CN106770158A - Electrochemistry in-situ high temperature Raman spectroscopy tests hot system - Google Patents

Abstract

The invention discloses an electrochemical high-temperature in-situ Raman spectrum test thermal state system, comprising: a thermal state cavity, which includes a base, a chamber main body and a sealed top cover; a temperature measurement and control component, which includes a heating component and a temperature measurement thermoelectric A pair; a sample carrying part, which includes a sample stage and a fastener, the sample stage has a second hollow corundum tube and a corundum top cover; a current collecting part, which includes a first electrode current collecting part and a second electrode current collecting part, the second The current collecting part of the first electrode adopts the probe rod to collect current, and the current collecting part of the second electrode adopts platinum wire and platinum mesh to collect current; the manual feeding part includes manual feeding rod, seal and crucible; the water cooling part consists of water cooling jacket and welding Composed of cooling water conduits on the water cooling jacket. The system can be applied to online measurement of electrochemical signals and Raman spectral information of electrochemical systems under high-temperature operating conditions, which can better meet the needs of use and is simple and easy to implement.

Description

Electrochemical high-temperature in-situ Raman spectroscopy testing hot state system

technical field

The invention relates to the technical field of high-temperature electrochemistry and spectral analysis, in particular to a thermal state system for electrochemical high-temperature in-situ Raman spectroscopy testing.

Background technique

At present, conventional electrochemical research and test methods mainly use electrical signals as excitation means to speculate on the reaction process and potential mechanism by measuring the electrical response of the electrochemical system. However, what this method obtains is the macroscopic sum of all the microscopic information of the system, resulting in the lack of intuitive information on intermediate processes and intermediate products, thus causing difficulties in the identification of reaction mechanisms.

Raman spectroscopy is an important modern molecular spectroscopy technology. Using the fingerprint characteristics of molecular Raman spectroscopy, it can intuitively identify the bonding mode between atoms in molecules. It is suitable for the characterization of groups and molecular structures, and is widely used in chemistry, Representation of matter in disciplines such as physics and biological sciences. Therefore, the development of in-situ electrochemical spectroscopy technology that combines electrochemical testing methods and Raman spectroscopy characterization methods is applied to the research of electrochemical systems, and the research of reaction mechanism is promoted to the level of in-situ molecular dynamics, and at the same time, it can be obtained online The macroscopic information reflecting the electrochemical performance can greatly promote the research of electrochemical systems.

In related technologies, electrochemical in-situ Raman spectroscopy testing devices mostly focus on the in-situ research of low-temperature solid-liquid phase electrochemical systems, such as direct liquid fuel cells, lithium batteries, and electrochemical research on metal corrosion. Some important progress has been made in the study of surface Raman spectroscopy. However, for high-temperature solid-phase electrochemical systems, including SOFC (SolidOxide Fuel Cell, solid oxide fuel cell), DCFC (direct carbon fuel cell, direct carbon fuel cell), etc. very lacking. Since the molecular Raman scattering signal is 10 ^-6 -10 ^-9 of the incident laser signal, the solid angle can be increased by reducing the working distance of the Raman optical system (the distance between the microlens and the sample) to enhance the collected However, as the working distance decreases and approaches the high temperature area where the sample is located, a large amount of thermal radiation will cause serious corrosion to the microscopic Raman lens.

Therefore, reconciling the contradiction between the working distance of optical testing and high-temperature thermal environment is a key problem for high-temperature electrochemical in-situ Raman testing devices. In addition, the test device has strict requirements on safety, air tightness, current collection and temperature measurement and temperature control. At the same time, it is hoped that it can be convenient and quick to load and unload and add samples in situ. For the above reasons, the design and processing of the electrochemical high-temperature in-situ Raman test device is relatively complicated, and it is difficult for existing similar devices at home and abroad to meet the above conditions at the same time.

Contents of the invention

The present invention aims to solve one of the technical problems in the related art at least to a certain extent.

For this reason, the object of the present invention is to propose a kind of electrochemical high-temperature in situ Raman spectroscopic testing thermal state system, this system can be applied to the electrochemical signal and Raman spectroscopic information of the electrochemical system under the high-temperature operating state of online measurement, more well meet the needs of use.

