CN106770158A - Electrochemistry in-situ high temperature Raman spectroscopy tests hot system - Google Patents
Electrochemistry in-situ high temperature Raman spectroscopy tests hot system Download PDFInfo
- Publication number
- CN106770158A CN106770158A CN201611069062.3A CN201611069062A CN106770158A CN 106770158 A CN106770158 A CN 106770158A CN 201611069062 A CN201611069062 A CN 201611069062A CN 106770158 A CN106770158 A CN 106770158A
- Authority
- CN
- China
- Prior art keywords
- sample
- hot
- electrochemistry
- high temperature
- raman spectroscopy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Hot system is tested the invention discloses a kind of electrochemistry in-situ high temperature Raman spectroscopy, including：Hot cavity, it includes base, chamber body and top pressure closure；Temperature-control units are surveyed, it includes heater block and temperature thermocouple；Sample load bearing component, it includes sample stage and fastener, and sample stage has the second hollow alundum tube and corundum top cover；Current collector part, it includes first electrode flow concentrating part and second electrode flow concentrating part, and first electrode flow concentrating part uses probe feeler lever afflux, second electrode flow concentrating part to use platinum filament platinum guaze afflux；Feed part manually, and it includes feed manually bar, seal and crucible；Water-cooling section, is made up of water collar and the coolant guide pipe being welded on water collar.The system can apply to the electrochemical signals and Raman spectral information of the electrochemical system under on-line measurement hot operation state, preferably meet use demand, simple easily to realize.
Description
Technical field
The present invention relates to high-temperature electrochemistry and field of spectral analysis technology, more particularly to a kind of electrochemistry high-temp in-situ Raman
The hot system of spectrum test.
Background technology
At present, conventional electrochemical research method of testing is main using electric signal as motivator, by measuring electrochemistry
The electrical response of system is so as to speculate course of reaction and potential mechanism.But, what the method was obtained is all microscopic informations of system
Macroscopical summation, cause to lack pilot process, the visual information of intermediate product, so as to cause difficulty to the discriminating of reaction mechanism.
Raman spectrum is an important modern molecular spectral technique, using the fingerprint characteristic of Molecular Raman spectrum, can be with
Intuitively differentiate interatomic bonded mode in molecule, be suitable for the sign of group and molecular structure, be widely used in chemistry, thing
The substance characterization of the ambits such as reason, bioscience.Therefore, develop electro-chemical test means and Raman Characterization means phase
With reference to electrochemical in-situ spectroscopy technique be applied to the research of electrochemical system, by the research lifting of reaction mechanism to molecule in situ
Dynamic level, while can online obtain the macroscopic information of reflection chemical property again, can greatly advance grinding for electrochemical system
Study carefully.
In correlation technique, electrochemical in-situ Raman spectroscopy test device focuses mostly in the original of low temperature solid liquid phase electrochemical system
Position research, such as：Direct liquid fuel battery, lithium battery, metal erosion electrochemical research etc., in the surface Raman of solid/liquid interfaces
Some impressive progresses are achieved in spectral investigation.But for suitable for high temperature solid-state electrochemical system, including SOFC (Solid
Oxide Fuel Cell, SOFC), DCFC (direct carbon fuel cell, direct carbon fuel electricity
Pond) etc. electrochemical in-situ Raman spectrum combination test system lack very much.Because Raman scattering of molecule signal is incident laser
The 10 of signal-6-10-9, can be increased by the operating distance the distance between (microlens with sample) for reducing Raman optical system
Big solid angle so as to strengthen the raman spectral signal being collected into, but as operating distance reduces near the high-temperature region where sample
Section, a large amount of heat radiations can cause heavy corrosion to microscopic Raman camera lens.
Therefore, the contradiction in operating distance of mediation optic test and high temperature hot state environment is high-temperature electrochemistry drawing in situ
The crucial problem of graceful test device.Additionally, test device is for the requirement such as security, air-tightness, current collector and measuring and controlling temp
It is more harsh, at the same time it is wished that disclosure satisfy that handling, addition sample in situ are convenient and swift.For above reason, electrochemistry high temperature is former
The design processing of position Raman test device is complex, and similar device existing both at home and abroad is difficult to while meeting above bar at present
Part.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.
Therefore, it is an object of the invention to propose that a kind of electrochemistry in-situ high temperature Raman spectroscopy tests hot system, this is
System can apply to the electrochemical signals and Raman spectral information of the electrochemical system under on-line measurement hot operation state, more preferably
Ground meets use demand.
