Experimental device for variable-temperature electrochemical Raman spectrum characterization

Abstract

The invention provides an experimental device for variable-temperature electrochemical Raman spectrum characterization, and relates to a device convenient for optical testing and Raman scattering. The experimental device comprises a cold and hot table assembly, an electrolytic tank assembly, a circulating water tank air pump assembly and an electric control assembly, and adopts a two-stage refrigeration technology (a cold end refrigeration part of a refrigeration sheet and a refrigeration part cool a cooling medium and then the cooling medium is introduced into a water cooling head); the problem that high-precision interface spectroscopy imaging is limited due to vibration of a small and medium-sized Dewar system in the prior art is effectively solved, and the bottleneck that a single semiconductor is low in refrigeration efficiency and difficult to realize long-time ultralow-temperature control is overcome. The novel Raman electrolytic tank suitable for the (high) low temperature electrochemical experiment is compact in structure, high in heat conduction efficiency and small in heat dissipation loss, a structure for low temperature potential correction is reserved, the novel Raman electrolytic tank is effectively suitable for a low temperature cold and hot platform, and the novel Raman electrolytic tank can be effectively suitable for other (high) low temperature devices on the market after being finely adjusted by related technicians in the field.

Description

Technical Field

[0001] The present invention relates to testing or analyzing materials by measuring the chemical or physical properties of materials, to a device or instrument for facilitating optical testing, to Raman scattering, to electrolytic cell components, and in particular to an experimental device for variable temperature electrochemical Raman spectroscopy characterization. Background Art

[0002] The research on variable temperature electrochemistry (temperature range of about -120 ℃ ~ 80 ℃) and variable temperature energy storage devices is an important research field at present. In particular, the research on low temperature battery materials (such as low temperature electrolytes) has attracted much attention recently, which also puts forward an urgent need for in-situ characterization of low temperature electrochemical systems under variable temperature conditions. Raman spectroscopy, as a powerful characterization tool, has become a common means of studying energy materials and interface processes because it can provide vibrational spectral information and can be used in conjunction with electrochemical research techniques.

[0003] In order to realize Raman spectroscopy testing under variable temperature conditions, the existing technology mainly adopts the following solutions: (1) Variable temperature hot and cold stages based on Dewar systems. Such devices usually use liquid gases such as liquid nitrogen or liquid helium as cooling media and can achieve extremely low temperatures. There are already a variety of (high) low temperature devices on the market that can be used with Raman spectrometers based on this principle. However, this solution has the following significant disadvantages: it is difficult to use with electrochemical devices. Existing commercially available devices based on Dewar systems are usually designed for low-temperature Raman research of simple solid, powder or liquid samples. They lack interfaces and functions for use with electrochemical devices and are difficult to meet the needs of low-temperature electrochemical Raman in-situ characterization; the device structure is complex and difficult to improve. The structure of the Dewar system is relatively complex, and it is difficult for users to improve it according to their own research needs, such as connecting to electrochemical equipment or other combined equipment, which limits the flexibility of the experiment; and there are vibration problems. Especially for small Dewar systems, the sample stage often has irregular vibrations during use, which seriously affects high-precision interface research. For example, when performing high-resolution imaging or micro-area Raman testing, vibration will cause image blur or spectral signal distortion.

[0004] (2) High and low temperature devices based on semiconductor refrigeration. This type of device uses semiconductor refrigeration chips for refrigeration and has the advantages of high temperature control accuracy and fast response speed. However, this solution also has obvious limitations: it is difficult to reach lower temperatures. Single-stage or simple multi-stage semiconductor refrigeration usually cannot reach lower temperatures, such as below -40°C, which limits its application in low-temperature electrochemical research that requires lower temperatures; and the refrigeration efficiency is low. In the low temperature range, the efficiency of semiconductor refrigeration will drop significantly, resulting in high energy consumption and difficulty in maintaining a stable low temperature state.

[0005] (3) (High) low temperature devices based on air compressor refrigeration. This type of device can achieve relatively low temperatures by compressing refrigerant gas for refrigeration. However, this solution also has shortcomings: the temperature control accuracy is poor. Compared with semiconductor refrigeration, the temperature control accuracy of air compressor refrigeration is relatively low, which is difficult to meet the needs of high-precision low-temperature electrochemical research.

[0006] In summary, the existing technology has many shortcomings in realizing variable temperature electrochemical Raman coupling, which mainly focus on the compatibility of the device, operational safety, temperature control range and accuracy, and vibration control.

[0007] Therefore, developing a device that can effectively overcome the above shortcomings and realize variable-temperature electrochemical Raman spectroscopy testing in the range of -120 ℃ ~ 80 ℃ is of great significance for in-depth research in the fields of variable-temperature energy chemistry, low-temperature electrochemistry, and low-temperature energy storage devices. Summary of the invention

[0008] The present invention is made to solve the above-mentioned problem, and aims to provide an experimental device for variable temperature electrochemical Raman spectroscopy characterization.

