the two clamping plate screws are preferably plastic screws made of PTFE materials, but stainless steel screws can also be adopted; and the specification of the two cover plate screws is preferably M3 type screws.
Specifically, the two screw caps 500 may also be made of the same material as the two-hole electrode holder 100; and the inner diameter of the electrode penetration holes 501 in the two screw caps 500 is the same as the outer diameter of the reference electrode and the counter electrode, and the diameters are both 6.6 mm.
Specifically, the diameters of the two electrode through holes 101 in the double-hole electrode holder 100 are both 6.6mm, and both the two electrode through holes are made to have positive tolerance, so that the reference electrode and the counter electrode can be inserted smoothly.
Specifically, the working electrode is preferably made of (hydrophilic) carbon paper, graphite paper, a conductive glass sheet, a glassy carbon electrode sheet or various conductive metal foils coated with a catalyst material, and has a thickness of 0.2mm, and the size of a loading region on the working electrode, on which a catalyst is loaded, is 1 × 1cm2(ii) a The clamping piece can be made of carbon cloth and has the thickness of 300-500 mu m; the reaction tank 110 has a cavity length of 28mm, a width of 24mm, a working area 112 depth of 17mm, and a testing area 111 depth of 16.7 mm.
Specifically, the test window film 300 is made of various corrosion-resistant films which have good transmittance to X-rays and do not have chemical reactions with aqueous electrolyte solution, and the thickness is 12.5-250 μm, and the thinner the film, the better the effect; the test window film 300 is preferably an organic Kapton film; it should be noted that, in the prior art, the Kapton film belongs to a polyimide film, has excellent high and low temperature resistance, electrical insulation, adhesion, radiation resistance and medium resistance, can be used for a long time in a temperature range of-269 ℃ to 280 ℃, but is generally used as an insulating material, and the high X-ray transmittance of the Kapton film is not found and utilized before the invention, and is applied to an in-situ XRD test to be used as a test window film 300.
Based on the electrolytic cell device (/ reaction chamber) suitable for in-situ X-ray diffraction test (/ characterization), the invention also provides a water system electrolyte test method suitable for in-situ XRD characterization, which comprises the following steps:
step S310, adding powdery catalyst (such as Li)3IrO4) The material is prepared into slurry and coated on hydrophilic carbon paper (i.e. a working electrode), and the size of a coating area (i.e. a load area) is 1 multiplied by 1cm2And after drying, as a working electrode;
step S320, uniformly winding hydraulic tapes on the outer walls of the reference electrode and the counter electrode, or sleeving an O-shaped rubber ring 600 on the outer walls, respectively installing the hydraulic tapes into the electrode through holes 101 of the double-hole electrode holder 100, and screwing the hydraulic tapes after sleeving the threaded caps 500 on the hydraulic tapes;
step S330, the working electrode is horizontally placed on the working electrode support 113 and the worktable 114 in the reaction cell 110, and one end loaded with the catalyst faces the working electrode support 113;
step S340, covering the test window film 300 above the test area 111 of the reaction tank 110, and screwing two clamping plate screws to enable the film clamping plates 400 at two sides of the double-hole electrode holder 100 to respectively clamp the test window film 300 and ensure that the surface of the test window film 300 is smooth and has no wrinkles;
step S350, placing the clamping piece at the leading-out end of the working electrode, covering the working electrode cover 200, and screwing down the two cover plate screws to enable the pressing edge 203 of the working electrode cover 200 to press the testing window film 300; the working electrode and the external electrochemical workstation electrode can be mutually connected by adopting a flexible electrode such as carbon cloth;
step S360, a small amount of aqueous electrolyte (for example, H with a concentration of 0.5 mol/L) is injected into the reaction cell 110 through the injection hole 201 of the working electrode cap 2002SO4Electrolyte) and causing the aqueous electrolyte to completely submerge the working electrode;
step S370, connecting the calibration platform 120 of the double-hole electrode holder 100 to a test platform of an X-ray diffractometer, and respectively connecting the working electrode, the reference electrode and the counter electrode to corresponding circuits of the X-ray diffractometer through respective binding posts;
and step S380, starting the X-ray diffractometer and the electrochemical workstation in sequence, setting relevant parameters according to test requirements, and carrying out in-situ XRD (X-ray diffraction) test on the working electrode to obtain in-situ XDR (X-ray diffraction) test data of the corresponding catalyst.
The water system electrolyte testing method suitable for in-situ XRD representation is suitable for water system electrolytes, can be used for carrying out continuous in-situ XRD testing on the same working electrode, and is simple and rapid in testing process; the used electrolytic cell device has the advantages of few components, compact structure, small volume, convenient assembly, good equipment universality and reusability; in the above steps, step S310 and step S320 are not chronologically separated.
For example, by using the above-described cell arrangement (/ reaction chamber), and by using the above-described procedure, the catalyst Li can be obtained3IrO4H at a concentration of 0.5 mol/L2SO4In situ XRD test data in electrolyte solution to H at 0.5 mol/L concentration2SO4Effectively testing catalyst Li in electrolyte3IrO4And (3) dynamic change process of the material structure.