To reach above-mentioned purpose, the embodiment of the present invention proposes a kind of electrochemistry in-situ high temperature Raman spectroscopy and tests hot system
System, including：Hot cavity, the hot cavity includes base, chamber body and top pressure closure, wherein, the chamber body
Top is set to opening, and the bottom of the chamber body is provided with through hole, and the chamber body passes through with the top pressure closure
Flange seal completes sealing, and top pressure closure inner side is coated with exotic material, and the middle part of the top pressure closure is inside
It is recessed and is provided with through hole, to be provided for the sapphire glass disk of laser signal discrepancy；Survey temperature-control units, the observing and controlling temperature portion
Part includes heater block and temperature thermocouple, and the heater block is fixed on the center of the chamber body, and the heating part
Part fills up porous insulation material layer with chamber inner wall, and the heater block has the first hollow alundum tube and heater strip, wherein, institute
The outer wall for stating the first hollow alundum tube is set by screw thread, to fix and support the heater strip, is set outside the temperature thermocouple
There is into the thin corundum sleeve pipe of section, and two thermocouples are provided with cavity, thermometric head and the sample of the first thermocouple keep
Identical height, to detect the temperature of response location, and the thermometric head of the second thermocouple is consistent with bringing-up section middle part, to supervise
Control cavity temperature highest point；Sample load bearing component, the sample load bearing component includes sample stage and fastener, the sample stage tool
There are the second hollow alundum tube and corundum top cover, fit sealing is carried out with by the described second hollow alundum tube and corundum top cover, its
In, the sample stage is stretched into from the bottom of the hot cavity, so that sample position is in the center of the heater block；Electric current
Flow concentrating part, the current collector part includes first electrode flow concentrating part and second electrode flow concentrating part, the hot cavity
Interior first electrode flow concentrating part uses probe feeler lever afflux, second electrode flow concentrating part to use platinum filament platinum guaze afflux；Add manually
Material part, the manual charging part includes charging bar, seal and crucible manually, wherein, the manual charging bar is provided with
Clamp structure, the crucible of sample is filled with to clamp；Water-cooling section, the water-cooling section is by water collar and is welded on described
Coolant guide pipe composition on water collar.
The electrochemistry in-situ high temperature Raman spectroscopy of the embodiment of the present invention tests hot system, it is possible to achieve to test battery
The functions such as sealing, addition sample in situ, current collector, the supply of anode and cathode gas, measuring and controlling temp, while can be by just to sample
The optical glass form of position is in situ to catch Raman spectrum, and by careful structure design, realizes compact conformation, dismounting
The functions such as convenient and local water-cooled cooling, such that it is able to apply to the electrochemical system under on-line measurement hot operation state
Electrochemical signals and Raman spectral information, and can preferably meet use demand, it is simple easily to realize.
In addition, electrochemistry in-situ high temperature Raman spectroscopy according to the above embodiment of the present invention tests hot system can also have
There is following additional technical characteristic：
Further, in one embodiment of the invention, the heater strip is Aludirome heater strip, described first
The outer wall of hollow alundum tube is machined with support and fixation of the external screw thread for the Aludirome heater strip.
Further, in one embodiment of the invention, the sample stage is corundum material, the second hollow corundum
One end of pipe processes fluted and external screw thread, and top cover is machined with internal thread, with the fixation sample.
Further, in one embodiment of the invention, the sample stage be design for disassembly, by O-shaped rubber ring,
Wedge-shaped inner sleeve and threaded cap coordinate the sealing and fixation for realizing the sample stage with the bottom of the hot cavity by screw thread.
Further, in one embodiment of the invention, when using probe feeler lever afflux, by being fixed on feeler lever end
The rhenium silk probe collected current in portion, and the electric current is drawn by the copper wire in the middle part of feeler lever.
Further, in one embodiment of the invention, feeler lever afterbody is provided with ambroin sleeve, by with base
With the connection of three-dimensional three coordinate translations platform, rhenium silk probe position in cavity is set to carry out on-line control.
Further, in one embodiment of the invention, connected by the fast acting flange at welded metal bellow and two ends
Connect and current-collecting device is sealed.
Further, in one embodiment of the invention, the manual charging part is arranged on the chamber body
Outer wall.
Further, in one embodiment of the invention, connected to described manual by level Four O-shaped rubber ring and flange
Charging part and the hot cavity are sealed.
Further, in one embodiment of the invention, the water-cooling section is arranged at the lower section of the chamber body
With top pressure closure top, cooled down with to the hot key position of high temperature.
The additional aspect of the present invention and advantage will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by practice of the invention.
Brief description of the drawings
The above-mentioned and/or additional aspect of the present invention and advantage will become from the following description of the accompanying drawings of embodiments
Substantially and be readily appreciated that, wherein：
Fig. 1 is that the structure for testing hot system according to the electrochemistry in-situ high temperature Raman spectroscopy of one embodiment of the invention is shown
It is intended to；
Fig. 2 is the structural representation of the sample stage according to one embodiment of the invention；
Fig. 3 is the structural representation of the metal feeler lever pole socket according to one embodiment of the invention；
Fig. 4 is the structural representation on the metal feeler lever chassis according to one embodiment of the invention；
Fig. 5 is the assembling schematic diagram of the probe feeler lever current-collecting device according to one embodiment of the invention
Fig. 6 is the Raman spectrum schematic diagram of the Zirconia electrolytic of the stabilized with yttrium oxide according to one embodiment of the invention；
Fig. 7 is the VA characteristic curve of the liquid antimony anode SOFC according to one embodiment of the invention
Schematic diagram.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
It is exemplary to scheme the embodiment of description, it is intended to for explaining the present invention, and be not considered as limiting the invention.
