CN117288740B - Raman probe-based battery charge-discharge gas production in-situ test device and test method - Google Patents
Raman probe-based battery charge-discharge gas production in-situ test device and test method Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 130
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 91
- 238000012360 testing method Methods 0.000 title claims abstract description 64
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 32
- 238000010998 test method Methods 0.000 title claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 58
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 26
- 238000007599 discharging Methods 0.000 claims abstract description 20
- 238000010926 purge Methods 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 17
- 239000013307 optical fiber Substances 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 7
- 230000008033 biological extinction Effects 0.000 claims description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000004868 gas analysis Methods 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 description 30
- 239000003792 electrolyte Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 11
- 230000000903 blocking effect Effects 0.000 description 9
- 238000007664 blowing Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
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- 239000000443 aerosol Substances 0.000 description 3
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The application discloses a battery charge-discharge gas production in-situ test device and a test method based on a Raman probe, and relates to the technical field of Raman spectrum gas analysis. The Raman probe is directly connected with a battery through an adapter; the charge-discharge equipment is used for being connected with the anode and the cathode of the battery; the working condition machine is connected with the charging and discharging equipment and is used for controlling a charging and discharging program; the gas production online detection system comprises a gas production output pipeline and a gas production test unit, wherein one end of the gas production output pipeline is connected with the gas inlet end of the Raman probe, and the gas outlet end of the gas production output pipeline is connected with the gas production test unit. The Raman probe is directly connected with the battery, a complicated gas collecting device or a filtering gas circuit is not needed, gas can be detected in situ of the battery, the gas inside the battery is prevented from being directly extracted, the influence on the working environment of the battery is reduced, and the service life of the battery is prolonged.
Description
Technical Field
The application relates to the technical field of Raman spectrum gas analysis, in particular to a battery charge-discharge gas production in-situ test device and test method based on a Raman probe.
Background
At present, the lithium ion battery is used as an important component of energy source cleaning, the occupation ratio of the lithium ion battery in the energy storage field, the portable electronic product field and the large-scale power supply field is improved year by the characteristics of high energy density, good cycle performance, low environmental pollution and the like, and the global demand of the lithium ion battery is increased year by year.
In the process of charging and discharging a lithium ion battery, the microstructure of substances in the battery can be changed, for example, the material composition, the shape and the like of substances such as a pole piece, electrolyte and the like in the battery can be changed, the charging and discharging capability of the battery can be represented by the change of the microstructure of the substances in the battery, and when the change is abnormal, the abnormality and the failure of the substances such as the pole piece, the electrolyte and the like in the battery can also be represented, for example, patent US9716295B2 of three-star electrons discloses a raman optical measurement system applied to real-time analysis of an in-situ button battery, and the state change of the electrode of the charge and the discharge of the button battery is analyzed by measuring scattered light emitted from the electrode. Patent US20210310975A1 of korean basic science support institute discloses a cell measurement module for in-situ optical and electrochemical analysis, which irradiates raman light onto a cell stack, and characterizes charge and discharge conditions of a battery by monitoring positive and negative active material changes. Meanwhile, a large amount of gas is generated in the cyclic charge and discharge process of the lithium battery, the electrode plate is expanded and the internal resistance of the battery is increased due to the generation of the gas, so that the cyclic performance and capacity of the battery are greatly influenced, the cyclic performance of the battery is poorer due to the larger amount of the gas, the capacity is rapidly attenuated, and battery manufacturers can be helped to improve the battery formula and the manufacturing process by detecting the concentration of the characteristic gas, which is the key point of research in recent years.
The current common analysis method is to extract a part of gas from the battery by a pinhole injector, then send the gas into a gas chromatograph for analysis and detection, as disclosed in patent CN205985250U, an online component analysis device for gas production in a square aluminum lithium battery is disclosed, the gas produced by the aluminum lithium battery in various charge and discharge processes is timely and accurately collected by a gas-taking needle, trace gas is enriched by a gas-collecting cavity, the trace gas is connected with the gas chromatograph by a multi-way valve, continuous gas production analysis can be carried out on a plurality of batteries,
however, this analytical method has problems in that: (1) The gas chromatography analysis time is long, and usually more than ten minutes are needed to finish sample detection; (2) The gas is extracted from the battery, which can change the working environment of the battery and affect the service life of the battery. Meanwhile, because the gas inside the battery needs to be extracted for detection, at the moment, the gas production amount of the battery in the charging and discharging process cannot be accurately judged, and further, the parameters in the charging and discharging process of the battery cannot be accurately monitored, so that the performance and the stability of the battery are guaranteed.