It should be understood that the above-mentioned embodiments are merely preferred examples of the present invention, and are not intended to limit the technical solutions of the present invention, and those skilled in the art can add, subtract, replace, change or modify the above-mentioned embodiments within the spirit and principle of the present invention, and all such technical solutions should fall within the protection scope of the appended claims.
Claims (5)
1. An electrolytic cell device suitable for in-situ X-ray diffraction tests is characterized by comprising a double-hole electrode holder, carbon paper coated with a catalyst material, a working electrode cover, a test window membrane, a membrane clamping plate, a reference electrode, a counter electrode and a threaded cap; wherein the content of the first and second substances,
the middle part of the double-hole electrode seat is provided with a reaction tank with the width exceeding the length of the X-ray slit; the reaction tank is divided into a test area and a working area, and the width of the test area exceeds the width of the X-ray slit;
the bottoms of two sides of the double-hole electrode seat at the test window respectively extend downwards to form lugs, threaded through holes are transversely formed in the lugs along the width direction of the double-hole electrode seat, and corresponding clamp plate screw through holes are formed in the corresponding positions of the membrane clamp plates;
the heights of the two side walls of the test area are lower than those of the two side walls of the working area, and the height difference can accommodate the thickness of a layer of test window film;
a test window is arranged between two side walls of the test area, and is covered on the test window; the two membrane clamping plates are respectively positioned on two outer side walls of the double-hole electrode seat at the test window;
working electrode pillars with the same height as the top surfaces of the two side walls of the testing area extend upwards from the bottom surface of the reaction tank on the inner side walls far away from the working area in the testing area; a workbench with the same height as the top surface of the working electrode strut extends upwards from the bottom surface of the reaction tank on the inner side wall far away from the test area in the working area;
the working electrode cover is buckled on the working area of the double-hole electrode seat, the working electrode cover is provided with a liquid injection hole, and the working electrode cover faces one side of the testing area and extends downwards to form a blank holder capable of pressing a testing window film;
the leading-out end of the carbon paper is provided with a clamping piece connected with a lead, and the clamping piece is positioned between the upper surface of the carbon paper and the lower surface of the working electrode cover; a calibration table is arranged on the upper part of the end face of the double-hole electrode seat close to the test area, and the upper surface of the calibration table is flush with the upper surfaces of the two side walls of the working area;
a baffle is arranged between the calibration table and the reaction tank, the height of the baffle is higher than the top surface of the calibration table, and two end surfaces of the baffle exceed the width of the double-hole electrode holder;
two electrode through holes communicated with the reaction tank are transversely arranged at intervals at one end, far away from the calibration table, of the double-hole electrode holder, an internal thread hole is further formed in the outer side end of each electrode through hole and used for screwing in a threaded cap to fix the reference electrode or the counter electrode in the double-hole electrode holder, and an electrode through hole matched with the reference electrode or the counter electrode and penetrating through the threaded cap is formed in the end face of the threaded cap along the axial lead of the threaded cap.
2. The electrolyzer unit suitable for in-situ X-ray diffraction tests of claim 1 characterized in that: the test window film is an organic Kapton film.
3. The electrolyzer unit suitable for in-situ X-ray diffraction tests of claim 1 characterized in that: o-shaped rubber rings are sleeved on the outer walls of the reference electrode and the counter electrode and used for preventing leakage of water system electrolyte.
4. The electrolyzer unit suitable for in-situ X-ray diffraction tests of claim 1 characterized in that: the double-hole electrode holder is made of a photosensitive resin 9400 material, nylon, PTFE, PEEK, PMMA or PLA material.
5. An aqueous electrolyte testing method suitable for in-situ X-ray diffraction characterization, using the cell device suitable for in-situ X-ray diffraction testing of any one of claims 1 to 4, wherein the aqueous electrolyte testing method suitable for in-situ X-ray diffraction characterization comprises the following assembly steps before performing in-situ XRD testing on the working electrode:
A. preparing a catalyst material into slurry, coating the slurry on a working electrode, and drying;
B. hydraulic tapes are uniformly wound on the outer walls of the reference electrode and the counter electrode, or O-shaped rubber rings are sleeved on the outer walls of the reference electrode and the counter electrode, and are respectively arranged in the electrode through holes of the double-hole electrode holder, and the reference electrode and the counter electrode are screwed down after being sleeved with threaded caps;
C. placing a working electrode on a working electrode support and a worktable in a reaction tank, and making one end loaded with a catalyst face the working electrode support;
D. covering a test window film above a test area of the reaction tank, and screwing two clamping plate screws to enable film clamping plates on two sides of the double-hole electrode holder to respectively clamp the test window film and ensure that the surface of the test window film is smooth and has no wrinkles;
E. placing the clamping piece at the leading-out end of the working electrode, covering the working electrode cover, and screwing the two cover plate screws to press the edge pressing of the working electrode cover against the testing window film; the working electrode and the external electrochemical workstation electrode are mutually connected by adopting a flexible electrode;
F. filling aqueous electrolyte into the reaction tank through a liquid filling hole on the working electrode cover to ensure that the aqueous electrolyte completely submerges the working electrode;
G. and connecting the calibration table of the double-hole electrode holder to a test table of the X-ray diffractometer, and respectively connecting the working electrode, the reference electrode and the counter electrode into corresponding circuits of the X-ray diffractometer through respective binding posts.
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