First, hot system is tested to the electrochemistry in-situ high temperature Raman spectroscopy for proposing according to embodiments of the present invention below to enter
Row is described in detail.
The electrochemistry in-situ high temperature Raman spectroscopy tests hot system to be included：Hot cavity, survey temperature-control units, sample are carried
Part, manually current collector part, charging part and water-cooling section.
Wherein, hot cavity includes base, chamber body and top pressure closure, wherein, it is set to open at the top of chamber body
Mouthful, and the bottom of chamber body is provided with through hole, chamber body completes to seal with top pressure closure by flange seal, and seals
Inside of top cover is coated with exotic material, and through hole is caved inward and be provided with the middle part of top pressure closure, to be provided for laser signal
The sapphire glass disk of discrepancy.Surveying temperature-control units includes heater block and temperature thermocouple, and heater block is fixed on chamber master
The center of body, and heater block and chamber inner wall fill up porous insulation material layer, heater block have the first hollow alundum tube and
Heater strip, wherein, the outer wall of the first hollow alundum tube is set by screw thread, with fixed and support heater strip, temperature thermocouple peripheral hardware
The thin corundum sleeve pipe of section is equipped with into, and two thermocouples are provided with cavity, thermometric head and the sample of the first thermocouple are protected
Identical height is held, to detect the temperature of response location, and the thermometric head of the second thermocouple is consistent with bringing-up section middle part, with
Monitoring cavity temperature highest point.Sample load bearing component include sample stage and fastener, sample stage have the second hollow alundum tube and
Corundum top cover, fit sealing is carried out with by the second hollow alundum tube and corundum top cover, wherein, sample stage is from the bottom of hot cavity
Portion stretches into, so that sample position is in the center of heater block.Current collector part includes first electrode flow concentrating part and second
Electrode current collecting part, the first electrode flow concentrating part in hot cavity uses probe feeler lever afflux, second electrode flow concentrating part to adopt
With platinum filament platinum guaze afflux.Charging part includes charging bar, seal and crucible manually manually, wherein, charging bar is provided with manually
Clamp structure, the crucible of sample is filled with to clamp.Water-cooling section is by water collar and the coolant guide pipe being welded on water collar
Composition.The system can apply to the electrochemical signals and Raman spectrum of the electrochemical system under on-line measurement hot operation state
Information, preferably meets use demand, simple easily to realize.
For example, in an embodiment of the present invention, the system of the embodiment of the present invention include hot main body, top pressure closure,
Survey temperature-control units, sample load bearing component, manually current collector part, charging part and water-cooling section.Wherein, hot body interior
Porous insulation material can be set；It is wrapped in and is machined with the heater strip such as Aludirome of externally threaded hollow corundum pipe outer wall and adds
Heated filament can be as hot built-in thermal source, installed in hot cavity center；Sample load bearing component is stretched by hot cavity lower section
Enter, be connected through a screw thread fixation, sample position is in the middle of cavity；Electrode current collecting in hot cavity uses probe feeler lever collection
Stream device, dynamic sealing is realized by welding bellows and three-dimensional three coordinate translations platform；Hot cavity wall is provided with charging manually
Device, charging bar Front-end Design has clamp structure, is connected by flange and level Four O-shaped rubber ring realizes dynamic sealing；Top pressure closure
Water-cooling cooling device is respectively arranged below with hot cavity, for protection device and personal security.
Further, in one embodiment of the invention, heater strip is Aludirome heater strip, the first hollow corundum
The outer wall of pipe is machined with support and fixation of the external screw thread for Aludirome heater strip.
That is, hollow corundum pipe outer wall is machined with external screw thread for the support and fixation of Aludirome heater strip,
Porous insulation material is filled up between heater block and hot cavity, hot cavity and top pressure closure inner-wall spraying have corundum.
Further, in one embodiment of the invention, sample stage is corundum material, one end of the second hollow alundum tube
Fluted and external screw thread is processed, top cover is machined with internal thread, to fix sample.
It is understood that sample stage can be corundum material, hollow alundum tube one end processes fluted and external screw thread, pottery
Porcelain top cover is machined with internal thread, is coordinated by screw thread and realizes that sample is fixed.
Further, in one embodiment of the invention, sample stage is design for disassembly, by O-shaped rubber ring, wedge shape
Inner sleeve and threaded cap coordinate the sealing and fixation for realizing sample stage with the bottom of hot cavity by screw thread.