[0009] The invention provides an experimental device for variable temperature electrochemical Raman spectroscopy characterization, which has the following characteristics: a cold and hot stage assembly, an electrolytic cell assembly, a circulating water tank air pump assembly and an electric control assembly, wherein the cold and hot stage assembly has a water cooling head, a cooling plate connected to the water cooling head and a heating plate connected to the water cooling head, the outer surface of the cold and hot stage assembly has a first optical window, the electrolytic cell assembly is arranged inside the cold and hot stage assembly and is located on the cooling plate, the electrolytic cell assembly performs an electrochemical experiment through a counter electrode, a working electrode and a reference electrode sealed inside the electrolytic cell assembly, the outer surface of the electrolytic cell assembly has a second optical window, the electrolytic cell assembly is used to perform a Raman spectroscopy characterization experiment through the first optical window and the second optical window, the circulating water tank air pump assembly comprises: a cooling medium circulation member connected and communicated with the water cooling head and used to provide a circulating cooling medium to the water cooling head, and an air supply member connected to the cooling medium circulation member and the cold and hot stage assembly and used to blow dry gas cooled by the cooling medium in the cooling medium circulation member to the upper surface of the first optical window to prevent it from frosting or fogging; the electric control assembly comprises: a DC A voltage-stabilized power supply is connected to and supplies power to the cooling plate and the heating plate; an AC power supply is connected to and supplies power to the circulating water tank air pump assembly; there are several temperature sensors, which are respectively arranged on the water-cooled head, the cooling plate, the heating plate and the electrolytic cell assembly; there are two temperature controllers, which are respectively arranged on the power supply lines of the water-cooled head and the cooling plate and are used to control the operating power of the water-cooled head and the cooling plate; a high liquid level sensor is arranged in the cooling medium circulation part and is used to detect the high liquid level of the cooling medium stored in the cooling medium circulation part; there are several current / voltage sensors, which are arranged on the output lines of the DC voltage-stabilized power supply and the AC power supply and are used to detect the current / voltage signals of the DC voltage-stabilized power supply and the AC power supply; there are several circuit switches, which are arranged on different circuits; a controller is connected to the temperature sensor, the temperature controller, the high liquid level sensor, the current / voltage sensor and the circuit switch and is used to dynamically adjust the working state of the circulating water tank air pump assembly and / or the hot and cold stage assembly according to the voltage / current data, different temperature data and the high liquid level data through a preset strategy.

[0010] In the experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the cooling plate is arranged above the water cooling head, and the space between the cooling plate and the water cooling head is filled with a heat conductive medium; the heating plate is arranged below the water cooling head, and the space between the heating plate and the water cooling head is filled with a heat conductive medium.

[0011] The experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention may also have the following characteristics: wherein, the water cooling head is externally connected with a liquid conduit, and the liquid conduit is connected with a cooling medium circulation part, so that the cooling medium circulation part circulates the cooling medium through the liquid conduit to the water cooling head.

[0012] The experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention may also have the following feature: the outer periphery of the liquid guiding tube is coated with a heat preservation tube for reducing heat loss.

[0013] In the experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the electrolytic cell assembly includes: an electrolytic cell body, having an inwardly recessed opening groove, in which a cylindrical protrusion is convexly provided; a working electrode connector, which is inserted into the cylindrical protrusion and connected to the electrochemical workstation through a wire outside the electrolytic cell assembly; a working electrode, which is arranged on the cylindrical protrusion and connected to the working electrode connector, and the working electrode is located inside the opening groove; a reference electrode, which is arranged in the opening groove and connected to the external electrochemical workstation through a wire inserted through the electrolytic cell body; a counter electrode, which is arranged in the opening groove and connected to the external electrochemical workstation through a wire inserted through the electrolytic cell body, and the counter electrode surrounds the working electrode; an electrolytic cell cover, which is detachably arranged on the electrolytic cell body and completely covers the opening groove, and the electrolytic cell cover has a second optical window; and a sealing ring, which is arranged between the electrolytic cell body and the electrolytic cell cover to ensure the sealing between the two.

[0014] In the experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the electrolytic cell body is made of a material with corrosion resistance and low-temperature stability, the optical window is made of a material with high transmittance, low fluorescence background and good chemical stability, the counter electrode is a metal wire with high conductivity and chemical stability, the working electrode connector is made of a material with high conductivity, corrosion resistance and mechanical strength, the reference electrode is a metal wire quasi-reference electrode, and the sealing ring is made of an elastic material with corrosion resistance and low-temperature sealing performance.

[0015] In the experimental device for variable-temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the cooling medium circulation component includes: a circulating water tank, which is filled with cooling medium, and the circulating water tank is connected to a water-cooled head so as to transport the circulating cooling medium to the water-cooled head; a refrigeration part, which is connected to the circulating water tank so as to cool the cooling medium; and a circulating pump, which is arranged on the passage connecting the circulating water tank and the water-cooled head so as to provide power for the circulation of the cooling medium.

[0016] In the experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the cooling medium circulation component also includes: an agitator, which is connected to the circulating water tank and stirs the cooling medium therein; and an insulating layer, which at least covers the circulating water tank to reduce the heat loss of the cooling medium.

[0017] In the experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the air supply component includes: an air supply pipeline, one end of which is connected to the atmosphere, and the other end is connected and connected to the hot and cold stage assembly and the pipe mouth is located beside the first optical window, and the pipe body of the air supply pipeline is at least partially immersed in the cooling medium; an air pump, which is arranged on the air supply pipeline, is used to provide blowing cold air to the first optical window through the air supply pipeline; and a dryer, which is arranged on the air supply pipeline, is used to dry the cold air it transports.

[0018] In the experimental device for variable temperature electrochemical Raman spectroscopy characterization provided by the present invention, it can also have the following characteristics: wherein, the electronic control component also includes a gas flow meter and a gas flow control valve, the gas flow meter and the gas flow control valve are arranged on the gas supply pipeline and connected to the controller, and the controller also controls the gas flow control valve according to a predetermined strategy based on the data transmitted by the gas flow meter.

[0019] The present invention provides an improved scheme for low-temperature electrochemical Raman testing, which significantly improves the performance and applicability of low-temperature electrochemical Raman testing and has the following beneficial effects: (1) In terms of the refrigeration system, the present invention adopts a two-stage refrigeration technology (refrigeration of the cold end of the refrigeration plate + cooling of the cooling medium by the refrigeration part and then passing it into the water cooling head), which effectively solves the problem of limited high-precision interface spectroscopy imaging caused by vibration of small and medium-sized Dewar systems in the prior art, and overcomes the bottleneck of low efficiency of single semiconductor refrigeration and difficulty in achieving long-term ultra-low temperature control. Specifically, the present invention uses the refrigeration part to provide low-temperature circulating coolant (cooling medium) to efficiently dissipate heat for the hot end of the refrigeration plate, greatly improving the refrigeration efficiency, and theoretically achieving precise control over an ultra-wide temperature range of -120 ℃ to 80 ℃. Compared with the traditional small liquid nitrogen Dewar system, the device of the present invention significantly reduces vibration interference and improves the accuracy and resolution of spectral imaging; at the same time, the device of the present invention does not need to frequently replenish liquid nitrogen, is easier to operate, and reduces experimental and maintenance costs. Compared with a single semiconductor refrigeration system, the device of the present invention expands the temperature control range and can achieve a lower test temperature.

[0020] (2) In terms of electrolytic cell design, the present invention designs a new Raman electrolytic cell suitable for (high) and low temperature electrochemical experiments. The electrolytic cell has a compact structure, high heat conduction efficiency, low heat loss, and a structure reserved for low temperature potential correction. It can be effectively applied to this low temperature hot and cold platform, or after fine-tuning by relevant technicians in the field, it can be effectively applied to other (high) and low temperature devices on the market.

[0021] (3) The present invention provides alternative reference solutions for different experimental needs and reserves room for upgrading. Users can flexibly select appropriate equipment configurations according to the specific requirements of their own experiments, thereby improving the versatility and applicability of the device, meeting the personalized needs of different users, and reducing the user's experimental costs.

[0022] (4) The present invention effectively solves the deficiencies of the prior art in low-temperature electrochemical Raman testing by improving the refrigeration system, electrolytic cell design and equipment scheme selection, and significantly improves the accuracy, efficiency, convenience and applicability of the test. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 1 is a perspective view and a top view of a hot and cold stage assembly in an embodiment of the present invention.

[0024] Figure 2 is a top view of an electrolytic cell assembly in an embodiment of the present invention.

[0025] Figure 3 It is a schematic structural diagram of a circulating water tank air pump assembly in an embodiment of the present invention.

[0026] Figure 4 It is a schematic diagram of the connection relationship of the electronic control components in the embodiment of the present invention.

[0027] Figure 5 yes Figure 1 Front cross-sectional view at line A-A'.

[0028] Figure 6 yes Figure 2 Exploded view of the main section at line B-B'. DETAILED DESCRIPTION

[0029] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the following embodiments and accompanying drawings specifically illustrate an experimental device for variable temperature electrochemical Raman spectroscopy characterization of the present invention.

[0030] <Example> Figure 1 are a perspective view and a top view of a hot and cold stage assembly in an embodiment of the present invention; Figure 2 is a top view of an electrolytic cell assembly in an embodiment of the present invention; Figure 3 is a schematic structural diagram of a circulating water tank air pump assembly in an embodiment of the present invention; Figure 4 It is a schematic diagram of the connection relationship of the electric control components in the embodiment of the present invention.

[0031] like Figure 1~Figure 4As shown, this embodiment provides an experimental device 100 for variable temperature electrochemical Raman spectroscopy characterization, including a hot and cold stage assembly 10 , an electrolytic cell assembly 20 , a circulating water tank air pump assembly 30 , and an electronic control assembly 40 .

[0032] Figure 5 yes Figure 1 Front cross-sectional view at line A-A'.

[0033] like Figure 1 and Figure 5 As shown, the hot and cold stage assembly 10 includes a housing 11 , a heating plate 12 , a water cooling head 13 , and a cooling plate 14 .