In order to achieve the above purpose, an embodiment of the present invention proposes a thermal state system for electrochemical high-temperature in-situ Raman spectroscopy testing, including: a thermal state chamber, which includes a base, a chamber body and a sealed top cover, Wherein, the top of the chamber body is open, and the bottom of the chamber body is provided with a through hole, the chamber body and the sealing top cover are sealed by flange sealing, and the sealing top The inside of the cover is spray-coated with high-temperature-resistant materials, and the middle part of the sealed top cover is recessed inwards and has a through hole to set a sapphire glass disc for laser signal access; temperature measurement and control components, the temperature measurement and control components include heating components and A temperature-measuring thermocouple, the heating component is fixed in the center of the chamber main body, and the heating component and the inner wall of the chamber are filled with a layer of porous insulation material, the heating component has a first hollow corundum tube and a heating wire, wherein , the outer wall of the first hollow corundum tube is provided with threads to fix and support the heating wire, the temperature measuring thermocouple is provided with segmented thin corundum sleeves, and two thermocouples are provided in the cavity, The temperature measuring head of the first thermocouple is kept at the same height as the sample to detect the temperature of the reaction position, and the temperature measuring head of the second thermocouple is kept in line with the middle of the heating section to monitor the highest temperature in the cavity; the sample holding part , the sample carrying part includes a sample stage and a fastener, the sample stage has a second hollow corundum tube and a corundum top cover, so as to perform fastening and sealing through the second hollow corundum tube and the corundum top cover, wherein the The sample stage protrudes from the bottom of the hot state chamber, so that the sample position is in the center of the heating part; the current collecting part, the current collecting part includes a first electrode current collecting part and a second electrode collecting part The current collecting part of the first electrode in the hot cavity adopts a probe rod to collect current, and the second electrode current collecting part adopts platinum wire and platinum mesh to collect current; the manual feeding part includes manual feeding A rod, a seal and a crucible, wherein the manual feeding rod is provided with a clamping structure to clamp the crucible filled with samples; a water-cooled part, the water-cooled part consists of a water-cooled jacket and welded on the water-cooled jacket Composition of cooling water conduits.

The electrochemical high-temperature in-situ Raman spectroscopy test thermal state system of the embodiment of the present invention can realize the functions of sealing the test battery, adding samples in situ, current collection, cathode and anode gas supply, temperature measurement and temperature control, etc. The optical glass window facing the sample position captures the Raman spectrum in situ, and through careful structural design, it realizes functions such as compact structure, convenient disassembly, and local water cooling, so it can be used for online measurement of electrochemical systems under high temperature operating conditions Electrochemical signals and Raman spectral information, and can better meet the needs of use, simple and easy to implement.

In addition, the electrochemical high-temperature in-situ Raman spectroscopy test thermal system according to the above-mentioned embodiments of the present invention may also have the following additional technical features:

Further, in one embodiment of the present invention, the heating wire is an iron-chromium-aluminum alloy heating wire, and the outer wall of the first hollow corundum tube is processed with external threads for the support of the iron-chromium-aluminum alloy heating wire and fixed.

Further, in one embodiment of the present invention, the sample stage is made of corundum, one end of the second hollow corundum tube is processed with grooves and external threads, and the top cover is processed with internal threads to fix the sample.

Further, in one embodiment of the present invention, the sample stage is designed to be detachable, and the sample stage is realized by threading the bottom of the thermal chamber through an O-shaped rubber ring, a wedge-shaped inner sleeve and a screw cap. Table sealing and fixing.

Further, in one embodiment of the present invention, when the probe rod is used for current collection, the current is collected through a rhenium wire probe fixed at the end of the probe rod, and the current is drawn out from the copper wire in the middle of the probe rod.

Further, in one embodiment of the present invention, an insulating plastic sleeve is provided at the end of the probe rod, and the position of the rhenium wire probe in the cavity can be adjusted online through the connection with the base and the three-dimensional three-coordinate translation platform.

Further, in one embodiment of the present invention, the current collecting device is sealed by welding metal bellows and quick-connect flange connections at both ends.

Further, in one embodiment of the present invention, the manual feeding part is arranged on the outer wall of the chamber main body.

Further, in an embodiment of the present invention, the manual feeding part and the hot cavity are sealed through a four-stage O-shaped rubber ring and a flange connection.

Further, in an embodiment of the present invention, the water cooling component is arranged below the chamber main body and above the sealed top cover, so as to cool down the high-temperature critical parts.

Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Description of drawings

The above and/or additional aspects and advantages of the present invention will become apparent and easy to understand from the following description of the embodiments in conjunction with the accompanying drawings, wherein:

Fig. 1 is a structural schematic diagram of an electrochemical high-temperature in-situ Raman spectroscopy testing thermal system according to an embodiment of the present invention;

Fig. 2 is a schematic structural view of a sample stage according to an embodiment of the present invention;

Fig. 3 is a structural schematic diagram of a metal probe rod base according to an embodiment of the present invention;

Fig. 4 is a structural schematic diagram of a metal probe chassis according to an embodiment of the present invention;

Fig. 5 is a schematic diagram of assembly of a probe probe rod current collecting device according to an embodiment of the present invention

6 is a schematic diagram of a Raman spectrum of a yttria-stabilized zirconia electrolyte according to an embodiment of the present invention;

Fig. 7 is a schematic diagram of the volt-ampere characteristic curve of a liquid antimony anode solid oxide fuel cell according to an embodiment of the present invention.

detailed description

Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.

Firstly, the hot-state system for electrochemical high-temperature in-situ Raman spectroscopy testing proposed according to the embodiments of the present invention will be described in detail below.

The electrochemical high-temperature in-situ Raman spectroscopy test hot state system includes: a hot state chamber, a temperature measurement and control part, a sample carrying part, a current collecting part, a manual feeding part and a water cooling part.

Wherein, the hot state chamber includes a base, a chamber main body and a sealing top cover, wherein the top of the chamber main body is set to be open, and the bottom of the chamber main body is provided with a through hole, and the chamber main body and the sealing top cover are connected through a flange The sealing is completed, and the inner side of the sealing top cover is sprayed with high-temperature-resistant materials, and the middle part of the sealing top cover is recessed inward and has a through hole to set a sapphire glass disc for laser signal access. The temperature measurement and control component includes a heating component and a temperature measuring thermocouple. The heating component is fixed in the center of the chamber body, and the heating component and the inner wall of the chamber are filled with a porous insulation material layer. The heating component has a first hollow corundum tube and a heating wire, wherein, The outer wall of the first hollow corundum tube is provided with threads to fix and support the heating wire. A section of thin corundum sleeve is arranged outside the temperature measuring thermocouple, and two thermocouples are arranged in the cavity. The temperature measuring of the first thermocouple The head is kept at the same height as the sample to detect the temperature of the reaction position, and the temperature measuring head of the second thermocouple is kept in line with the middle of the heating section to monitor the highest temperature in the chamber. The sample carrying part includes a sample stage and a fastener, and the sample stage has a second hollow corundum tube and a corundum top cover to perform fastening and sealing through the second hollow corundum tube and the corundum top cover, wherein the sample stage is removed from the hot state cavity The bottom protrudes so that the sample position is centered on the heating element. The current collecting parts include the first electrode current collecting part and the second electrode current collecting part. The first electrode current collecting part in the hot chamber adopts a probe rod to collect current, and the second electrode current collecting part adopts platinum wire and platinum net to collect current. flow. The manual feeding part includes a manual feeding rod, a seal and a crucible, wherein the manual feeding rod is provided with a clamping structure to clamp the crucible filled with samples. The water-cooling part consists of a water-cooling jacket and a cooling water conduit welded on the water-cooling jacket. The system can be applied to online measurement of electrochemical signals and Raman spectral information of electrochemical systems under high-temperature operating conditions, which can better meet the needs of use and is simple and easy to implement.

For example, in an embodiment of the present invention, the system of the embodiment of the present invention includes a thermal body, a sealed top cover, a temperature measurement and control component, a sample carrying component, a current collecting component, a manual feeding component and a water cooling component. Among them, the interior of the hot body can be provided with porous insulation materials; the heating wire wound on the outer wall of the hollow corundum tube processed with external threads, such as the iron-chromium-aluminum alloy heating wire, can be used as a built-in heat source in the hot state and installed in the center of the hot cavity; the sample The bearing part extends through the bottom of the hot chamber and is fixed by screw connection so that the sample position is in the middle of the chamber; the electrode current collection in the hot chamber adopts a probe rod current collection device, through welding bellows and three-dimensional three-dimensional translation The platform realizes dynamic sealing; the side wall of the hot chamber is equipped with a manual feeding device, and the front end of the feeding rod is designed with a clamping structure, which realizes dynamic sealing through flange connections and four-stage O-shaped rubber rings; the top cover and the bottom of the hot chamber are sealed Water-cooling cooling devices are respectively provided for the protection of equipment and personnel safety.

Further, in one embodiment of the present invention, the heating wire is an Fe-Cr-Al alloy heating wire, and the outer wall of the first hollow corundum tube is processed with external threads for supporting and fixing the Fe-Cr-Al alloy heating wire.