It should be noted that sample stage is design for disassembly, by O-shaped rubber ring, wedge-shaped inner sleeve and threaded cap and heat
State cavity bottom coordinates the sealing and fixation for realizing sample stage by screw thread.
Further, in one embodiment of the invention, when using probe feeler lever afflux, by being fixed on feeler lever end
The rhenium silk probe collected current in portion, and by the copper wire extracted current in the middle part of feeler lever.
That is, the current collection mode of hot inside cavity electrode uses probe feeler lever afflux, by being fixed on feeler lever end
The rhenium silk probe collected current in portion, by the copper wire extracted current in the middle part of feeler lever.
Further, in one embodiment of the invention, feeler lever afterbody is provided with ambroin sleeve, by with base
With the connection of three-dimensional three coordinate translations platform, rhenium silk probe position in cavity is set to carry out on-line control.
Say, feeler lever afterbody is equipped with ambroin sleeve, by the connection with base and three-dimensional three coordinate translations platform, realize
The on-line control of rhenium silk probe position in cavity.
Further, in one embodiment of the invention, connected by the fast acting flange at welded metal bellow and two ends
Connect and current-collecting device is sealed.
It is understood that connect realizing the close of current-collecting device by the fast acting flange at welded metal bellow and two ends
Envelope.
Further, in one embodiment of the invention, charging part is arranged on the outer wall of chamber body manually.
That is, hot chamber outer wall is provided with manual feeding device, charging bar Front-end Design has clamp structure manually,
Crucible is clamped using the toughness of stainless steel, is realized online to sample position charging.
Further, in one embodiment of the invention, connected to charging manually by level Four O-shaped rubber ring and flange
Part and hot cavity are sealed.
Say, connected by level Four O-shaped rubber ring and flange and realize its dynamic sealing with hot main body.
Further, in one embodiment of the invention, water-cooling section is arranged at the lower section of chamber body and sealing is pushed up
The side of covering, cools down with to the hot key position of high temperature.
It is understood that top pressure closure top is designed with chilled water unit for reducing the temperature of optical window superjacent air space
Degree, hot cavity envisaged underneath has chilled water unit that the temperature of O-shaped rubber ring is sealed for reducing sample stage.
Specifically, in one embodiment of the invention, the electrochemistry in-situ high temperature Raman spectroscopy of the embodiment of the present invention
Testing hot system includes hot capsule components, survey temperature-control units, sample load bearing component, gas supply member, current collector portion
Part, manually charging part and water-cooling section.
Wherein, hot capsule components include base, chamber body and top pressure closure, and base and chamber body are integrated and set
Meter, is stainless steel.Chamber body is the core of whole test device, and its top is open design, and outer wall circumference is respectively
Design is machined with manual feeding device, probe feeler lever current-collecting device and gas supply device, and bottom is provided with through hole for loading and unloading sample
Product bogey.Chamber body uses flange seal with top pressure closure, by O-shaped O-ring seal and 8 equally distributed fastenings
Bolt forms sealing.Top pressure closure inner side is coated with exotic material, and top cover middle part caves inward and is provided with through hole, equipped with being used for
The sapphire glass disk that laser signal comes in and goes out, sealing is formed by O-shaped O-ring seal and fastening bolt.
Further, surveying temperature-control units includes heater block and temperature thermocouple.Heater block include hollow alundum tube and
Heater strip.Corundum pipe outer wall is threaded, for fixed and support winding Aludirome heater strip.Heater block is fixed
In chamber body center, as the built-in thermal source of hot chamber.Heater block fills up porous insulation material layer with chamber inner wall, many
The effect of hole insulation material is to increase thermal conduction resistance, reduces hot chamber outer wall temperature, it is ensured that experimental implementation security.Thermocouple
The outer thin corundum sleeve pipe for having into section, is disposed with two thermocouples in cavity, a thermocouple temperature measurement head is identical with sample holding
Highly, for detecting the temperature of response location；Another thermocouple temperature measurement head is consistent with bringing-up section middle part, in monitoring chamber
Temperature highest point, protects heater block.
Further, sample load bearing component includes sample stage and fastener two parts.Sample stage is corundum material, including one
Determine the hollow alundum tube and corundum top cover of thickness, the conventional circular batteries substrate of experiment test is placed on alundum tube side groove
It is interior, coordinated using the screw thread of alundum tube and corundum top cover and realize fit sealing.Sample stage is stretched into from hot cavity bottom so that sample
Grade is put and is in heater block center.The installation of sample stage and the fixed screw thread by hot cavity bottom and overcoat top cover coordinate
Realize, while realizing that cavity is sealed built with taper inner sleeve and O-shaped rubber ring.