[0034] The shell 11 is used to support internal components, provide certain thermal insulation performance and form a relatively closed space.

[0035] The housing 11 is divided into a test area 111 and a storage area 112 by a grid plate 11 a therein, and the atmospheres of the test area 111 and the storage area 112 are connected.

[0036] The top detachable cover plate of the test area 111 is provided with a first optical window sheet 111a, and the side wall of the test area 111 is provided with a plurality of through holes for passing circuits and / or pipes, wherein the corresponding through holes are closed by detachable sealing plugs 111b when not in use.

[0037] The storage area 112 has a detachable cover, and the interior of the cover is used to place desiccant and sensors required for the experiment.

[0038] The heating plate 12 is disposed at the inner bottom of the test area 111. Specifically in this embodiment, the heating plate 12 is an alumina ceramic heating plate or a resistance wire heating plate.

[0039] The water cooling head 13 is disposed on the heating plate 12 , and a heat conducting medium is filled between the water cooling head 13 and the heating plate 12 to improve the heat conducting efficiency and reduce the thermal resistance.

[0040] The water cooling head 13 has an integrally formed water inlet pipe 13a and a water outlet pipe 13b, both of which pass through the inner bottom of the test area 111, and are used for cooling medium to flow into and out of the water cooling head 13 respectively.

[0041] The water inlet pipe 13a and the water outlet pipe 13b are respectively connected to two liquid guide tubes, and the outer periphery of the liquid guide tubes is coated with an insulation tube for reducing heat loss. When the cooling medium is a water-based coolant (water, salt water), the liquid guide tube material includes a silicone tube and a rubber tube; when the cooling medium is an organic solvent, the liquid guide tube material is a hose material resistant to organic solvent corrosion, including a fluororubber tube; in this embodiment, when performing a low-temperature electrochemical Raman spectroscopy experiment, in order to improve the stability and durability of the device, a silicone tube is selected for the liquid guide tube.

[0042] The cooling fin 14 is disposed on the water cooling head 13, and the hot end of the cooling fin 14 contacts the water cooling head 13, so that the water cooling head 13 cools down the temperature. A heat conducting medium is filled between the cooling fin 14 and the water cooling head 13 to improve the heat conduction efficiency and reduce the thermal resistance.

[0043] Specifically in the present embodiment, the cooling plate 14 is a semiconductor cooling plate, and cooling plates of different models and stages (single-stage, two-stage to five-stage semiconductor cooling plates) are selected according to the required cooling capacity.

[0044] Among the above heating plate 12 , water cooling head 13 and refrigeration plate 14 , the water cooling head 13 is used to transfer the heat generated by the refrigeration plate 14 and the heating plate 12 to the cooling medium therein.

[0045] Figure 6 yes Figure 2 Exploded view of the main section at line B-B'.

[0046] like Figure 2 and Figure 6 As shown, the electrolytic cell assembly 20 includes an electrolytic cell body 21, a working electrode connector 22, a working electrode 23, a reference electrode 24, a counter electrode 25, an electrolytic cell cover 26, a sealing ring 27 and an electrolytic cell cover reinforcement 28.

[0047] The electrolytic cell body 21 has an inwardly concave opening groove 21a, and a cylindrical protrusion 21b is convexly provided in the opening groove 21a. The electrolytic cell body 21 is arranged above the cold end of the cooling plate 14, and the electrolytic cell body 21 is made of a material with corrosion resistance and low temperature stability.

[0048] Specifically in this embodiment, the electrolytic cell body 21 is cylindrical in shape as a whole. The electrolytic cell body 21 is made of polytetrafluoroethylene (PTFE) or polyetheretherketone (PEEK), which has excellent corrosion resistance and low temperature stability, and can effectively resist the erosion of the electrolyte and the influence of the low temperature environment.

[0049] The side wall of the electrolytic cell body 21 has four reserved holes with a diameter of 0.5 mm, which are respectively marked as a first reserved hole, a second reserved hole, a third reserved hole and a fourth reserved hole.

[0050] The working electrode connector 22 is inserted into the cylindrical protrusion 21b and connected to the electrochemical workstation through a wire outside the electrolytic cell assembly 20. The working electrode connector 22 is made of a material with high conductivity, corrosion resistance and mechanical strength, and can achieve reliable connection and electrical signal transmission with the working electrode 23, and minimize interference with electrochemical testing.

[0051] Specifically in this embodiment, the material of the working electrode connector 22 is pure titanium, titanium alloy, gold, silver or copper.

[0052] The working electrode 23 is disposed on the cylindrical protrusion 21 b and connected to the working electrode connector 22 . The working electrode 23 is located inside the opening groove 21 a .

[0053] Specifically in this embodiment, the selection of the specific material of the working electrode connector 22 should be comprehensively considered based on the material of the working electrode 23 and the type of electrolyte to avoid the working electrode connector 22 participating in the electrochemical reaction or electrochemical corrosion with the working electrode 23. The material of the working electrode connector 22 is preferably the same material as the working electrode 23.