That is to say, the outer wall of the hollow corundum tube is processed with external threads for the support and fixation of the iron-chromium-aluminum alloy heating wire. The space between the heating part and the hot cavity is filled with porous insulation materials. The inner wall of the hot cavity and the sealed top cover is sprayed. There is corundum.

Further, in one embodiment of the present invention, the sample stage is made of corundum, one end of the second hollow corundum tube is processed with grooves and external threads, and the top cover is processed with internal threads to fix the sample.

It can be understood that the sample stage can be made of corundum, one end of the hollow corundum tube is processed with grooves and external threads, and the ceramic top cover is processed with internal threads, and the sample is fixed by thread fit.

Further, in one embodiment of the present invention, the sample stage is designed to be detachable, and the O-shaped rubber ring, wedge-shaped inner sleeve and screw cap are screwed together with the bottom of the hot chamber to realize the sealing and fixing of the sample stage.

It should be noted that the sample stage is designed to be detachable, and the seal and fixation of the sample stage are realized by threading the O-shaped rubber ring, wedge-shaped inner sleeve and threaded cover with the bottom of the hot chamber.

Further, in one embodiment of the present invention, when the probe rod is used for current collection, the current is collected through the rhenium wire probe fixed at the end of the probe rod, and the current is drawn out from the copper wire in the middle of the probe rod.

That is to say, the current collection method of the internal electrode of the hot cavity adopts the current collection method of the probe rod, the current is collected through the rhenium wire probe fixed at the end of the probe rod, and the current is drawn out from the copper wire in the middle of the probe rod.

Further, in one embodiment of the present invention, an insulating plastic sleeve is provided at the end of the probe rod, and the position of the rhenium wire probe in the cavity can be adjusted online through the connection with the base and the three-dimensional three-coordinate translation stage.

That is to say, the end of the probe rod is equipped with an insulating plastic sleeve, and through the connection with the base and the three-dimensional three-coordinate translation stage, the online adjustment of the position of the rhenium wire probe in the cavity is realized.

Further, in one embodiment of the present invention, the current collecting device is sealed by welding metal bellows and quick-connect flange connections at both ends.

It can be understood that the sealing of the current collecting device is realized by welding metal bellows and quick-connect flange connections at both ends.

Further, in one embodiment of the present invention, the manual feeding part is arranged on the outer wall of the chamber main body.

That is to say, the outer wall of the hot chamber is equipped with a manual feeding device, and the front end of the manual feeding rod is designed with a clamping structure, which uses the toughness of stainless steel to clamp the crucible to realize online feeding to the sample position.

Further, in one embodiment of the present invention, the manual feeding part and the hot cavity are sealed through four-stage O-shaped rubber rings and flange connections.

That is to say, the dynamic sealing with the hot main body is realized through the four-stage O-shaped rubber ring and the flange connection.

Furthermore, in one embodiment of the present invention, the water cooling component is arranged below the chamber main body and above the sealed top cover, so as to cool down the high-temperature critical parts.

It can be understood that a cooling water device is designed above the sealing top cover to reduce the temperature of the space above the optical window, and a cooling water device is designed below the thermal chamber to reduce the temperature of the O-shaped rubber ring sealed on the sample stage.

Specifically, in one embodiment of the present invention, the electrochemical high-temperature in-situ Raman spectroscopic test thermal system of the embodiment of the present invention includes a thermal chamber part, a temperature measurement and control part, a sample carrying part, a gas supply part, an electric current Collecting parts, manual feeding parts and water cooling parts.

Among them, the hot chamber part includes a base, a chamber main body and a sealing top cover, and the base and the chamber main body are designed as one body, and are made of stainless steel. The main body of the chamber is the core of the whole testing device, the top of which is open, and the outer wall is designed and processed with manual feeding device, probe rod collecting device and gas supply device respectively, and the bottom has a through hole for loading and unloading samples. device. The main body of the chamber and the sealing top cover are sealed by a flange, and the seal is formed by an O-shaped sealing rubber ring and 8 evenly distributed fastening bolts. The inner side of the sealed top cover is sprayed with high-temperature resistant materials, and the middle part of the top cover is recessed inward and has a through hole, which is equipped with a sapphire glass disc for laser signal access, and is sealed by an O-shaped sealing rubber ring and fastening bolts.