Compared with the weather chromatography, the Raman spectrum technology can analyze dynamic change information of the released gas (CO 2, CO, H2, CH4, C2H 4) and the air component (N2, O2) of the lithium ion battery in second level time, but the Raman probe is required to be placed in the battery body for realizing in-situ detection of the battery, but the size of the battery is limited due to small volume of the battery, the probe is too small to detect the light signal and weak, and the Raman probe is easy to be corroded by electrolyte in the battery body.
Disclosure of Invention
In order to improve the detection efficiency and detection precision of battery charge and discharge gas while ensuring normal operation of a battery, the application provides a Raman probe-based battery charge and discharge gas production in-situ test device and a test method.
The application provides a battery charge and discharge gas production normal position testing arrangement based on Raman probe adopts following technical scheme:
first aspect
A battery charge-discharge gas production in-situ test device based on a Raman probe comprises:
the Raman probe is directly connected with the battery through the adapter, the detection end of the Raman probe is connected into one end of the adapter, the battery is provided with a battery connector, and the other end of the adapter is connected with the battery connector and used for collecting and detecting gas generated by the battery;
the Raman spectrum analyzer is connected with the Raman probe and is used for testing the component concentration of the generated gas at each stage of battery charging and discharging;
the charge-discharge device is used for being connected with the anode and the cathode of the battery to charge or discharge the battery;
the working condition machine is connected with the charging and discharging equipment and used for controlling a charging and discharging program;
the gas production online detection system comprises a gas production output pipeline and a gas production test unit, wherein one end of the gas production output pipeline is connected with the gas inlet end of the Raman probe, and the gas outlet end of the gas production output pipeline is connected with the gas production test unit.
By adopting the technical scheme, the working condition machine controls the charging and discharging equipment to charge or discharge the battery, gas generated in the charging and discharging process of the battery is diffused into the inner cavity of the Raman probe, the Raman probe converts a gas signal into an optical signal and transmits the optical signal to the Raman spectrum analyzer, and the Raman spectrum analyzer analyzes the concentration of each gas component through a spectrum. On one hand, the gas production on-line detection system can realize on-line detection of the component concentration of the gas produced in each stage of battery cyclic charge and discharge, and on the other hand, the gas production in each stage of battery charge and discharge can be detected, and the quality of the battery is poorer as the gas production is more. Thus, by cell gas-generating component concentration and gas production, improvements in cell processing and assessment of cell quality are facilitated. On one hand, the Raman spectrum online detection is directly carried out on the gas in the battery in situ, and compared with a traditional gas chromatograph, the Raman spectrum online detection has high response speed, and the chromatograph generally takes tens of minutes and has Raman second level response; on the other hand, the Raman probe is directly connected with the battery, a complex gas collecting device or a filtering gas circuit is not needed, gas can be detected in situ of the battery, the gas in the battery is prevented from being directly extracted, the influence on the working environment of the battery is reduced, and the service life of the battery is prolonged.
Optionally, the system still includes the system of blowing, the system of blowing includes the pipeline of blowing and blows the gas cylinder, the pipeline of blowing one end with the inlet end of Raman probe is connected, the other end with the gas cylinder of blowing is connected, be provided with first on-off valve on the pipeline of blowing, be provided with the second on-off valve between gas production output pipeline and the gas production test unit.
Through adopting above-mentioned technical scheme, before detecting, switch the second and open and close the valve to the passageway of blowing, open first and open the valve, pass through the purge gas cylinder and blow the gas cylinder and blow in the pipeline, blow and to Raman probe detection end, blow and can get rid of impurity such as dust, grease, dirt that adhere to in probe surface or pore, improve the accuracy of testing result and extension probe life.