[0054] The reference electrode 24 is disposed in the opening groove 21 a and is connected to an external electrochemical workstation via a wire passing through a first reserved hole on the side wall of the electrolytic cell body 21 .

[0055] Under non-extreme temperature conditions, traditional reference electrodes, such as silver / silver chloride electrode (Ag / AgCl), saturated calomel electrode (SCE), etc., can be used. However, in high and low temperature environments, the potential of the traditional reference electrode is greatly affected by temperature, and the reference electrode supporting electrolyte is prone to ice in extreme low temperature environments, resulting in the inability of the traditional reference electrode to work properly. Therefore, this embodiment uses a metal wire as a quasi-reference electrode (QRE), including a platinum wire or a gold wire, and performs a rapid reference electrode potential correction through the fourth reserved hole.

[0056] When the reference electrode 24 is used, its potential may drift to a certain extent depending on the experimental conditions. In order to obtain an accurate potential reference, the reference electrode 24 needs to be calibrated.

[0057] The calibration method includes: (1) Calibration using a room temperature reference electrode: Using the fourth reserved hole, measure the potential difference between a reference electrode (such as an Ag / AgCl reference electrode) of the same system but at room temperature and a quasi-reference electrode at low temperature to obtain a more accurate electrode potential in the system at the test temperature. (2) Design a low-temperature reference electrode: In order to obtain a more stable potential reference at low temperatures, design a reference electrode suitable for low-temperature environments. For example, in a silver / silver chloride electrode, replace the saturated potassium chloride solution with other electrolyte solutions with a lower freezing point, such as lithium chloride, acetonitrile lithium salt, etc. This method can effectively reduce the lower temperature limit of the reference electrode. (3) According to the specific experimental conditions and temperature range, select a suitable reference electrode or quasi-reference electrode, and adopt corresponding calibration methods to ensure the accuracy of potential measurement.

[0058] The counter electrode 25 is disposed in the opening groove 21a and is connected to an external electrochemical workstation through a wire passing through a second reserved hole on the side wall of the electrolytic cell body 21. The counter electrode 25 surrounds the working electrode 23 to provide uniform current distribution. The counter electrode 25 is a material with high conductivity and chemical stability, and the counter electrode 25 is a gold wire, a silver wire, glassy carbon, a platinum wire or stainless steel. Specifically in this embodiment, the counter electrode 25 is a platinum wire with a diameter of 0.5 mm.

[0059] The electrolytic cell cover 26 is detachably disposed on the electrolytic cell body 21 and completely covers the opening slot 21a. The electrolytic cell cover 26 has a second optical window 26a. The second optical window 26a is made of a material with high transmittance, low fluorescence background and good chemical stability.

[0060] Specifically, in this embodiment, the material of the second optical window 26a is sapphire (Al2O3), fused quartz (SiO2), ultraviolet grade fused quartz (JGS1), calcium fluoride (CaF2) or zinc selenide. Among them, sapphire (Al2O3) material has high transmittance in the ultraviolet-visible-near infrared band, and does not produce fluorescence background interference, which can meet the requirements of Raman spectrum testing. At the same time, sapphire (Al2O3) has excellent chemical stability and mechanical strength, as well as good low-temperature performance; fused quartz and ultraviolet grade fused quartz (JGS1) also have good transmittance and low fluorescence background in the deep ultraviolet to visible band, but their mechanical strength and corrosion resistance are slightly inferior to sapphire (Al2O3); calcium fluoride (CaF2) has good transmittance from ultraviolet to mid-infrared, low birefringence, and low scattering rate, but it is sensitive to temperature changes and has relatively poor mechanical strength; zinc selenide has good transmittance in the mid-infrared band, good transmittance in the mid-infrared band, good mechanical strength, and good chemical stability.

[0061] The sealing ring 27 is disposed between the electrolytic cell body 21 and the electrolytic cell cover 26 to ensure the sealing between the two. The sealing ring 27 is made of an elastic material with corrosion resistance and low temperature sealing performance.

[0062] Specifically in this embodiment, the sealing ring 27 is made of fluororubber, which has excellent corrosion resistance and low-temperature sealing performance, and can provide reliable sealing in a low-temperature environment to prevent electrolyte leakage.

[0063] The electrolytic cell cover reinforcement 28 is a circular cover plate, which covers the electrolytic cell cover 26 and does not block the second optical window 26a. The electrolytic cell cover 26 and the electrolytic cell body 21 have a plurality of threaded holes on the edge side of the axial direction thereof, and the electrolytic cell cover reinforcement 28 has a plurality of countersunk through holes on the edge side of the axial direction thereof, which correspond to the positions of the plurality of threaded holes of the electrolytic cell cover 26 and the electrolytic cell body 21. The electrolytic cell cover reinforcement 28, the electrolytic cell cover 26 and the electrolytic cell body 21 are tightly fixed to each other by the mutual cooperation of the bolts 1 and nuts 2 which are passed through them in sequence, and a closed space is formed between the electrolytic cell body 21 and the electrolytic cell cover 26 through the sealing ring 27.

[0064] The electrolytic cell assembly 20 is placed as a whole above the cold end of the cooling sheet 14, and its second optical window 26a is located below the first optical window 111a. The electrolytic cell assembly 20 is used to perform electrochemical experiments through the counter electrode 25, the working electrode 23 and the reference electrode 24 sealed inside the electrolytic cell assembly 20. At the same time, the user performs Raman spectroscopy characterization of the electrochemical experiment performed in the electrolytic cell assembly 20 through the first optical window 111a and the second optical window 26a.

[0065] like Figure 3 As shown, the circulating water tank air pump assembly 30 includes a housing 31 , a cooling medium circulation component 32 and an air supply component 33 .

[0066] The outer shell 31 is used as the overall package of the circulating water tank air pump assembly 30 to place various components, protect the internal components, and provide support and fixing. The outer shell 31 is made of a material with sufficient strength and protective performance.

[0067] Specifically in this embodiment, the housing 31 is made of ABS plastic.

[0068] The cooling medium circulation member 32 includes a circulating water tank 321 , a refrigeration part 322 , an agitator 323 , a heat insulating layer 324 and a circulating pump 325 .

[0069] The circulating water tank 321 is disposed in the housing 31 and is filled with cooling medium. The circulating water tank 321 is connected to two liquid guide pipes connected to the water inlet pipe 13a and the water outlet pipe 13b, thereby providing cooling medium to the water cooling head 13 through the two liquid guide pipes.

[0070] The circulating water tank 321 is a container with corrosion resistance and heat insulation performance. Specifically in this embodiment, the circulating water tank 321 is made of polytetrafluoroethylene (PTFE).

[0071] The refrigeration part 322 is connected to the circulating water tank 321 to cool the cooling medium therein.

[0072] Specifically in this embodiment, the refrigeration part 322 adopts a compressor refrigeration method, which realizes refrigeration through the cyclic phase change of the refrigerant.

[0073] The stirrer 323 is connected to the circulating water tank 321 and stirs the cooling medium therein, thereby ensuring the temperature uniformity of the cooling medium inside the circulating water tank 321 .

[0074] The heat insulation layer 324 covers the circulating water tank 321 to reduce the heat loss of the cooling medium therein, reduce heat exchange, and improve the refrigeration efficiency. Specifically in this embodiment, the heat insulation layer 324 is a heat insulating material.

[0075] The circulation pump 325 is disposed on one of the two liquid guide tubes, and is used to provide circulation power for the cooling medium in the circulation loop formed between the circulation water tank 321, the two liquid guide tubes, and the water cooling head 13. The flow rate and lift of the circulation pump 325 are selected according to the cooling requirements of the hot and cold stage assembly 10 and the physical properties of the cooling medium such as viscosity.

[0076] Specifically in this embodiment, the circulation pump 325 is a centrifugal pump.

[0077] The air supply component 33 includes an air supply pipeline 331 , an air pump 332 and a dryer 333 .

[0078] One end of the air supply pipeline 331 is connected to the atmosphere, and the other end is located beside the first optical window 111a of the test area 111. The pipe body of the air supply pipeline 331 passes through the wall of the circulating water tank 321 and is immersed in the cooling medium therein.

[0079] The air pump 332 is disposed on the air supply pipeline 331 , and is used to provide cold air cooled by a cooling medium to the first optical window sheet 111 a through the air supply pipeline 331 .

[0080] Specifically in this embodiment, the air pump 332 is a diaphragm pump.

[0081] The dryer 333 is disposed on the air supply pipeline 331 and is used to dry the cold air transported therein.

[0082] Specifically in this embodiment, the dryer 333 is a dryer filled with a desiccant.

[0083] The above-mentioned gas supply pipeline 331, air pump 332 and dryer 333 cooperate with each other so that the dry gas is blown onto the upper surface of the first optical window 111a to prevent condensation or frost on the surface.

[0084] like Figure 4As shown, the electronic control component 40 includes a DC regulated power supply 41, an AC power supply 42, a temperature sensor 43, a temperature controller 44, a circuit switch, an RS485 to USB converter, a high liquid level sensor 45, a current / voltage sensor 46, a gas flow meter 47, a gas flow control valve 48 and a controller 49.

[0085] The DC regulated power supply 41 is connected to the cooling plate 14 and the heating plate 12 and supplies power thereto.

[0086] The AC power source 42 is connected to the circulation pump 325 and the air pump 332 and supplies power to them.

[0087] The temperature sensor 43 includes a first temperature sensor 431 , a first temperature transmitter 432 , a second temperature sensor 433 , a second temperature transmitter 434 , a third temperature sensor 435 , a third temperature transmitter 436 , a fourth temperature sensor 437 and a fourth temperature transmitter 438 .

[0088] The first temperature sensor 431, the second temperature sensor 433, the third temperature sensor 435 and the fourth temperature sensor 437 are all thermocouple temperature measuring wires, and are respectively arranged on the cooling plate 14, the heating plate 12, the water cooling head 13 and the opening groove 21a. Among them, the fourth temperature sensor 437 passes through the third reserved hole of the side wall of the electrolytic cell body 21 and probes into the opening groove 21a.