Further, the temperature measurement and control components include heating components and temperature measurement thermocouples. The heating element consists of a hollow corundum tube and a heating wire. The outer wall of the corundum tube is threaded to fix and support the wound iron-chromium-aluminum alloy heating wire. The heating element is fixed in the center of the chamber body as a built-in heat source for the hot chamber. The heating part and the inner wall of the chamber are filled with a layer of porous insulation material. The function of the porous insulation material is to increase the thermal resistance of heat conduction, reduce the temperature of the outer wall of the thermal chamber, and ensure the safety of the experimental operation. There are sections of thin corundum sleeves outside the thermocouple, and two thermocouples are arranged in the cavity. One thermocouple temperature measuring head is kept at the same height as the sample, and is used to detect the temperature of the reaction position; the other thermocouple measures the temperature The head is consistent with the middle part of the heating section to monitor the highest temperature in the cavity and protect the heating components.

Further, the sample carrying part includes two parts: a sample stage and a fastener. The sample stage is made of corundum, including a hollow corundum tube of a certain thickness and a corundum top cover. The circular battery substrate commonly used in experiments is placed in the groove on one side of the corundum tube, and the corundum tube and the corundum top cover are fastened by threading. seal. The sample stage extends from the bottom of the hot chamber so that the sample position is in the center of the heating element. The installation and fixation of the sample stage are realized through the threaded cooperation between the bottom of the hot cavity and the top cover of the outer casing, and a conical inner sleeve and an O-shaped rubber ring are installed inside to realize the sealing of the cavity.

Further, the gas supply components respectively include gas inlet and outlet pipes of the bipolar chambers. The two poles of the test battery are mainly separated by the sample stage. The gas inlet and outlet pipes in the main chamber are made of stainless steel. The gas passes the sample through the side wall inlet pipe to fill the chamber, and then is discharged from the gas outlet pipe on the same side. The electrode chamber on the other side is composed of the inner space of the corundum tube of the sample table. The gas inlet pipe is a corundum tube. The gas flows through the annular cavity between the corundum tube of the sample table and the gas inlet pipe after passing through the porous current-collecting platinum mesh, and passes through the gas outlet. hole drain.

Further, the current collecting components respectively include two-pole current collecting components. The electrode current collecting part in the hot chamber adopts a probe probe rod to collect current. The rhenium wire probe at the front end of the probe rod is in close contact with the electrode surface to collect current, and the current signal is drawn out of the cavity through the copper wire pressed in the middle of the probe rod by the reed; the end of the probe rod away from the electrode is equipped with an insulating plastic sleeve, The metal base is fixed on the three-dimensional three-coordinate translation platform to realize the online adjustment of the current collection position; the seal between the three-dimensional coordinate translation platform and the cavity is adjustable and sealed by welding bellows. The electrode on the other side uses platinum wire and platinum mesh to collect current. The gas inlet tube is used to press the platinum mesh tightly on the electrode surface to collect current signals, and the current collecting platinum wire passes through the gas inlet pipe to lead out the current.

Further, the manual feeding part includes a manual feeding rod, a seal and a crucible. The front end of the manual feeding rod is designed with a clamping structure for clamping the TGA crucible filled with samples. The fixing and sealing of the feeding rod and the hot cavity are realized through flange connection and four-stage rubber ring.

Further, the water-cooling component includes a water-cooling jacket and a cooling water conduit welded thereon. In order to realize the cooling of the key parts in the high-temperature thermal state, the device is designed with two-way water cooling. One way is fixed in the middle of the thermal top cover through a flange connection, which is used to reduce the temperature at the position of the optical window and protect the optical window and the optical lens for Raman spectrum collection above. The other water cooling is installed at the bottom of the hot state to cool the O-shaped sealing rubber ring that realizes the sealing of the sample stage to prevent sealing failure.

Secondly, the thermal state system for electrochemical high-temperature in-situ Raman spectroscopy testing proposed according to the embodiments of the present invention will be described below with reference to the accompanying drawings.

As shown in FIG. 1 , FIG. 1 is a schematic structural diagram of a hot-state system for electrochemical high-temperature in-situ Raman spectroscopy testing according to an embodiment of the present invention.