Optionally, the raman probe is detachably connected with the battery through an adapter.
Through adopting above-mentioned technical scheme, the inside gas of battery can get into in the raman probe through the adapter, ensures that battery gas does not leak, simultaneously, can realize the quick assembly disassembly of raman probe and battery.
Optionally, the adapter includes the adapter sleeve, raman probe's detection end threaded connection in the one end of adapter sleeve, install the battery on the battery and connect, adapter sleeve's the other end is used for with battery joint threaded connection.
Through adopting above-mentioned technical scheme, in the battery gas gets into the adapter sleeve through the battery joint to in the raman probe is got into by the adapter sleeve, threaded connection's mode both makes things convenient for the dismouting, also can ensure the leakproofness, reduces the gas and leaks.
Optionally, the air inlet of raman probe detection end is along radial direction towards switching sleeve lateral wall, the one end that the raman probe was followed the axis and is equipped with the shutoff end towards battery connector, the air inlet periphery cover of raman probe detection end is equipped with the filter, be provided with gas passage between filter and the inner wall of switching sleeve.
By adopting the technical scheme, the gas overflowed from the inside of the battery does not directly flow to the gas inlet of the detection end of the Raman probe, but is blocked by the blocking end, so that the blocking end can slow down the flow rate of the gas on one hand, the gas can more uniformly enter the Raman probe, and the detection result is improved; on the other hand, the electrolyte aerosol carried in the gas can be blocked by the blocking end and the filter, so that the electrolyte is prevented from entering the Raman probe, the lens is prevented from being polluted by the electrolyte, and the service life of the probe is prolonged.
Optionally, the in-situ testing device further comprises a purging system, the purging system comprises a purging pipeline and a purging gas cylinder, one end of the purging pipeline is connected with the adapter, the other end of the purging pipeline is connected with the purging gas cylinder, a first opening and closing valve is arranged on the purging pipeline, a purging air inlet is formed in the side wall of the switching sleeve, the purging air inlet is connected with the purging pipeline, and the purging air inlet faces towards the plugging end along the radial direction of the switching sleeve.
By adopting the technical scheme, because the plugging end is easy to accumulate electrolyte, dust and other impurities, before detection, the air inlets of the plugging end and the Raman probe detection end can be purged by using the purging system, so that the probe detection result is improved and the service life of the probe is prolonged.
Optionally, the gas production testing unit is a U-shaped pipe or a buoyancy testing device.
Through adopting above-mentioned technical scheme, based on archimedes' principle, utilize U type pipe or buoyancy testing arrangement can measure the battery gas production fast and comparatively accurately, reduce detection cost and improve detection efficiency.
Optionally, the raman probe includes signal emission portion, collimating lens, spectroscope, first focusing lens, extinction piece, filter, second focusing lens and signal receiving part, the laser that signal emission portion was launched is through collimating lens collimation becomes parallel light, and is incident to the spectroscope again, the spectroscope changes the light beam direction to first focusing lens, first focusing lens focuses laser, collides each other in focus position laser and gas sample, produces raman scattered light, and unnecessary laser continues to travel forward and is absorbed by extinction piece, raman scattered light passes through first focusing lens collimation becomes parallel light, from the spectroscope transmission, through filter filtering Rayleigh scattered light, and gets into after the focusing of second focusing lens signal receiving part.
Through adopting above-mentioned technical scheme, this fiber probe compact structure, and the component is less, therefore the light path debugging is simple, directly is connected raman probe and battery, and raman spectrum analyzer can be placed in the good region of environment, can effectively reduce the influence of on-the-spot environment to raman spectrum analyzer, can detect gas component concentration in real time, also can prolong raman spectrum analyzer's life.
Second aspect
A battery charge-discharge gas production in-situ test method based on a Raman probe comprises the following steps:
the Raman probe is connected to the outer side of the battery, and the gas circuit and the circuit are connected; the Raman probe is directly connected with the battery through the adapter, the detection end of the Raman probe is connected into one end of the adapter, the battery is provided with a battery connector, and the other end of the adapter is connected with the battery connector;
switching the second on-off valve to a purging passage, opening the first on-off valve, introducing purging gas, and purging the Raman probe for a period of time;
closing the first opening and closing valve, switching the second opening and closing valve to a gas production testing passage, setting a standard charge and discharge program on the industrial personal computer, clicking and starting, and starting charge and discharge of the battery;
the gas generated in the battery cell is freely diffused to the inner cavity of the Raman probe through the side wall of the battery, the Raman spectrum analyzer is excited by the optical fiber and collects Raman scattering spectrums, and the concentration of each gas component is analyzed through the spectrums;
and the gas generated by the charge and discharge of the battery enters a gas production testing unit through a second start-stop valve, and the gas production testing unit detects the gas production of the battery in the charge and discharge stage.
Through adopting above-mentioned technical scheme, at first sweep the probe before detecting, improve probe testing result and extension probe life, in the testing process, can carry out normal operating to battery gas production concentration, improve testing result and guarantee battery, can also measure the battery gas production simultaneously, through battery gas production concentration and gas production, help improving battery technology and aassessment battery quality.
Optionally, a battery connector is mounted on the battery, and the raman probe is detachably connected with the battery connector through an adapter.
Through adopting above-mentioned technical scheme, the gas that produces in the battery charge-discharge process can be through battery joint diffusion to the adapter to diffuse Raman probe by the adapter, detect by Raman probe. The scheme can accurately detect the gas concentration and the gas production in real time.
In summary, the present application includes at least one of the following beneficial technical effects:
the Raman spectrum online in-situ detection is carried out on the gas inside the battery, the Raman probe is directly connected with the battery, a complex gas collecting device or a filtering gas circuit is not needed, the gas can be detected in the battery in-situ, the gas inside the battery is prevented from being directly extracted, the influence on the working environment of the battery is reduced, and the service life of the battery is prolonged.
The method and the device can detect the concentration of the gas generating component and the gas generating quantity of the battery at the same time, and are beneficial to improving the battery process and evaluating the quality of the battery.
The gas overflowed from the inside of the battery does not directly flow to the gas inlet of the detection end of the Raman probe, but is blocked by the blocking end, so that the blocking end can slow down the flow rate of the gas on one hand, the gas can enter the Raman probe more uniformly, and the detection result is improved; on the other hand, the electrolyte aerosol carried in the gas can be blocked by the blocking end and the filter, so that the electrolyte is prevented from entering the Raman probe, the lens is prevented from being polluted by the electrolyte, and the service life of the probe is prolonged.
Drawings
Fig. 1 is a schematic connection diagram of the overall structure of the embodiment of the present application.
Fig. 2 is a schematic structural diagram of a raman probe according to an embodiment of the present application.
Fig. 3 is a schematic diagram of a connection structure between a raman probe and a battery according to an embodiment of the present application.
Fig. 4 is a schematic diagram mainly showing an internal structure of the adapter according to the embodiment of the present application.
Reference numerals illustrate:
100. a battery; 110. a battery terminal; 200. a raman probe; 210. a housing; 211. an incident channel; 212. a reflective cavity; 213. a detection channel; 214. an exit channel; 215. a step; 216. plugging the end; 217. a filter; 218. a gas channel; 220. a signal transmitting section; 230. a collimating lens; 240. a beam splitter; 250. a first focusing lens; 260. a light-eliminating sheet; 270. a light filter; 280. a second focusing lens; 290. a signal receiving section; 300. a raman spectrum analyzer; 400. a charge-discharge device; 500. a working condition machine; 600. the gas production amount on-line detection system; 610. a gas production output pipeline; 620. a gas production amount testing unit; 630. a second on-off valve; 700. a purge system; 710. purging the pipeline; 720. purging the gas cylinder; 730. a first on-off valve; 800. a transfer sleeve; 810. a gas yield outlet; 820. purging the air inlet.
Detailed Description
The present application is described in further detail below in conjunction with figures 1-4.
In the related art, the battery 100 is surface-mounted with the battery connector 110, and the gas released from the battery 100 during the charge and discharge can be transmitted to the outside through the battery connector 110.