Further, gas supply member includes the gas inlet and outlet pipe of the two poles of the earth chamber respectively.Test battery the two poles of the earth are main
Separated by sample stage, outlet pipe is entered in main chamber for stainless steel, gas skims over sample full of chamber by side wall entrance pipe
Body, then discharged by the gas outlet tube of homonymy.Opposite side electrode chambers are made up of space in sample stage alundum tube, gas inlet tube
It is alundum tube, gas flows through by after porous afflux platinum guaze from the annular housing between sample stage alundum tube and gas inlet tube,
Discharged via gas outlet hole.
Further, current collector part includes the two poles of the earth flow concentrating part respectively.Electrode current collecting part in hot cavity is adopted
With probe feeler lever afflux.Rhenium silk probe and the electrode surface of feeler lever front end are in close contact collected current, are pressed on by by reed
Current signal is drawn cavity by the copper wire in the middle part of feeler lever；Feeler lever is equipped with ambroin sleeve away from the end of electrode, by metal
Base is fixed on three-dimensional three coordinate translations platform, realizes the on-line control of current acquisition position；Three-dimensional coordinate translation stage and cavity
Between sealing adjustable dynamic sealing is realized by welding bellows.Opposite side electrode current collecting uses platinum filament platinum guaze afflux, using gas
Platinum guaze is pressed on electrode surface collected current signal by body inlet tube, and afflux platinum filament draws electric current through gas inlet tube.
Further, charging part includes charging bar, seal and crucible manually manually.Charging bar Front-end Design has manually
Clamp structure, the TGA crucibles for clamping filling sample.Charging bar and hot cavity fixation and sealing by flange connect with
Level Four rubber ring is realized.
Further, water-cooling section includes water collar and the coolant guide pipe composition being welded thereon.In order to realize high temperature
Hot key position cools, and device is designed with two-way water-cooled.Lead up to flange and be fastened on hot top cover middle part,
The optical lens of the temperature for reducing optical window position, protection optical window and the collection of top Raman spectrum.Another road
Water-cooled is arranged on hot bottom, and the O-shaped O-ring seal of sample stage sealing is realized for cooling down, and prevents seal failure.
Secondly, the electrochemistry in-situ high temperature Raman spectroscopy for describing to propose according to embodiments of the present invention below with reference to accompanying drawings is surveyed
Try hot system.
As shown in figure 1, Fig. 1 is to test hot system according to the electrochemistry in-situ high temperature Raman spectroscopy of one embodiment of the invention
The structural representation of system.
As shown in figure 1, hot cavity (2) is fixed on base (1).Aludirome heater strip (7) is wrapped in and is machined with
Externally threaded hollow alundum tube (6) outer wall, alundum tube is fixed on hot cavity center as built-in thermal source, there is provided temperature needed for reaction
Degree.Porous insulation material is filled up between alundum tube and hot cavity inner wall.Hot cavity bottom is provided with through hole, for carrying sample
Sample stage (9) stretched into from bottom, realize hot cavity using the extruding force of cone-shaped metal sleeve (11) and O-shaped rubber ring (12)
The sealing of bottom, the fixation for realizing sample stage is connected by the external screw thread of internal thread top cover (10) and hot cavity bottom.It is fixed
Sample position is near heater strip top one end afterwards.The K-type thermocouple (8) of thermometric is through porous insulation material so that thermometric head
It is consistent with height of specimen, the real time temperature for monitoring sample position.Hot cavity is designed for open top, with top pressure closure
(3) connected by flange and O-shaped rubber ring (4) realizes top sealing.Top pressure closure center is machined with stepped hole, equipped with for drawing
The sapphire optical glass (5) of the laser optical path turnover of graceful spectra collection, is connected using the flange of water collar (22) and top cover
Realize the sealing of optical glass.Hot cavity wall is designed with manual feeding device.Charging bar (18) Front-end Design has folder manually
Structure is held, is used to load the crucible (19) of sample using the elastic clamping of stainless steel thin slice, for online to sample in test process
Sample platform position feeds.The fastening and sealing of charging bar are connected by the flange of fastener (20) and hot chamber outer wall structure
Connect, and level Four O-shaped rubber ring (21) is realized.Test galvanic anode afflux in hot cavity uses probe feeler lever afflux
Device.Rhenium silk probe (14) is fixed on the front end of feeler lever long (15), and collected current signal is touched by the contiguity with anode surface, by
Feeler lever conduction long, then derive cavity by being connected to the copper wire in the middle of feeler lever long.Feeler lever afterbody long is designed with ambroin sleeve, leads to
Cross plastic sleeve to be connected with feeler lever base (17), feeler lever base is fixed with the three-dimensional three coordinate translations platform of commercialization, so as to realize visiting
Three-dimensional regulation of the pin in test process.The sealing of probe feeler lever current-collecting device uses flexible metal welding bellows (16),
Connected by flange and realize that sealing is fixed.Cathode chamber is made up of space in sample stage alundum tube, and cathode collector uses platinum filament platinum
Net afflux, cathode surface collected current signal is pressed on by thin alundum tube (13) by platinum guaze, then by being connected on platinum guaze
Platinum filament draws electric current.Water collar (22) is designed with top pressure closure and is surveyed for cooling down optical glass environment temperature, protection top
The Raman optical lens of examination.Hot cavity bottom is also configured with water collar (23) for reducing the temperature of O-shaped rubber ring (12), prevents
Only sample stage seal failure.