As shown in Figure 1, the hot chamber (2) is fixed on the base (1). The iron-chromium-aluminum alloy heating wire (7) is wound on the outer wall of the hollow corundum tube (6) processed with external threads, and the corundum tube is fixed in the center of the hot cavity as a built-in heat source to provide the temperature required for the reaction. Porous insulation material is filled between the corundum tube and the inner wall of the hot cavity. There is a through hole at the bottom of the hot chamber, and the sample stage (9) used to carry the sample extends from the bottom, and the extrusion force of the conical metal sleeve (11) and the O-shaped rubber ring (12) is used to realize the hot chamber. The bottom of the body is sealed, and the sample stage is fixed by connecting the internal thread top cover (10) with the external thread at the bottom of the hot chamber. After fixing, the sample position is close to the top end of the heating wire. The K-type thermocouple (8) for temperature measurement passes through the porous insulation material, so that the temperature measurement head is at the same height as the sample, and is used to monitor the real-time temperature of the sample position. The hot chamber is designed with an open top, and is connected with the sealing top cover (3) through a flange connection and an O-shaped rubber ring (4) to realize top sealing. The center of the sealed top cover is processed with a stepped hole, which is equipped with sapphire optical glass (5) for the entrance and exit of the laser light path used for Raman spectrum collection, and the sealing of the optical glass is realized by the flange connection between the water cooling jacket (22) and the top cover. The side wall of the hot cavity is designed with a manual feeding device. The front end of the manual feeding rod (18) is designed with a clamping structure, and the crucible (19) for filling the sample is clamped by the elasticity of the stainless steel sheet, which is used for online feeding to the position of the sample stage during the test. The fastening and sealing of the feeding rod are realized through the flange connection between the fastener (20) and the outer wall structure of the hot cavity, and the four-stage O-shaped rubber ring (21). The anode current collection of the test battery in the hot cavity adopts a probe probe rod current collection device. The rhenium wire probe (14) is fixed on the front end of the long probe rod (15), collects current signals through close contact with the anode surface, conducts them through the long probe rod, and leads out of the cavity through the copper wire connected in the middle of the long probe rod. The tail of the long probe rod is designed with an insulating plastic sleeve, which is connected to the base of the probe rod (17), and the base of the probe rod is fixed to a commercial three-dimensional three-coordinate translation stage, thereby realizing the three-dimensional adjustment of the probe during the test. A flexible metal welded bellows (16) is used for the sealing of the current collecting device of the probe probe rod, which is sealed and fixed through flange connection. The cathode chamber is composed of the space inside the corundum tube of the sample table. The cathode current is collected by platinum wire and platinum mesh. The platinum mesh is pressed tightly on the surface of the cathode through the fine corundum tube (13) to collect current signals, and then the current signal is collected through the platinum wire connected to the platinum mesh. Draw the current out. A water cooling jacket (22) is designed on the sealed top cover to cool the surrounding temperature of the optical glass and protect the Raman optical lens tested above. A water-cooling jacket (23) is also designed at the bottom of the hot chamber to reduce the temperature of the O-shaped rubber ring (12) and prevent the sample stage from sealing failure.

Further, as shown in Figure 2, the top of the thick-walled hollow corundum tube (9-1) is processed with grooves for supporting the commonly used test battery substrate (9-3), and then coated with high-temperature sealant to achieve sealing. The top of the corundum tube is machined with external threads, and the battery substrate is pressed tightly by the threads of the ceramic top cover (9-2). After the sample stage is fixed and sealed in the hot chamber, the separation of the two pole chambers of the battery is also realized, wherein the anode is in the main chamber of the hot state, and the cathode chamber is the inner chamber of the corundum tube.

Further, as shown in Figure 3, the tail of the anode current collecting probe rod is fitted with a plastic sleeve through a tight fit, and the sleeve and the through hole (26) are tightly fitted so that the probe rod is fixed on the rod seat, and the through hole (25) It is used for the lead-out of current-collecting wires.

Further, as shown in FIG. 4 , the through hole ( 24 ) on the rod seat of the probe rod is matched with the threaded hole ( 27 ) on the chassis, so that the rod seat of the probe rod is fixed on the chassis. The chassis is fixed on the three-dimensional three-coordinate translation platform through four through holes (28), so as to meet the requirements for three-dimensional coordinate adjustment of the probe rod current collecting system. The through hole (29) on the chassis is used for the lead-out of current collecting wire.

In addition, as shown in Fig. 5, after the probe rod and the rod base (30) are fixed by tight fit, the rod base is fixed on the chassis (17) by bolts. The chassis and the welded bellows (16) are connected by flanges to realize sealing. The seal between the welded bellows and the hot cavity is also realized through flange connection.