[0089] Specifically in this embodiment, the first temperature sensor 431 , the second temperature sensor 433 , the third temperature sensor 435 and the fourth temperature sensor 437 are T-type thermocouples, K-type thermocouples, Pt100 or thermal resistors.

[0090] The first temperature transmitter 432, the second temperature transmitter 434, the third temperature transmitter 436 and the fourth temperature transmitter 438 are respectively connected to the first temperature sensor 431, the second temperature sensor 433, the third temperature sensor 435 and the fourth temperature sensor 437, and have linearization and cold end compensation functions for converting the signal of the thermocouple temperature measuring line into a standard electrical signal.

[0091] The temperature controller 44 includes a first temperature controller 441 and a second temperature controller 442. The first temperature controller 441 is arranged on a circuit connecting the DC regulated power supply 41 and the cooling plate 14. The second temperature controller 442 is arranged on a circuit connecting the DC regulated power supply 41 and the heating plate 12. The first temperature controller 441 and the second temperature controller 442 are used to control the operating power of the cooling plate 14 and the heating plate 12, respectively.

[0092] There are a number of circuit switches, which are arranged on different lines (not shown in the figure) and are used to open and close according to a preset strategy.

[0093] The RS485 to USB converter is connected to the first temperature transmitter 432, the second temperature transmitter 434, the third temperature transmitter 436, the fourth temperature transmitter 438, the first temperature controller 441 and the second temperature controller 442, and is used to transmit temperature data to the computer through the USB interface, so as to remotely monitor the temperature and control the first temperature controller 441 and the second temperature controller 442 through the computer.

[0094] The high liquid level sensor 45 is disposed in the circulating water tank 321 to detect the high liquid level of the cooling medium stored therein.

[0095] The current / voltage sensor 46 includes a first current / voltage sensor 461 and a second current / voltage sensor 462 , which are respectively arranged on the output lines of the DC regulated power supply 41 and the AC power supply 42 , and are used to detect the current / voltage signals of the DC regulated power supply 41 and the AC power supply 42 .

[0096] The gas flow meter 47 is disposed on the gas supply pipeline 331 to detect the flow rate of the gas transported therein.

[0097] The gas flow control valve 48 is disposed on the gas supply pipeline 331 to control the flow of gas transported therein.

[0098] The controller 49 is a PLC, a single-chip microcomputer or an industrial computer with a preset strategy, and the control algorithm is a PID algorithm, a fuzzy control or a neural network control. The controller 49 is connected with the first temperature transmitter 432, the second temperature transmitter 434, the third temperature transmitter 436, the fourth temperature transmitter 438, the temperature controller 44, the liquid level sensor 45, the current / voltage sensor 46, the gas flow meter 47, the gas flow control valve 48, and a number of circuit switches, and is used to dynamically adjust the working state of the circulation pump 325, the air pump 332, the cooling plate 14, the heating plate 12, the DC stabilized power supply 41 and the AC power supply 42 according to the preset strategy and voltage / current data, different temperature data, liquid level data and gas flow data.

[0099] Specifically in this embodiment, the controller 49 is a PLC that uses a PID algorithm to perform temperature control, and the target temperature control accuracy is ±0.1°C.

[0100] The use process of the experimental device 100 for variable temperature electrochemical Raman spectroscopy characterization: First, after the electrolyte is added into the electrolytic cell body 21 through the third reserved hole on the side wall thereof, the electrochemical experiment is started in cooperation with an external electrochemical workstation.

[0101] Subsequently, in the electrochemical experiment, the hot and cold stage assembly 10 controls the overall temperature of the electrolytic cell assembly 20 through the cooperation of the heating plate 12, the water cooling head 13 and the cooling plate 14, and performs Raman spectroscopy characterization of the electrochemical experiment performed in the electrolytic cell assembly 20 through the first optical window 111a and the second optical window 26a.

[0102] During the entire electrochemical experiment, the temperature of the electrolytic cell assembly 20 and the air pump blowing are controlled according to a predetermined strategy through the circulating water tank air pump assembly 30 and the electronic control assembly 40.

[0103] Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. An experimental device for variable temperature electrochemical Raman spectroscopy characterization, characterized in that: Including hot and cold stage components, electrolytic cell components, circulating water tank air pump components and electronic control components, The hot and cold stage assembly has a water cooling head, a cooling plate connected to the water cooling head, and a heating plate connected to the water cooling head. The hot and cold stage assembly has a first optical window on its outer surface. The electrolytic cell assembly is arranged inside the hot and cold stage assembly and located on the refrigeration plate. The electrolytic cell assembly performs electrochemical experiments through the counter electrode, the working electrode and the reference electrode sealed inside the electrolytic cell assembly. The outer surface of the electrolytic cell assembly has a second optical window. The electrolytic cell assembly is used to perform Raman spectroscopy characterization experiments through the first optical window and the second optical window. The circulating water tank air pump assembly comprises: a cooling medium circulation member connected to and in communication with the water cooling head and used for providing circulating cooling medium to the water cooling head, and an air supply member connected to the cooling medium circulation member and the hot and cold stage assembly, and used for blowing dry gas cooled by the cooling medium in the cooling medium circulation member to the upper surface of the first optical window to prevent frost or fogging; The electronic control assembly comprises: A DC regulated power supply is connected to the cooling plate and the heating plate and supplies power to them. An AC power source is connected to the circulating water tank air pump assembly and supplies power to it, There are several temperature sensors, which are respectively arranged on the water cooling head, the cooling plate, the heating plate and the electrolytic cell assembly. The temperature controllers, 2 in number, are respectively arranged on the power supply lines of the water cooling head and the cooling plate, and are used to control the operating power of the water cooling head and the cooling plate. A liquid level sensor is provided in the cooling medium circulation part and is used to detect the liquid level of the cooling medium stored in the cooling medium circulation part. A plurality of current / voltage sensors are provided on the output lines of the DC regulated power supply and the AC power supply to detect the current / voltage signals of the DC regulated power supply and the AC power supply. Circuit switches, a number of which are installed on different circuits. A controller is connected to the temperature sensor, the temperature controller, the liquid level sensor, the current / voltage sensor and the circuit switch, and is used to dynamically adjust the working state of the circulating water tank air pump assembly and / or the hot and cold stage assembly according to voltage / current data, different temperature data and liquid level data through a preset strategy.

2. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 1, characterized in that: in, The cooling plate is arranged above the water cooling head, and a heat conducting medium is filled between the cooling plate and the water cooling head. The heating plate is arranged below the water cooling head, and a heat conducting medium is filled between the heating plate and the water cooling head.

3. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 1, characterized in that: in, The water cooling head is externally connected to a liquid guide pipe. The liquid guide pipe is in communication with the cooling medium circulation member, so that the cooling medium is circulated and transported to the water cooling head through the cooling medium circulation member.

4. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 3, characterized in that: in, The outer periphery of the liquid guiding tube is coated with a heat preservation tube for reducing heat loss.

5. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 1, Features: in, The electrolytic cell assembly comprises: The electrolytic cell body has an inwardly recessed opening groove, wherein a columnar protrusion is convexly arranged in the opening groove; A working electrode connector is inserted into the cylindrical protrusion and connected to the electrochemical workstation via a wire outside the electrolytic cell assembly; A working electrode, disposed on the cylindrical protrusion and connected to the working electrode connector, wherein the working electrode is located inside the open groove; A reference electrode is disposed in the open slot and connected to an external electrochemical workstation via a wire passing through the electrolytic cell body; A counter electrode is disposed in the open groove and connected to an external electrochemical workstation via a wire passing through the electrolytic cell body, wherein the counter electrode surrounds the working electrode; an electrolytic cell cover, which is detachably disposed on the electrolytic cell body and completely covers the open slot, and the electrolytic cell cover has the second optical window; and A sealing ring is arranged between the electrolytic cell body and the electrolytic cell cover to ensure the sealing between the two.

6. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 5, characterized in that: in, The electrolytic cell body is made of a material having corrosion resistance and low temperature stability. The optical window is made of a material with high transmittance, low fluorescence background and good chemical stability. The counter electrode is a metal wire with high conductivity and chemical stability. The working electrode connector is made of a material with high conductivity, corrosion resistance and mechanical strength. The reference electrode is a metal wire quasi-reference electrode, The sealing ring is made of an elastic material with corrosion resistance and low-temperature sealing performance.

7. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 1, Features: in, The cooling medium circulation member comprises: A circulating water tank filled with a cooling medium, the circulating water tank being connected to the water cooling head so as to convey the circulating cooling medium to the water cooling head; A refrigeration part, connected to the circulating water tank to cool the cooling medium; as well as A circulation pump is arranged on a passage connecting the circulating water tank and the water cooling head to provide power for the circulation of the cooling medium.

8. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 7, Features: in, The cooling medium circulation member also includes: an agitator connected to the circulating water tank and stirring the cooling medium therein; and The heat insulation layer at least covers the circulating water tank to reduce the heat loss of the cooling medium.

9. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 1, Features: in, The gas supply member comprises: An air supply pipeline, one end of which is connected to the atmosphere, and the other end of which is connected and connected to the hot and cold stage assembly and the pipe mouth is located beside the first optical window, and the pipe body of the air supply pipeline is at least partially immersed in the cooling medium; an air pump, disposed on the air supply pipeline, for providing blowing cold air to the first optical window sheet through the air supply pipeline; as well as The dryer is arranged on the air supply pipeline and is used for drying the cold air transported by the air supply pipeline.

10. The experimental device for variable temperature electrochemical Raman spectroscopy characterization according to claim 9, characterized in that: in, The electronic control assembly also includes a gas flow meter and a gas flow control valve. The gas flow meter and the gas flow control valve are arranged on the gas supply pipeline and connected to the controller. The controller also controls the gas flow control valve according to a predetermined strategy based on the data transmitted by the gas flow meter.

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