Further, it is conventional for supporting as shown in Fig. 2 hollow alundum tube (9-1) the top processing of heavy wall is fluted
Test cell substrate (9-3), then coat high-temperature seal adhesive realization sealing.Alundum tube top threading, pushes up by with ceramics
The screw thread cooperation for covering (9-2) compresses cell substrate.By sample stage fixing seal after hot cavity, battery the two poles of the earth are also achieved
The separation of chamber, its Anodic is in hot main chamber, and cathode chamber is alundum tube inner cavity chamber.
Further, as shown in figure 3, anode current collector feeler lever afterbody is equipped with plastic sleeve, sleeve and through hole by tight fit
(26) by tight fit so that feeler lever is fixed on pole socket, extraction of the through hole (25) for afflux wire.
Further, as shown in figure 4, being coordinated by the screwed hole (27) on the through hole (24) on feeler lever pole socket and chassis,
So as to feeler lever pole socket is fixed on chassis.Chassis is fixed on three-dimensional three coordinate translations platform by four through holes (28), so that
Meet the requirement of probe feeler lever afflux system three-dimensional coordinate regulation.The extraction of through hole (29) on chassis for afflux wire.
In addition, as shown in figure 5, feeler lever and pole socket (30) by being tightly fixed after, pole socket is bolted on chassis
(17) on.Chassis is connected realization sealing with welding bellows (16) by flange.Welding bellows is same with the sealing of hot cavity
Sample is connected by flange and realized.
For example, and the embodiment of the present invention hot system support Raman spectrometer for Ocean Optics companies
QE65Pro Raman spectrometers, laser is the 473nm blue lasers of power 100mW, and electrochemical workstation is Germany Zahner
Company's IM6ex electrochemical workstations.
Test hot system using the electrochemistry high-temp in-situ Raman of the embodiment of the present invention carries out liquid under the conditions of 1073K
Antimony metal anode solid oxide fuel cell system is tested, and specific operation process is as follows：
Zirconium oxide (YSZ) electrolyte matrix that one side is brushed with the stabilized with yttrium oxide of platinum slurry is placed on sample stage alundum tube
In groove, high-temperature seal adhesive is coated and ceramic coping of screwing on.Sample stage is fixed on hot cavity, cell piece position is in
The end of heater strip.The position of thermocouple temperature measurement head is adjusted, it is adjacent to ceramic coping.To adding appropriate metallic antimony in crucible
Powder, crucible is clamped on charging bar manually.Top pressure closure is prevented, bolt is tightened and is realized that cavity is sealed.Open two-way circulation
Cooling water, to be passed through in chamber body argon gas as protection gas.Heating schedule is set, starts heating.When temperature reaches 1073K
When, the metallic antimony powder in crucible is poured on YSZ substrate surfaces by the bar that manually feeds, and makes its rapid thawing balling-up.Negative electrode profit
Platinum guaze is pressed close in cathode surface with thin alundum tube, anode is caused in metal probe contact by operating three-dimensional three coordinate translations platform
Antimony drop, electro-chemical test is carried out using electrochemical workstation.Can be to carrying out Raman spectrum in system in whole temperature-rise period
Collection.
Raman spectrum under the normal temperature and high temperature of the electrolyte YSZ substrates measured using Raman spectrometer as shown in fig. 6,
It can be seen that system can be obtained, signal to noise ratio is very high, characteristic peak clearly Raman spectrum, and the temperature of Raman spectrum is reflected well
Effect.
Liquid antimony metal anode SOFC remains able to maintain electricity by autoxidation in the case where anode is without fuel
The operation in pond, the pattern is referred to as " battery mode ".Its operation principle is：O2Obtained at the cathode-electrolyte interfacial of cathode side
It is electronically generated O2-, O2-Anode-electrolyte interface being transported to through electrolyte, oxidation reaction, electrochemistry occur with liquid antimony metal
Reaction is mainly：
2Sb+3O2-→Sb2O3+6e-。
Therefore, liquid antimony metal anode SOFC battery mode operation under overall reaction be：
2Sb+3O2→Sb2O3。
As shown in fig. 7, Fig. 7 is the liquid antimony metal anode soild oxide measured using electrochemical workstation under 1073K
The high s/n ratio of fuel cell and steady and audible VA characteristic curve, so demonstrate electrochemical test system result can
By property.