For example, the Raman spectrometer matched with the thermal system of the embodiment of the present invention is the QE65Pro Raman spectrometer of Ocean Optics, the laser is a 473nm blue laser with a power of 100mW, and the electrochemical workstation is the IM6ex electrochemical workstation of Zahner, Germany.

The electrochemical high-temperature in-situ Raman test thermal system of the embodiment of the present invention is used to test the liquid antimony metal anode solid oxide fuel cell system under the condition of 1073K. The specific operation process is as follows:

A yttria-stabilized zirconia (YSZ) electrolyte substrate brushed with platinum paste on one side is placed in the groove of the corundum tube of the sample stage, coated with high-temperature sealant and screwed on the ceramic top cover. Fix the sample stage on the hot chamber so that the position of the cell is at the end of the heating wire. Adjust the position of the thermocouple temperature measuring head so that it is close to the ceramic top cover. Add an appropriate amount of metal antimony powder into the crucible, and clamp the crucible on the manual feeding rod. To prevent sealing the top cover, tighten the bolts to achieve a cavity seal. Two circuits of circulating cooling water are turned on, and argon gas is introduced into the main body of the chamber as a protective gas. Set the heating program and start heating. When the temperature reaches 1073K, the metal antimony powder in the crucible is poured on the surface of the YSZ substrate through a manual feeding rod to make it melt into balls rapidly. The cathode uses a thin corundum tube to close the platinum mesh to the surface of the cathode, and the anode makes the metal probe contact the antimony droplet by operating the three-dimensional three-coordinate translation platform, and uses the electrochemical workstation to perform electrochemical tests. Raman spectra can be collected in the system during the whole heating process.

The Raman spectra of the electrolyte YSZ substrate at room temperature and high temperature measured by a Raman spectrometer are shown in Figure 6. It can be seen that the system can obtain a Raman spectrum with a high signal-to-noise ratio and clear characteristic peaks, which well reflects Temperature effects in Raman spectroscopy.

Liquid antimony metal anode SOFC can still maintain the operation of the battery through self-oxidation without adding fuel to the anode. This mode is called "battery mode". Its working principle is: O ₂ gets electrons at the cathode-electrolyte interface on the cathode side to generate O ^2- , and O ^2- is transported to the anode-electrolyte interface through the electrolyte to undergo oxidation reaction with liquid antimony metal. The electrochemical reaction is mainly :

2Sb+3O ²⁻ →Sb ₂ O ₃ +6e ⁻ .

Therefore, the overall reaction of SOFC with liquid antimony metal anode under battery mode operation is:

2Sb+3O ₂ →Sb ₂ O ₃ .

As shown in Figure 7, Figure 7 shows the high signal-to-noise ratio and clear and stable volt-ampere characteristic curve of the liquid antimony metal anode solid oxide fuel cell measured by the electrochemical workstation at 1073K, which further proves the accuracy of the results of the electrochemical test system reliability.

According to the electrochemical high-temperature in-situ Raman spectroscopy testing thermal state system of the embodiment of the present invention, the functions of sealing the test battery, adding samples in situ, current collection, cathode and anode gas supply, temperature measurement and temperature control can be realized, and at the same time, the The Raman spectrum is captured in situ through the optical glass window facing the sample position, and through careful structural design, functions such as compact structure, convenient disassembly, and local water cooling are realized, so that it can be used for online measurement of electrochemistry under high temperature operating conditions The electrochemical signal and Raman spectrum information of the system can better meet the needs of use, it is safer and more reliable, and it is simple and easy to implement.

In describing the present invention, it is to be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " Back", "Left", "Right", "Vertical", "Horizontal", "Top", "Bottom", "Inner", "Outer", "Clockwise", "Counterclockwise", "Axial", The orientation or positional relationship indicated by "radial", "circumferential", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying the referred device or element Must be in a particular orientation, be constructed in a particular orientation, and operate in a particular orientation, and therefore should not be construed as limiting the invention.

In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

In the present invention, unless otherwise clearly specified and limited, terms such as "installation", "connection", "connection" and "fixation" should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection , or integrated; it may be mechanically connected or electrically connected; it may be directly connected or indirectly connected through an intermediary, and it may be the internal communication of two components or the interaction relationship between two components, unless otherwise specified limit. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.

In the present invention, unless otherwise clearly specified and limited, the first feature may be in direct contact with the first feature or the first and second feature may be in direct contact with the second feature through an intermediary. touch. Moreover, "above", "above" and "above" the first feature on the second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. "Below", "beneath" and "beneath" the first feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is less horizontally than the second feature.

In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.