The embodiment of the application discloses a battery charge-discharge gas production in-situ test device based on a Raman probe. Referring to fig. 1, the system includes a raman probe 200, a raman spectrum analyzer 300, a charge and discharge device 400, a working machine 500, a gas production online detection system 600, and a purge system 700. The Raman probe 200 is detachably connected with the battery connector 110 and used for collecting and detecting gas generated by the battery 100, the Raman spectrum analyzer 300 is connected with the Raman probe 200 and used for testing the component concentration of the gas generated in each stage of charging and discharging of the battery 100, the charging and discharging equipment 400 is connected with the anode and the cathode of the battery 100 and used for charging or discharging the battery 100, and the working condition machine 500 is connected with the charging and discharging equipment 400 and used for controlling a charging and discharging program; the gas production online detection system 600 is used for detecting gas production in the charge and discharge processes of the battery 100, and the purging system 700 is used for purging the Raman probe 200 before detection, so that the detection result is ensured, and the service life of the Raman probe 200 is prolonged.
Referring to fig. 1 and 2, the raman probe 200 includes a housing 210, the housing 210 including an incident channel 211, a reflection cavity 212, a detection channel 213, and an exit channel 214, the reflection cavity 212 being respectively communicated with the incident channel 211, the detection channel 213, and the exit channel 214, a signal emitting part 220 and a collimator lens 230 being sequentially installed in the incident channel 211 along an optical transmission direction; a beam splitter 240 is mounted in the reflective cavity 212; the first focusing lens 250 and the extinction lens 260 are sequentially installed in the detection channel 213 along the optical path transmission direction, the light filter 270, the second focusing lens 280 and the signal receiving part 290 are sequentially installed in the exit channel 214 along the optical path transmission direction, and the signal transmitting part 220 and the signal receiving part 290 are respectively connected with the raman spectrum analyzer 300.
The laser emitted from the signal emitting part 220 is collimated into parallel light by the collimating lens 230 and then enters the beam splitter 240, the beam splitter 240 focuses the laser beam to the first focusing lens 250 after changing the direction of the beam by 90 degrees, the laser beam and the gas sample collide with each other at the focal point position by the first focusing lens 250 to generate raman scattered light, the redundant laser beam continues to propagate forward and is absorbed by the extinction piece 260, the raman scattered light is collimated into parallel light by the first focusing lens 250, transmitted by the beam splitter 240, the rayleigh scattered light is filtered by the filter 270, and enters the signal receiving part 290 after being focused by the second focusing lens 280.
In an embodiment, the signal emitting portion 220 is an incident optical fiber, the signal receiving portion 290 is an outgoing optical fiber, and the raman probe 200 is connected to the raman spectrum analyzer 300 through both the incident optical fiber and the outgoing optical fiber, and the optical fiber length can reach hundreds of meters, so that the raman spectrum analyzer 300 can be placed at a place far from the detection site, the influence of the site environment on the raman spectrum analyzer 300 is reduced, and the stability and the service life of the raman spectrum analyzer 300 are ensured.
Meanwhile, in the present embodiment, the filter 270 is a long-pass filter, and the long-pass filter mainly blocks short-wavelength light, selectively transmits long-wavelength light, and performs adjustment and correction in the optical system. In another embodiment, filter 270 is a filter wheel that may be used for correction of the optical system. By selecting proper optical filters, the spectral characteristics, light intensity, color balance and the like in the light path can be adjusted so as to achieve the aims of correcting and optimizing the optical system.
Referring to fig. 3 and 4, in the present embodiment, the raman probe 200 is detachably connected to the battery connector 110 through an adapter. The adapter comprises an adapter sleeve 800, a detection end of the Raman probe 200 is in threaded connection with one end of the adapter sleeve 800, a step 215 is arranged on the periphery of the detection end of the Raman probe 200, and the step 215 limits the length of the Raman probe 200 screwed into the adapter sleeve 800. The other end of the adapter sleeve 800 is screwed to the inner wall of the battery connector 110 after the diameter thereof is reduced, and the end of the battery connector 110 abuts against the end of the adapter sleeve 800, thereby limiting the length of the adapter sleeve 800 screwed into the battery connector 110. In other embodiments, the raman probe 200 may also be directly connected to the battery connector 110, and the gas generated during the charging and discharging process of the battery 100 can diffuse into the raman probe 200 through the battery connector 110, so that the raman probe 200 can perform the detection.
Meanwhile, an air inlet of the detection end of the Raman probe 200 faces the side wall of the adapter sleeve 800 along the radial direction, a plugging end 216 is arranged at one end of the Raman probe 200 facing the battery connector 110 along the axis, a filter 217 is sleeved on the periphery of the air inlet of the detection end of the Raman probe 200, and a gas channel 218 is arranged between the outer wall of the filter 217 and the inner wall of the adapter sleeve 800. The gas released during the charge and discharge of the battery 100 enters the adapter sleeve 800 through the battery connector 110, flows through the gas channel 218 from the adapter sleeve 800, enters the raman probe 200 through the filter 217, irradiates the sample with laser light and transmits the frequency shift of the scattered light to the raman spectrum analyzer 300, thereby acquiring the information of the sample. In one embodiment, the filter 217 is a stainless steel cartridge.
The gas overflowed from the interior of the battery 100 does not directly flow to the gas inlet of the detection end of the raman probe 200, but is blocked by the blocking end 216, so that the blocking end 216 can slow down the flow rate of the gas, and the gas can more uniformly enter the interior of the raman probe 200, thereby improving the detection result; on the other hand, the electrolyte aerosol carried in the gas can be blocked by the blocking end 216 and the filter 217, so that the electrolyte is prevented from entering the Raman probe 200, the lens is prevented from being polluted by the electrolyte, and the service life of the probe is prolonged.
Referring to fig. 1 and 4, the gas yield on-line detection system 600 includes a gas yield output pipe 610 and a gas yield test unit 620, one end of the gas yield output pipe 610 is connected with the adapter sleeve 800, a gas yield gas outlet 810 is provided on the side wall of the adapter sleeve 800, gas can enter the gas yield output pipe 610 through the gas yield gas outlet 810, the gas yield test unit 620 is connected with the gas outlet end of the gas yield output pipe 610, gas can enter the gas yield test unit 620 through the gas yield output pipe 610, and the gas yield in the charging and discharging processes of the battery 100 is detected on line by the gas yield test unit 620.
In one embodiment, the gas production test unit 620 is a U-shaped tube, which is a U-shaped water column tube, and the gas production is measured by recording the water column height change based on the Archimedes principle. In another embodiment, the gas production testing unit 620 may also be a buoyancy testing device, which uses an archimedes buoyancy method to dip the battery 100 into silicone oil and test the buoyancy change to measure the gas production. Both of the above two gas production test units 620 are conventional and are not described in detail herein. Similarly, other prior art techniques may be used to test gas production.
Referring to fig. 1 and 4, the purge system 700 includes a purge pipe 710 and a purge gas cylinder 720, one end of the purge pipe 710 is connected with the adapter sleeve 800, a purge gas inlet 820 is provided on the sidewall of the adapter sleeve 800, purge gas can enter the adapter sleeve 800 through the purge gas inlet 820, the other end of the purge pipe 710 is connected with the purge gas cylinder 720, a first on-off valve 730 is provided on the purge pipe 710, and a second on-off valve 630 is provided between the gas yield output pipe 610 and the gas yield testing unit 620.
In this embodiment, the first on-off valve 730 is a solenoid valve, and the second on-off valve 630 is a three-way valve. Before detection, the three-way valve is switched to a purging passage, the electromagnetic valve is opened, purging gas is introduced into the purging pipeline 710 through the purging gas cylinder 720, the detection end of the Raman probe 200 is purged, and the purged gas flows through the gas yield output pipeline 610 and flows to the outside. When gas needs to be detected, the electromagnetic valve is closed, the three-way valve is switched to a gas production testing passage, and gas released in the charging and discharging process of the battery 100 can enter the gas production testing unit 620 through a gas production testing pipeline, and the gas production is detected online by the gas production testing unit 620. Meanwhile, the gas released during the charge and discharge of the battery 100 is also detected and analyzed by the raman probe 200, and finally the raman spectrum analyzer 300 detects the concentration of the components of the gas produced during the charge and discharge of the battery 100.
In addition, when the detection is not performed, the Raman probe 200 can be periodically purged, so that the pollution of lenses is prevented, and the service life of the Raman probe 200 is prolonged.
The implementation principle of the battery charge-discharge gas production in-situ test device based on the Raman probe is as follows: on the one hand, the Raman spectrum online detection can be directly carried out on the gas in the battery 100 in situ, compared with a traditional gas chromatograph, the online detection response speed is high, the chromatograph generally takes tens of minutes, and the Raman second level response is carried out; on the other hand, the raman probe 200 is directly connected with the battery 100, a complex gas collecting device or a filtering gas circuit is not needed, gas can be detected in situ in the battery 100, the gas in the battery 100 is prevented from being directly extracted, the influence on the working environment of the battery 100 is reduced, the service life of the battery 100 is prolonged, the concentration of gas production components and the gas production quantity of the battery 100 can be detected at the same time, and the process of the battery 100 is improved and the quality of the battery 100 is evaluated.
The embodiment of the application also discloses a battery charge-discharge gas production in-situ test method based on the Raman probe, which comprises the following steps:
the raman probe 200 is screwed to the battery connector 110, and the gas circuit and the electric circuit are connected.
The three-way valve is switched to a purging passage, the electromagnetic valve is opened, purging gas is introduced to purge the Raman probe 200 for a period of time, the three-way valve can be purged for three minutes, and the purging time can be prolonged or shortened according to actual conditions.
Closing the electromagnetic valve, switching the three-way valve to a gas production testing passage, setting a standard charge and discharge program in the industrial personal computer, clicking to start, and starting the charge and discharge of the battery 100.
The gas generated in the battery 100 is freely diffused into the inner cavity of the raman probe 200 through the battery connector 110, and the raman spectrum analyzer 300 is excited by the optical fiber and collects raman scattering spectra, so as to analyze the concentration of each gas component by the spectra.
The gas generated by the charge and discharge of the battery 100 passes through the three-way valve and enters the gas production testing unit 620, and the gas production testing unit 620 detects the gas production of the battery 100 in the charge and discharge stage.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (10)
1. The utility model provides a battery charge and discharge gas production normal position testing arrangement based on Raman probe which characterized in that includes:
the Raman probe (200) is directly connected with the battery (100) through an adapter, the adapter comprises an adapter sleeve (800), a detection end of the Raman probe (200) is connected into one end of the adapter sleeve (800), the battery (100) is provided with the battery connector (110), the other end of the adapter sleeve (800) is used for being connected with the battery connector (110), an air inlet of the detection end of the Raman probe (200) faces towards the side wall of the adapter sleeve (800) along the radial direction, and an air channel (218) is arranged between the periphery of the air inlet of the detection end of the Raman probe (200) and the inner wall of the adapter sleeve (800);
the charge-discharge device (400) is used for being connected with the anode and the cathode of the battery (100) to charge or discharge the battery (100);
the working condition machine (500) is connected with the charging and discharging equipment (400) and is used for controlling a charging and discharging program;
the gas released in the charging and discharging process of the battery (100) enters the adapter sleeve (800) through the battery connector (110), then flows through the gas channel (218) from the adapter sleeve (800), and finally enters the Raman probe (200) to detect the gas generated by the battery (100);
the gas production online detection system (600) comprises a gas production output pipeline (610) and a gas production test unit (620), wherein one end of the gas production output pipeline (610) is connected with the gas inlet end of the Raman probe (200), and the gas outlet end of the gas production output pipeline (610) is connected with the gas production test unit (620).
2. The raman probe-based battery charge-discharge gas production in-situ test device according to claim 1, wherein: still include purge system (700), purge system (700) include purge line (710) and purge gas cylinder (720), purge line (710) one end with the inlet end of raman probe (200) is connected, the other end with purge gas cylinder (720) are connected, be provided with first on-off valve (730) on purge line (710), be provided with second on-off valve (630) between gas production output pipeline (610) and gas production test unit (620).
3. The raman probe-based battery charge-discharge gas production in-situ test device according to claim 1, wherein: the Raman probe (200) is detachably connected with the battery (100) through an adapter.
4. A raman probe based battery charge-discharge gas production in situ test device according to claim 3, wherein: the detection end of the Raman probe (200) is in threaded connection with one end of the switching sleeve (800), and the other end of the switching sleeve (800) is in threaded connection with the battery connector (110).
5. The raman probe-based battery charge-discharge gas production in-situ test device according to claim 4, wherein: the Raman probe (200) is provided with a plugging end (216) along one end of the axis towards the battery connector (110), and a filter (217) is sleeved on the periphery of an air inlet of the detection end of the Raman probe (200).
6. The raman probe-based battery charge-discharge gas production in-situ test device according to claim 5, wherein: the in-situ testing device further comprises a purging system (700), the purging system (700) comprises a purging pipeline (710) and a purging gas cylinder (720), one end of the purging pipeline (710) is connected with the adapter, the other end of the purging pipeline is connected with the purging gas cylinder (720), a first opening and closing valve (730) is arranged on the purging pipeline (710), a purging gas inlet (820) is formed in the side wall of the adapter sleeve (800), the purging gas inlet (820) is connected with the purging pipeline (710), and the purging gas inlet (820) faces towards the plugging end (216) along the radial direction of the adapter sleeve (800).
7. The raman probe-based battery charge-discharge gas production in-situ test device according to claim 1, wherein: the gas production testing unit (620) is a U-shaped pipe or a buoyancy testing device.
8. The raman probe-based battery charge-discharge gas production in situ test device according to any one of claims 1-7, wherein: the Raman probe (200) comprises a signal transmitting part (220), a collimating lens (230), a beam splitter (240), a first focusing lens (250), an extinction sheet (260), a filter (270), a second focusing lens (280) and a signal receiving part (290), laser emitted by the signal transmitting part (220) is collimated into parallel light through the collimating lens (230) and then enters the beam splitter (240), the beam splitter (240) changes the direction of the light beam to the first focusing lens (250), the first focusing lens (250) focuses the laser, laser and a gas sample collide with each other at the focus position to generate Raman scattered light, the redundant laser continuously propagates forwards and is absorbed by the extinction sheet (260), the Raman scattered light is collimated into parallel light through the first focusing lens (250), the parallel light is transmitted through the beam splitter (240), the Rayleigh scattered light is filtered through the filter (270), and enters the signal receiving part (290) after being focused through the second focusing lens (280).
9. The battery charge-discharge gas production in-situ test method based on the Raman probe, which is based on the battery charge-discharge gas production in-situ test device based on the Raman probe as claimed in claim 2, is characterized by comprising the following steps:
the Raman probe (200) is connected to the outer side of the battery (100), and an air circuit and a circuit are connected; the Raman probe (200) is directly connected with the battery (100) through an adapter, the detection end of the Raman probe (200) is connected into one end of the adapter, the battery (100) is provided with a battery connector (110), and the other end of the adapter is connected with the battery connector (110);
switching the second on-off valve (630) to a purging passage, opening the first on-off valve (730), introducing purging gas, and purging the Raman probe (200) for a period of time;
closing the first opening and closing valve (730), switching the second opening and closing valve (630) to a gas production testing passage, setting a standard charge and discharge program on the industrial personal computer, clicking to start, and starting charge and discharge of the battery (100);
the gas generated in the battery core of the battery (100) is freely diffused into the inner cavity of the Raman probe (200) through the side wall of the battery (100), the Raman spectrum analyzer (300) is excited by the optical fiber and collects Raman scattering spectrums, and the concentration of each gas component is analyzed through the spectrums;
and gas generated by charging and discharging the battery (100) enters a gas production testing unit (620) through a second on-off valve (630), and the gas production testing unit (620) detects the gas production of the battery (100) in the charging and discharging stage.
10. The raman probe-based battery charge-discharge gas production in-situ test method according to claim 9, wherein: the Raman probe (200) is detachably connected with the battery connector (110) through an adapter.
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