Electrochemistry in-situ high temperature Raman spectroscopy according to embodiments of the present invention tests hot system, it is possible to achieve to test electricity
The functions such as the sealing in pond, addition sample in situ, current collector, the supply of anode and cathode gas, measuring and controlling temp, while can be by just right
The optical glass form of sample position is in situ to catch Raman spectrum, and by careful structure design, realize compact conformation,
The function such as convenient disassembly and local water-cooled cooling, such that it is able to apply to the electrochemistry body under on-line measurement hot operation state
The electrochemical signals and Raman spectral information of system, and can preferably meet use demand, it is more safe and reliable, it is simple easily real
It is existing.
In the description of the invention, it is to be understood that term " " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", " on ", D score, "front", "rear", "left", "right", " vertical ", " level ", " top ", " bottom " " interior ", " outward ", " up time
The orientation or position relationship of the instruction such as pin ", " counterclockwise ", " axial direction ", " radial direction ", " circumference " be based on orientation shown in the drawings or
Position relationship, is for only for ease of the description present invention and simplifies description, must rather than the device or element for indicating or imply meaning
With specific orientation, with specific azimuth configuration and operation, therefore must be not considered as limiting the invention.
Additionally, term " first ", " second " are only used for describing purpose, and it is not intended that indicating or implying relative importance
Or the implicit quantity for indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or
Implicitly include at least one this feature.In the description of the invention, " multiple " is meant that at least two, such as two, three
It is individual etc., unless otherwise expressly limited specifically.
In the present invention, unless otherwise clearly defined and limited, term " installation ", " connected ", " connection ", " fixation " etc.
Term should be interpreted broadly, for example, it may be fixedly connected, or be detachably connected, or integrally；Can be that machinery connects
Connect, or electrically connect；Can be joined directly together, it is also possible to be indirectly connected to by intermediary, can be in two elements
The connection in portion or two interaction relationships of element, unless otherwise clearly restriction.For one of ordinary skill in the art
For, can as the case may be understand above-mentioned term concrete meaning in the present invention.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score can be with
It is the first and second feature directly contacts, or the first and second features are by intermediary mediate contact.And, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature are directly over second feature or oblique upper, or be merely representative of
Fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " can be
One feature is immediately below second feature or obliquely downward, or is merely representative of fisrt feature level height less than second feature.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611069062.3A CN106770158B (en) | 2016-11-28 | 2016-11-28 | Electrochemistry in-situ high temperature Raman spectroscopy tests hot system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611069062.3A CN106770158B (en) | 2016-11-28 | 2016-11-28 | Electrochemistry in-situ high temperature Raman spectroscopy tests hot system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106770158A true CN106770158A (en) | 2017-05-31 |
| CN106770158B CN106770158B (en) | 2019-07-02 |
Family
ID=58904247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611069062.3A Active CN106770158B (en) | 2016-11-28 | 2016-11-28 | Electrochemistry in-situ high temperature Raman spectroscopy tests hot system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106770158B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706470A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院化学研究所 | A kind of optical observation solid state battery interface detection device in situ |
| TWI648525B (en) * | 2017-12-18 | 2019-01-21 | 國家中山科學研究院 | Device for measuring thermal field distribution inside crucible |
| CN109540870A (en) * | 2019-01-15 | 2019-03-29 | 大连齐维科技发展有限公司 | Confocal laser-scanning microscopy instrument reaction tank |
| CN111913094A (en) * | 2020-06-24 | 2020-11-10 | 中国电子科技集团公司第五十五研究所 | GaN chip high junction temperature testing device based on Raman method |
| CN113390935A (en) * | 2021-07-21 | 2021-09-14 | 清华大学 | High-temperature electrochemical test system |
| CN114062345A (en) * | 2021-11-01 | 2022-02-18 | 北京科技大学 | Method for in-situ measurement of components of phase change or oxidation ablation products of materials under extreme conditions |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203881684U (en) * | 2014-04-15 | 2014-10-15 | 深圳市贝特瑞新能源材料股份有限公司 | In-situ Raman electrolytic cell |
| CN104502324A (en) * | 2014-12-29 | 2015-04-08 | 东北大学 | Micro heating platform for measuring molten salt electriochemistry in-situ Raman spectrum and sample cell |
| CN204903401U (en) * | 2015-08-21 | 2015-12-23 | 深圳市华天通科技有限公司 | Lithium cell electrode material life -span detecting system based on normal position raman and electrochemistry composite algorithm |