Claims (10)

1. a kind of electrochemistry in-situ high temperature Raman spectroscopy tests hot system, it is characterised in that including：

Hot cavity, the hot cavity includes base, chamber body and top pressure closure, wherein, the top of the chamber body Opening is set to, and the bottom of the chamber body is provided with through hole, the chamber body passes through flange with the top pressure closure Sealing completes sealing, and top pressure closure inner side is coated with exotic material, is caved inward in the middle part of the top pressure closure And through hole is provided with, to be provided for the sapphire glass disk of laser signal discrepancy；

Temperature-control units are surveyed, the survey temperature-control units include heater block and temperature thermocouple, and the heater block is fixed on described The center of chamber body, and the heater block and chamber inner wall fill up porous insulation material layer, the heater block has the One hollow alundum tube and heater strip, wherein, the outer wall of the first hollow alundum tube is set by screw thread, described with fixed and support Heater strip, is provided with into the thin corundum sleeve pipe of section, and two thermocouples, first are provided with cavity outside the temperature thermocouple The thermometric head height identical with sample holding of thermocouple, to detect the temperature of response location, and the second thermocouple temperature measuring head Portion is consistent with bringing-up section middle part, to monitor cavity temperature highest point；

Sample load bearing component, the sample load bearing component includes sample stage and fastener, and the sample stage is hollow firm with second Jade pipe and corundum top cover, fit sealing is carried out with by the described second hollow alundum tube and corundum top cover, wherein, the sample stage Stretched into from the bottom of the hot cavity, so that sample position is in the center of the heater block；

Current collector part, the current collector part includes first electrode flow concentrating part and second electrode flow concentrating part, described First electrode flow concentrating part in hot cavity uses probe feeler lever afflux, second electrode flow concentrating part to use platinum filament platinum guaze collection Stream；

Manual charging part, the manual part that feeds includes feed manually bar, seal and crucible, wherein, it is described to add manually Material bar is provided with clamp structure, and the crucible of sample is filled with to clamp；And

Water-cooling section, the water-cooling section is made up of water collar and the coolant guide pipe being welded on the water collar.

2. electrochemistry in-situ high temperature Raman spectroscopy according to claim 1 tests hot system, it is characterised in that described to add Heated filament is Aludirome heater strip, and the outer wall of the first hollow alundum tube is machined with external screw thread and is closed for the ferrum-chromium-aluminum The support and fixation of golden heater strip.

3. electrochemistry in-situ high temperature Raman spectroscopy according to claim 1 tests hot system, it is characterised in that the sample Sample platform is corundum material, and one end of the second hollow alundum tube processes fluted and external screw thread, and top cover is machined with internal thread, with The fixation sample.

4. electrochemistry in-situ high temperature Raman spectroscopy according to claim 1 tests hot system, it is characterised in that the sample Sample platform is design for disassembly, and screw thread is passed through by O-shaped rubber ring, wedge-shaped inner sleeve and threaded cap and the bottom of the hot cavity The sealing and fixation of the sample stage are realized in cooperation.

5. electrochemistry in-situ high temperature Raman spectroscopy according to claim 1 tests hot system, it is characterised in that using During probe feeler lever afflux, by being fixed on the rhenium silk probe collected current of feeler lever end, and drawn by the copper wire in the middle part of feeler lever The electric current.

6. electrochemistry in-situ high temperature Raman spectroscopy according to claim 5 tests hot system, it is characterised in that feeler lever tail Portion is provided with ambroin sleeve, by the connection with base and three-dimensional three coordinate translations platform, makes rhenium silk probe position in cavity Putting carries out on-line control.

7. electrochemistry in-situ high temperature Raman spectroscopy according to claim 6 tests hot system, it is characterised in that by weldering The fast acting flange connection for connecing metal bellows and two ends is sealed to current-collecting device.

8. electrochemistry in-situ high temperature Raman spectroscopy according to claim 1 tests hot system, it is characterised in that the hand Dynamic charging part is arranged on the outer wall of the chamber body.

9. electrochemistry in-situ high temperature Raman spectroscopy according to claim 8 tests hot system, it is characterised in that by four Level O-shaped rubber ring and flange connection are sealed to the manual charging part and the hot cavity.

10. electrochemistry in-situ high temperature Raman spectroscopy according to claim 1 tests hot system, it is characterised in that described Water-cooling section is arranged at the lower section and top pressure closure top of the chamber body, cold to carry out to the hot key position of high temperature But lower the temperature.