| CN105403553A (en) * | 2015-12-31 | 2016-03-16 | 中国科学技术大学 | Thin-layer flow electrolytic cell applicable to electrochemical in-situ Raman spectrum detection |
| CN105738344A (en) * | 2016-04-26 | 2016-07-06 | 东北大学 | Microscope hot stage and sample pool system used for electrochemistry in-situ Raman spectrum measurement |
| CN105866097A (en) * | 2016-04-01 | 2016-08-17 | 西南科技大学 | Method for producing carbon fiber sample for Raman spectrum test |
-
2016
- 2016-11-28 CN CN201611069062.3A patent/CN106770158B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203881684U (en) * | 2014-04-15 | 2014-10-15 | 深圳市贝特瑞新能源材料股份有限公司 | In-situ Raman electrolytic cell |
| CN104502324A (en) * | 2014-12-29 | 2015-04-08 | 东北大学 | Micro heating platform for measuring molten salt electriochemistry in-situ Raman spectrum and sample cell |
| CN204903401U (en) * | 2015-08-21 | 2015-12-23 | 深圳市华天通科技有限公司 | Lithium cell electrode material life -span detecting system based on normal position raman and electrochemistry composite algorithm |
| CN105403553A (en) * | 2015-12-31 | 2016-03-16 | 中国科学技术大学 | Thin-layer flow electrolytic cell applicable to electrochemical in-situ Raman spectrum detection |
| CN105866097A (en) * | 2016-04-01 | 2016-08-17 | 西南科技大学 | Method for producing carbon fiber sample for Raman spectrum test |
| CN105738344A (en) * | 2016-04-26 | 2016-07-06 | 东北大学 | Microscope hot stage and sample pool system used for electrochemistry in-situ Raman spectrum measurement |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706470A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院化学研究所 | A kind of optical observation solid state battery interface detection device in situ |
| TWI648525B (en) * | 2017-12-18 | 2019-01-21 | 國家中山科學研究院 | Device for measuring thermal field distribution inside crucible |
| CN109540870A (en) * | 2019-01-15 | 2019-03-29 | 大连齐维科技发展有限公司 | Confocal laser-scanning microscopy instrument reaction tank |
| CN111913094A (en) * | 2020-06-24 | 2020-11-10 | 中国电子科技集团公司第五十五研究所 | GaN chip high junction temperature testing device based on Raman method |
| CN113390935A (en) * | 2021-07-21 | 2021-09-14 | 清华大学 | High-temperature electrochemical test system |
| CN114062345A (en) * | 2021-11-01 | 2022-02-18 | 北京科技大学 | Method for in-situ measurement of components of phase change or oxidation ablation products of materials under extreme conditions |
| CN114062345B (en) * | 2021-11-01 | 2022-11-15 | 北京科技大学 | Method for in-situ measurement of components of phase change or oxidation ablation products of materials under extreme conditions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106770158B (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106770158A (en) | Electrochemistry in-situ high temperature Raman spectroscopy tests hot system | |
| CN105738344B (en) | A kind of electrochemical in-situ raman spectroscopy measurement microscopic heating stand and sample cell system | |
| CN104502324B (en) | Melten salt electriochemistry original position Raman spectral measurement microscopic heating stands | |
| US8152978B2 (en) | Apparatus and method for measuring hydrogen concentration in molten metals | |
| US4636292A (en) | Electrode for electrochemical measurements in aqueous solutions of high temperatures | |
| CN205719980U (en) | A kind of electrochemical in-situ raman spectroscopy measurement microscopic heating stand and sample cell system | |
| WO2017080005A1 (en) | Sensor and method for measuring content of hydrogen in metal melt | |
| CN109731531A (en) | A kind of hydro-thermal large cavity high temperature and high voltage experimental device and experimental method | |
| RU2718077C1 (en) | Improved sampler of molten metal | |
| JP2010175416A (en) | Corrosion potential sensor | |
| CN109682937B (en) | Large-cavity high-temperature high-pressure gas-liquid two-phase flow experimental device and experimental method | |
| CN106770440A (en) | A kind of Ceramic Balls bed efficient thermal conductivity test platform | |
| CN100595959C (en) | Direct carbon fuel cell reaction device | |
| CN104634837B (en) | Electrochemical sensor and preparation method thereof | |
| CN112129824A (en) | Device and method for nondestructively measuring hydrogen content in solid steel | |
| CN109738594B (en) | Hydrothermal large-cavity high-temperature high-pressure flow experimental device and experimental method | |
| CN204405549U (en) | Melten salt electriochemistry original position Raman spectral measurement microscopic heating stand and sample cell | |
| CN114324536B (en) | Hydrogen probe device is decided to metal melt | |
| CN114324535B (en) | Detachable metal melt hydrogen measuring sensor device | |
| FR3064748A1 (en) | DEVICE, SYSTEM AND METHOD FOR DIFFRACTION ANALYSIS OF X-RAYS OF AN ELECTRODE OF AN ELECTROCHEMICAL CELL AT TEMPERATURE AND UNDER CURRENT | |
| CN105806739B (en) | A kind of sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid | |
| CN209727895U (en) | A kind of hydro-thermal large cavity high temperature and high voltage experimental device | |
| CN209911259U (en) | Portable synchrotron radiation state in-situ imaging experiment solidification device | |
| Tan et al. | A small sample-size automated adiabatic calorimeter from 70 to 580 K: Molar heat capacities of α-Al 2 O 3 | |
| CN104093886B (en) | The method of measurement surface profile in the aluminium cell of work |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |