CN115598108A - Real-time analysis device and system under electric core working condition - Google Patents
Real-time analysis device and system under electric core working condition Download PDFInfo
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- CN115598108A CN115598108A CN202211405071.0A CN202211405071A CN115598108A CN 115598108 A CN115598108 A CN 115598108A CN 202211405071 A CN202211405071 A CN 202211405071A CN 115598108 A CN115598108 A CN 115598108A
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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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
- H01M10/482—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for several batteries or cells simultaneously or sequentially
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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
Abstract
The invention discloses a real-time analysis device and a real-time analysis system under a cell working condition, which are applied to the technical field of cell detection.A carrier gas source is hermetically connected with a battery test module, a gas-liquid separation module is hermetically connected with the battery test module, and a gas analysis device is connected with the gas-liquid separation module; the gas-liquid separation module is provided with a separation membrane and is used for separating gas to be detected and volatilized electrolyte from mixed gas through the separation membrane, so that the gas to be detected enters the gas analysis device through the separation membrane, and meanwhile, the electrolyte flows back to the battery test module; the battery testing module and the gas analysis device are both connected with the electrochemical workstation, and the electrochemical workstation is used for analyzing the battery in real time under the working condition state. The mixed gas formed after the carrier gas is introduced is separated by arranging the separation membrane, electrolyte steam is prevented from passing through, the electrolyte is effectively intercepted, and long-time battery cycle test can be realized, so that various batteries can perform gas analysis for thousands of hours.
Description
Technical Field
The invention relates to the technical field of battery cell detection, in particular to a real-time analysis device and a real-time analysis system under a battery cell working condition.
Background
Under the circumstances that global environmental problems and energy crisis are becoming prominent, the development of clean renewable energy is imminent. Due to the limitations of wind energy, solar energy and the like, energy storage technology must be synchronously developed while the development of renewable energy sources is greatly promoted. The energy storage is the key for realizing the high-efficiency utilization of clean energy, and the energy storage serves as a medium, so that the problem of asynchronous generation and use of energy can be solved, and the cooperation and interconnection among various energy forms are facilitated. The lithium ion battery is an energy storage device which is most widely applied at present based on the advantages of high energy density, small self-discharge, long service life and the like, and the appearance of the soft package battery greatly improves the safety and the design flexibility. However, as the service life is prolonged, the problems of swelling, non-ideal safety performance and accelerated cycle decay exist, and the problems can be related to factors such as temperature, humidity, pressure, current fluctuation and the like. In order to further improve the energy storage application of the battery, the generation analysis and mechanism analysis of products in the battery circulation under various controllable conditions are key, and the real-time continuous detection of the products is one of key factors for guaranteeing the uncovering of complex reactions in the battery, so that the electrode/electrolyte interface reaction mechanism is understood, and the efficient battery material is rationally designed.
At present most commercial lithium cell uses organic liquid electrolyte such as dimethyl carbonate, it all has certain volatility, going on like the mass spectrum, when electrochemical gas analysis tests such as chromatogram, the carrier gas sweeps the in-process and can lead to electrolyte to consume totally, the battery is one to two rings after capacity decay, it can get into the instrument to be difficult to catch battery internal state in the longer period of time, and the electrolyte that constantly volatilizees can get into the instrument along with the target, the signal that the electrolyte ionization produced can disturb test data accuracy on the one hand, on the other hand organic solvent can block up the pipeline, the pollution detection source, cause not little cost of maintenance. During the electrolyte replenishment, the cell reaction is usually interrupted, resulting in inconsistent testing.
Therefore, how to provide an electrolyte circulation device capable of continuously performing battery reaction is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a real-time analysis device under the working condition of a battery core, which can realize long-time battery cycle test; the invention also aims to provide a real-time analysis system under the working condition of the battery core, which can realize long-time battery cycle test.
In order to solve the technical problem, the invention provides a real-time analysis device under the working condition of an electric core, which comprises a carrier gas source, a battery test module, a gas-liquid separation module, a gas analysis device and an electrochemical workstation, wherein the carrier gas source is connected with the battery test module;
the gas-carrying source is hermetically connected with the battery testing module, the gas-liquid separation module is hermetically connected with the battery testing module, and the gas analysis device is connected with the gas-liquid separation module;
the carrier gas source is used for introducing carrier gas into the battery testing module to react with battery liquid in the battery loaded by the battery testing module to generate mixed gas containing gas to be tested and the mixed gas enters the gas-liquid separation module;
the gas-liquid separation module is provided with a separation membrane and is used for separating the gas to be tested and the volatilized electrolyte from the mixed gas through the separation membrane, so that the gas to be tested enters the gas analysis device through the separation membrane, and meanwhile, the electrolyte flows back to the battery test module; the gas analysis device is used for detecting the gas to be detected;
the battery testing module and the gas analysis device are connected with the electrochemical workstation, and the electrochemical workstation is used for analyzing the battery in real time under the working condition state.
Optionally, the carrier gas source includes a gas cylinder, an industrial oil pump connected to an air outlet of the gas cylinder, and a timing switch valve connected to the industrial oil pump; the timing switch valve is used for being opened at regular time, so that residual gas between the gas cylinder and the battery test module is discharged from the timing switch valve through the industrial oil pump.
Optionally, the carrier gas source further comprises a filter column and a flow meter, the filter column is connected with the gas outlet of the gas cylinder, and the flow meter is connected between the filter column and the time switch valve.
Optionally, the gas-liquid separation module includes a vacuum pump disposed between the separation membrane and the gas analysis device to drive the gas to be detected to enter the gas analysis device.
Optionally, the battery test module is positioned on the surface of the displacement table; the battery test module is provided with a window, and an electrolyte analyzer is arranged on the outer side of the window.
Optionally, the electrolyte analyzer includes a raman spectrometer and a lens, the lens is located between the raman spectrometer and the window, and the raman spectrometer is connected to the electrochemical workstation;
the Raman spectrometer is used for carrying out surface composition analysis on the battery in the battery testing module through the lens and the window.
Optionally, the electrochemical workstation is specifically configured to:
based on preset battery working parameters, when the battery is reacted through the battery testing module, the gas analysis device detects the gas to be detected in real time, and the electrolyte analyzer analyzes the surface components of the battery in real time.
Optionally, the battery testing module includes a heating device for heating the battery, and a cooling device for cooling the battery.
Optionally, the separation membrane is provided with an interlayer channel, and the interlayer distance of the separation membrane is between the size of the electrolyte gas molecule and the size of the gas molecule to be detected.
The invention also provides a real-time analysis system under the working condition of the battery cell, which comprises the real-time analysis device under the working condition of the battery cell.
The invention provides a real-time analysis device under a cell working condition, which comprises a carrier gas source, a battery testing module, a gas-liquid separation module, a gas analysis device and an electrochemical workstation, wherein the carrier gas source is connected with the battery testing module; the gas-carrying source is hermetically connected with the battery testing module, the gas-liquid separation module is hermetically connected with the battery testing module, and the gas analysis device is connected with the gas-liquid separation module; the carrier gas source is used for introducing carrier gas into the battery testing module to react with battery liquid in the battery loaded by the battery testing module to generate mixed gas containing gas to be tested and entering the gas-liquid separation module; the gas-liquid separation module is provided with a separation membrane and is used for separating gas to be detected and volatilized electrolyte from mixed gas through the separation membrane, so that the gas to be detected enters the gas analysis device through the separation membrane, and meanwhile, the electrolyte flows back to the battery test module; the gas analysis device is used for detecting gas to be detected; the battery testing module and the gas analysis device are both connected with the electrochemical workstation, and the electrochemical workstation is used for analyzing the battery in real time under the working condition state.
The mixed gas formed after the carrier gas is introduced is separated by arranging the separation membrane, electrolyte steam is prevented from passing through, the electrolyte is effectively intercepted, and the electrolyte is directly refluxed into the battery, so that the long-time battery cycle test can be realized, and the gas analysis can be carried out for thousands of hours on various batteries. And the existence of the gas-liquid separation module provided with the separation membrane does not influence the reaction continuity, so that the real-time analysis under the working condition state of the battery can be realized. This gas-liquid separation module does not need extra energy just can realize the separation of volatile electrolyte and the gas that awaits measuring, and simple structure, can avoid electrolyte to consume when using, and repeatedly usable simultaneously is high-efficient swift safe environmental protection.
The invention also provides a real-time analysis system under the working condition of the battery cell, which also has the beneficial effects and is not repeated herein.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the present invention will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a real-time analysis device under a cell condition according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a real-time analysis device under a specific cell condition according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a gas-liquid separation module according to an embodiment of the present invention.
In the figure: 1. the device comprises a carrier gas source, 11 gas cylinders, 12 industrial oil pumps, 13 timing switch valves, 14 filter columns, 15 flow meters, 16 first valves, 17 air inlet valves, 18 air outlet valves, 19 second valves, 2 battery test modules, 21 displacement tables, 22 windows, 23 lenses, 24 Raman spectrometers, 25 heating devices, 26 refrigerating devices, 3 gas-liquid separation modules, 31 air outlets, 32 upper shells, 33 air-permeable supporting bodies, 34 protective layers, 35 separating membranes, 36 gaskets, 37 porous stainless steel plates, 38 conical lower shells, 4 gas analysis devices, 41 vacuum pumps and 5 electrochemical work stations.
Detailed Description
The core of the invention is to provide a real-time analysis device under the working condition of the battery core. In prior art, the carrier gas sweeps the in-process and can lead to electrolyte to consume totally, and the battery capacity decay after one to two circles is difficult to catch the battery internal state in the longer period of time, and the electrolyte that constantly volatilizees can get into the instrument along with the target, and the signal that electrolyte ionization produced can disturb test data accuracy on the one hand, and on the other hand organic solvent can block up the pipeline, pollutes the testing source, causes not little cost of maintenance. When the steam is recovered, the steam is usually condensed back to liquid state by using a condensation method for recovery. However, for electrolyte vapor, the volume of the condensing device is usually very large for recovering the electrolyte by a condensation method, which results in long response time and failure to realize long-time real-time analysis of the battery.
The real-time analysis device under the cell working condition comprises a carrier gas source, a battery test module, a gas-liquid separation module, a gas analysis device and an electrochemical workstation, wherein the carrier gas source is connected with the battery test module; the gas-carrying source is hermetically connected with the battery testing module, the gas-liquid separation module is hermetically connected with the battery testing module, and the gas analysis device is connected with the gas-liquid separation module; the carrier gas source is used for introducing carrier gas into the battery testing module to react with battery liquid in the battery loaded by the battery testing module to generate mixed gas containing gas to be tested and entering the gas-liquid separation module; the gas-liquid separation module is provided with a separation membrane and is used for separating gas to be detected and volatilized electrolyte from mixed gas through the separation membrane, so that the gas to be detected enters the gas analysis device through the separation membrane, and meanwhile, the electrolyte flows back to the battery test module; the gas analysis device is used for detecting gas to be detected; the battery testing module and the gas analysis device are both connected with the electrochemical workstation, and the electrochemical workstation is used for analyzing the battery in real time under the working condition state.
The mixed gas formed after the carrier gas is introduced is separated by arranging the separation membrane, electrolyte steam is prevented from passing through, the electrolyte is effectively intercepted, and the electrolyte is directly refluxed into the battery, so that the long-time battery cycle test can be realized, and the gas analysis can be carried out for thousands of hours on various batteries. And the existence of the gas-liquid separation module provided with the separation membrane does not influence the reaction continuity, so that the real-time analysis under the working condition state of the battery can be realized. This gas-liquid separation module does not need extra energy just can realize the separation of volatile electrolyte and the gas that awaits measuring, and simple structure, can avoid electrolyte to consume when using, and repeatedly usable simultaneously is high-efficient swift safe environmental protection.
In order that those skilled in the art will better understand the disclosure, reference will now be made in detail to the embodiments of the disclosure as illustrated in the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a real-time analysis device under a cell condition according to an embodiment of the present invention.
Referring to fig. 1, in the embodiment of the present invention, the real-time analysis apparatus under the battery core working condition includes a carrier gas source 1, a battery test module 2, a gas-liquid separation module 3, a gas analysis apparatus 4, and an electrochemical workstation 5;
the gas-carrying source 1 is hermetically connected with the battery testing module 2, the gas-liquid separation module 3 is hermetically connected with the battery testing module 2, and the gas analysis device 4 is connected with the gas-liquid separation module 3; the carrier gas source 1 is used for introducing carrier gas into the battery test module 2 to react with battery liquid in the battery loaded by the battery test module 2 to generate mixed gas containing gas to be tested, and the mixed gas enters the gas-liquid separation module 3; the gas-liquid separation module 3 is provided with a separation membrane 35, and the gas-liquid separation module 3 is configured to separate the gas to be tested and the volatilized electrolyte from the mixed gas through the separation membrane 35, so that the gas to be tested enters the gas analysis device 4 through the separation membrane 35, and the electrolyte flows back to the battery test module 2; the gas analysis device 4 is used for detecting the gas to be detected; the battery testing module 2 and the gas analysis device 4 are both connected with the electrochemical workstation 5, and the electrochemical workstation 5 is used for analyzing the battery in real time under the working condition state.
The battery test module 2 is a module for placing batteries and mainly reacting and controlling the batteries, and the carrier gas source 1 is used for providing carrier gas for the battery test module 2. According to the experimental requirements, the carrier gas may be Ar (argon) or He (helium), and the battery test module 2 may be various types of soft package batteries or mold batteries, that is, batteries to be tested. The gas-liquid separation module 3 is usually disposed above the battery test module 2, and the separation membrane 35 in the gas-liquid separation module 3 can separate the gas to be tested from the volatilized electrolyte vapor in the mixed gas generated by the battery, so that the gas to be tested passes through the separation membrane 35, traps the electrolyte vapor and is re-aggregated into liquid electrolyte.
Because most of the commercial lithium batteries use organic liquid electrolyte, the molecules of the evaporated electrolyte vapor are large, and the molecules of the gas to be detected, which needs to be detected, are small, the gas to be detected can pass through the separation membrane 35 by adjusting the size of the channel in the separation membrane 35, and the molecules of the electrolyte vapor are blocked from passing through the separation membrane 35, so that the separation of the mixed gas is realized. Specifically, the separation membrane 35 is specifically disposed above the battery test module 2, so that after the intercepted electrolyte vapor is intercepted and re-converged into electrolyte, the electrolyte vapor can flow back to the battery test module 2 under the action of gravity to perform a circulation test. The gas to be measured passing through the separation membrane 35 enters the gas analyzer 4 for analysis, and the specific structure of the gas analyzer 4 needs to be set according to the specific analysis content, which is not specifically limited herein.
In the embodiment of the present invention, both the battery test module 2 and the gas analysis device 4 are connected to the electrochemical workstation 5, and the electrochemical workstation 5 is configured to analyze the battery in real time under the operating condition. The electrochemical workstation 5 is connected with the battery test module 2, can control charging and discharging of the battery to be tested and record, and the electrochemical workstation 5 is connected with the gas analysis device 4, so that storage and operation of data generated after the gas to be tested is analyzed can be realized. The recovery of the electrolyte by combining the gas-liquid separation module 3 can realize the real-time analysis of the battery under the working condition state. The real-time analysis under the working condition state is to analyze and calculate each parameter of the battery when the battery continuously reacts. The gas analyzer 4 may be a chromatograph or a mass spectrometer, and is not particularly limited herein.
According to the real-time analysis device under the working condition of the battery core, the separation membrane 35 is arranged to separate the mixed gas formed after the carrier gas is introduced, so that the electrolyte vapor is prevented from passing through, the electrolyte is effectively intercepted and directly flows back to the battery, the long-time battery cycle test can be realized, and the gas analysis of various batteries can be carried out for thousands of hours. And the existence of the gas-liquid separation module 3 provided with the separation membrane 35 does not affect the reaction continuity, so that the real-time analysis under the working condition state of the battery can be realized. This gas-liquid separation module 3 does not need extra energy just can realize the separation of volatile electrolyte and the gas that awaits measuring, and simple structure, can avoid electrolyte to consume when using, and repeatedly usable simultaneously, high-efficient swift safety ring protects.
The details of the real-time analysis apparatus under the cell condition provided by the present invention will be described in detail in the following embodiments of the invention.
Referring to fig. 2, fig. 2 is a schematic structural diagram of a specific real-time analysis device under a cell condition according to an embodiment of the present invention.
Different from the embodiment of the invention, the embodiment of the invention is further limited on the basis of the embodiment of the invention, and the structure of the real-time analysis device under the cell working condition is further limited. The rest of the contents are already described in detail in the above embodiments of the present invention, and are not described herein again.
Referring to fig. 2, in the embodiment of the present invention, the carrier gas source 1 includes a gas cylinder 11, an industrial oil pump 12 connected to an outlet of the gas cylinder 11, and a timing switch valve 13 connected to the industrial oil pump 12; the timing switch valve 13 is used for being opened at a timing, so that gas remained between the gas cylinder 11 and the battery test module 2 is discharged from the timing switch valve 13 through the industrial oil pump 12.
The gas cylinder 11 contains carrier gas, the gas cylinder 11 provides a power source for the reaction gas to enter the detecting instrument, wherein the type of the carrier gas is required to be set according to the actual situation. The carrier gas source 1 may retain gas during long-term use. In order to increase the detection speed, in the embodiment of the present invention, the industrial oil pump 12 and the time switch valve 13 are specifically matched to extract the gas retained in the carrier gas source 1, so as to increase the detection speed.
Specifically, the gas outlet of the gas cylinder 11 is connected with an industrial oil pump 12, and the industrial oil pump 12 is connected with a timing switch valve 13. This time switch valve 13 is used for regularly opening, and industrial oil pump 12 can extract the gas that is detained in carrier gas source 1 and discharge from the time switch valve 13 of opening this moment to guarantee that follow-up carrier gas can get into battery test module 2 smoothly, so that improve detection speed.
In the embodiment of the present invention, the carrier gas source 1 further includes a filter column 14 and a flow meter 15, the filter column 14 is connected to the gas outlet of the gas cylinder 11, and the flow meter 15 is connected between the filter column 14 and the time switch valve 13. Namely, the outlet end of the gas cylinder 11 is connected with the filter column 14 through a pressure regulating valve, and the filter column 14 is usually provided with a treated 4A type molecular sieve for drying carrier gas to avoid introducing moisture to influence the experimental result. The flow meter 15 is provided specifically at the rear end of the filter column 14, and the flow meter 15 is used to control the flow rate of the carrier gas. The adjustment range is mostly 0.2mL/min-1mL/min according to the experimental requirements, the transfer efficiency of the product is easily reduced due to too low flow rate, the response time of an instrument is prolonged, and the volatilization of the product is easily accelerated due to too high flow rate.
In the embodiment of the present invention, the gas-liquid separation module 3 includes a vacuum pump 41 disposed between the separation membrane 35 and the gas analysis device 4 to drive the gas to be measured into the gas analysis device 4. The vacuum pump 41 is a power source provided on the gas outlet side of the battery test module 2, and the vacuum pump 41 is used for driving the gas to be tested into the gas analysis device 4. The vacuum pump 41 provides another power source for gas transmembrane transmission, and is combined with the gas cylinder 11 in the carrier gas source 1 and the industrial oil pump 12, so that the level sample injection detection can be realized, and the real working condition detection is realized. The vacuum pump 41 may be a separately provided oil pump, and its specific structure may be set according to actual conditions.
In practical situations, the charging rate of the lithium ion battery is also an important consideration factor of battery performance, the local reaction speed in the soft package battery can be seriously influenced by the rapid charging or discharging rate, the soft package battery is damaged more quickly, the battery state under rapid charging needs to be researched to determine an appropriate reaction condition, however, the constant current fluctuates when rapid charging and discharging are carried out, if the electrochemical gas production situation is analyzed in situ, the time resolution is too low, the charging and discharging process of the battery needs to be suspended and then analyzed by a testing instrument, so that data delay is caused, and the authenticity of an experimental result is difficult to ensure. In the embodiment of the invention, the gas cylinder 11, the industrial oil pump 12 and the vacuum pump 41 are used as power sources, so that the sampling detection at millisecond level can be realized, and the real working condition detection can be realized.
In the embodiment of the invention, the battery test module 2 is positioned on the surface of the triaxial displacement table 21; the battery testing module 2 is provided with a window 22, and an electrolyte analyzer is arranged outside the window 22. When needing to set up electrolyte analysis appearance and carry out analysis and detection to the battery in the operating mode, can set up window 22 at battery test module 2, later be provided with electrolyte analysis appearance in the window 22 outside for electrolyte analysis appearance can see through window 22 and carry out the analysis to battery test module 2 interior electrolyte, realizes the comprehensive analysis to the battery. In order to measure the electrolyte, the battery testing module 2 may be located on the surface of the displacement table 21, and the displacement table 21 may specifically be an x-y-z three-axis displacement table 21, so as to drive the battery to move and measure the electrolyte. The window 22 may be a quartz window 22, so as to prevent the electrolyte in the battery from volatilizing to the outside and ensure that the electrolyte can be observed through the window 22.
Specifically, the electrolyte analyzer comprises a raman spectrometer 24 and a lens 23, the lens 23 is located between the raman spectrometer 24 and the window 22, and the raman spectrometer 24 is connected with the electrochemical workstation 5; the raman spectrometer 24 is used to analyze the surface composition of the cells in the cell testing module 2 through the lens 23 and the window 22. The raman spectrometer 24 can specifically analyze the surface composition of the electrolyte through the lens 23 and the window 22, and the detection process does not interrupt the reaction of the battery, i.e. the analysis of the surface composition of the electrolyte under the working condition of the battery can be realized.
Specifically, in the embodiment of the present invention, the electrochemical workstation 5 is specifically configured to: based on preset battery working parameters, when the battery is reacted through the battery testing module 2, the gas analysis device 4 detects the gas to be detected in real time, and the electrolyte analyzer analyzes the surface components of the battery in real time.
That is, the electrochemical workstation 5 is connected to the battery test module 2, the electrolyte analyzer, and the gas analyzer 4 at the same time, so as to control each operating module or device and obtain corresponding data. Specifically, the electrochemical workstation 5 may react the battery through the battery test module 2 based on preset battery operating parameters. In the reaction, the gas to be detected is detected in real time through the gas analysis device 4, and meanwhile, the surface component analysis is carried out on the battery in real time through the electrolyte analyzer, so that the battery is comprehensively analyzed under the working condition of the battery. Meanwhile, due to the existence of the three power sources of the gas cylinder 11, the industrial oil pump 12 and the vacuum pump 41, millisecond-level sample injection detection can be realized, and therefore real working condition detection is achieved.
In the embodiment of the present invention, the battery testing module 2 includes a heating device 25 for heating the battery, and a cooling device 26 for cooling the battery. Namely, the battery testing module 2 can be further provided with a heating device 25 for heating the battery, and a cooling device 26 for cooling the battery. Through the cooperation of heating device 25 and the command device, the temperature of battery can be controlled to satisfy and measure the battery under different operating modes.
In the embodiment of the present invention, a first valve 16 is disposed between the gas cylinder 11 and the filter column 14, an air inlet valve 17 is disposed between the air inlet of the battery test module 2 and the industrial oil pump 12, an air outlet valve 18 is disposed between the air outlet of the battery test module 2 and the gas-liquid separation module 3, and a second valve 19 is disposed between the gas-liquid separation module 3 and the vacuum pump 41. The valve can be used for specifically controlling the flow of gas in the real-time analysis device under the working condition of the battery core, so that the working conditions of all parts are controlled.
In the process of using the real-time analysis device under the cell working condition provided by the embodiment of the invention, the self-made separation membrane 35 is firstly installed in the gas-liquid separation module 3, and the battery test module 2 is connected below the self-made separation membrane. Before testing, the air inlet valve 17 is closed, the timing switch valve 13 is opened, and gas left in the pipeline is extracted for 10nim-30min, so that the experimental result is prevented from being influenced until negative pressure is maintained in the pipeline, and the timing switch valve 13 is closed after good air tightness is ensured.
The electrochemical workstation 5 is used for charging and discharging the battery, the heating device 25 or the refrigerating device 26 is adjusted to a target state, the air inlet valve 17, the air outlet valve 18, the second valve 19 and the flowmeter 15 are opened, and the carrier gas is controlled to drive the gas to circulate at a specific flow rate.
Specifically, the valve 13 can be opened and updated automatically every 5min to prevent gas accumulation and block the detection rate. After the carrier gas flows into the battery testing module 2, the target product and the electrolyte volatile gas are taken out together to form mixed gas; when the mixed gas passes through the gas-liquid separation module 3, the gas to be measured (mostly CO) 2 、O 2 Small molecule gas) can easily penetrate through the separation membrane 35 and enter the gas analysis device 4, and organic solvent (mostly organic molecules are large) cannot penetrate through the separation membrane 35, and is agglomerated along with blocked electrolyte vapor molecules, so that the local pressure is slowly increased, and the organic solvent flows back into the battery under the action of gravity. The separation membrane 35 is usually fixed between the air-permeable support body 33 and the gasket 36 by bolts, and protective films are respectively adhered to two sides of the outer layer to prevent direct contact from being corroded to damage an interlayer channel, so that the separation membrane 35 can continuously intercept electrolyte in a test time of thousands of hours, the flow rate of carrier gas and products is not influenced by the existence of the membrane, and continuous analysis and detection can be realized.
The details of the real-time analysis apparatus under the battery cell operating condition provided by the present invention will be described in detail in the following embodiments of the present invention.
Referring to fig. 3, fig. 3 is a schematic structural diagram of a gas-liquid separation module according to an embodiment of the present invention.
In contrast to the above-described embodiment of the present invention, the embodiment of the present invention is further limited to the structure of the gas-liquid separation module 3 in addition to the above-described embodiment of the present invention. The rest of the contents are already described in detail in the above embodiments of the present invention, and are not described herein again.
Referring to fig. 3, in the embodiment of the present invention, the gas-liquid separation module 3 includes an upper housing 32, a gas-permeable support 33, a protective layer 34, a separation membrane 35, a gasket 36, a porous stainless steel plate 37, and a tapered lower housing 38, which are sequentially disposed from top to bottom. The upper shell 32 is connected with the gas analysis device 4 through the gas outlet 31, two grooves with different diameters are arranged in the upper shell 32, and a gas-permeable support body 33 with smaller diameter is arranged close to the gas outlet 31 and used for supporting the membrane but not hindering the gas permeation; in the embodiment of the invention, the separation membrane 35 is fixed on the support body by using viscous glue, a protective layer 34 is respectively added on two sides of the membrane to prevent the gasket 36 from directly contacting and corroding the separation membrane 35, the gasket 36 and the porous stainless steel plate 37, the separation membrane 35 and the upper shell 32 are fixed by bolts, and the conical lower shell 38 is convenient for trapped electrolyte gas molecules to quickly return to the battery so as to realize continuous detection of gas analysis.
The gas-liquid separation module 3 can replace the separation membrane 35 made of different materials so as to meet various special experimental requirements. For the requirement of isolating volatile electrolyte, the embodiment of the present invention prepares a separation membrane 35, and specifically selects a material having a good screening property for gas-liquid separation, such as graphene oxide, graphite-like phase carbon nitride, and the like. The specific preparation process of the separation membrane 35 in the embodiment of the present invention is as follows: dispersing the commercial separation membrane 35 material in deionized water, and uniformly stirring for 1h on a magnetic stirrer to obtain a dispersion liquid with the concentration of 0.2 mg/mL; the supernatant obtained after ultrasonic centrifugation can be used for the subsequent coating process, and the ultrasonic centrifugation frequency can be 1-3 times; and dripping the supernatant on a support body such as polyether sulfone, polyvinylidene fluoride and the like by adopting a spin coating mode, drying the obtained membrane layer, taking down the membrane layer, and drying the membrane layer at room temperature for 24 hours to obtain the separation membrane 35 with the membrane thickness of 20nm-100nm and the interlayer spacing of 0.5nm-1nm. Because the thickness of the film is small, in order to avoid the influence of structural collapse caused by extrusion of an external device in long circulation on an experimental result, a layer of protective film, such as polyimide, is adhered to two sides of the film by quick-drying glue, and the protective film has the characteristics of high temperature resistance and no adhesive residue. The inner diameter of the protective film is smaller than the outer diameter of the separation membrane 35, and the inner ring area is the effective area of the separation membrane 35. When the separation membrane 35 obtained by the preparation method is used for gas analysis and detection, 99.9% of electrolyte can be intercepted, and different types of membranes can be formulated according to different organic solvent molecules for repeated use.
Based on the self-made membrane, the circulation of various batteries for thousands of hours can be realized, the detection is not influenced by the existence of the module, the gas analysis can be continuously carried out, the carrier gas sample introduction and the differential pressure sample introduction are combined to realize the sample introduction at millisecond level, and the real working condition detection is realized.
According to the real-time analysis device under the working condition of the battery cell, special protection treatment is carried out on two sides of the separation membrane 35, and the internal special structure can be maintained without damage in thousands of hours of tests; an industrial oil pump 12 is arranged at the front end of the battery, and accumulated gas in the pipe is extracted at regular time, so that the high-efficiency sampling rate is ensured; three power sources are combined to realize carrier gas and differential pressure combined sample injection, and the response of the instrument can reach millisecond level; the interlayer spacing of the separation membrane 35 can be adjusted according to different electrolyte requirements, so that various electrolyte tests can be met; the separation membrane 35 can effectively intercept the electrolyte, reduce the loss to the instrument, avoid the organic solvent from entering the analysis along with the product, and improve the authenticity of the detection data; the gas analysis is combined with the raman spectrometer 24 for surface composition analysis, which realizes the complete analysis of the internal state of the cell while inputting current.
The invention also provides a real-time analysis system under the working condition of the battery core, which comprises the real-time analysis device under the working condition of the battery core provided by any one of the embodiments of the invention. The rest of the structure of the real-time analysis system under the battery core working condition can refer to the prior art, and is not described herein again.
The real-time analysis device under the battery core working condition provided by the embodiment of the invention can realize real-time analysis under the battery working condition. And this gas-liquid separation module 3 does not need extra energy just can realize the separation of volatile electrolyte and the gas that awaits measuring, and simple structure, can avoid electrolyte to consume when using, and repeatedly usable simultaneously is high-efficient swift safety ring protects. The real-time analysis system under corresponding electric core operating mode also can realize the real-time analysis under the battery operating mode state, under the prerequisite that does not break the battery operating mode, realizes the sample introduction of rank and detects, has high time resolution.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other.
Those of skill would further appreciate that the various illustrative components and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware, computer software, or combinations of both, and that the components and steps of the various examples have been described above generally in terms of their functionality in order to clearly illustrate this interchangeability of hardware and software. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the implementation. Skilled artisans may implement the described functionality in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the present invention.
The steps of a method or algorithm described in connection with the embodiments disclosed herein may be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module may reside in Random Access Memory (RAM), memory, read-only memory (ROM), electrically programmable ROM, electrically erasable programmable ROM, registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art.
Finally, it should also be noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The device and the system for real-time analysis under the working condition of the battery cell provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A real-time analysis device under a cell working condition is characterized by comprising a carrier gas source, a battery test module, a gas-liquid separation module, a gas analysis device and an electrochemical workstation;
the gas-carrying source is hermetically connected with the battery testing module, the gas-liquid separation module is hermetically connected with the battery testing module, and the gas analysis device is connected with the gas-liquid separation module;
the carrier gas source is used for introducing carrier gas into the battery testing module to react with battery liquid in the battery loaded by the battery testing module to generate mixed gas containing gas to be tested and the mixed gas enters the gas-liquid separation module;
the gas-liquid separation module is provided with a separation membrane and is used for mutually separating the gas to be tested and the volatilized electrolyte from the mixed gas through the separation membrane, so that the gas to be tested enters the gas analysis device through the separation membrane, and meanwhile, the electrolyte flows back to the battery test module; the gas analysis device is used for detecting the gas to be detected;
the battery testing module and the gas analysis device are both connected with the electrochemical workstation, and the electrochemical workstation is used for analyzing the battery in real time under the working condition state.
2. The device for real-time analysis under the working condition of the battery cell of claim 1, wherein the carrier gas source comprises a gas cylinder, an industrial oil pump connected with a gas outlet of the gas cylinder, and a timing switch valve connected with the industrial oil pump; the timing switch valve is used for being opened at regular time, so that residual gas between the gas cylinder and the battery test module is discharged from the timing switch valve through the industrial oil pump.
3. The device for real-time analysis under the working condition of the battery cell of claim 2, wherein the carrier gas source further comprises a filter column and a flow meter, the filter column is connected with the gas outlet of the gas cylinder, and the flow meter is connected between the filter column and the timing switch valve.
4. The device according to claim 2, wherein the gas-liquid separation module comprises a vacuum pump disposed between the separation membrane and the gas analysis device to drive the gas to be detected into the gas analysis device.
5. The device for real-time analysis under the working condition of the battery cell of claim 1, wherein the battery testing module is positioned on the surface of a displacement table; the battery test module is provided with a window, and an electrolyte analyzer is arranged on the outer side of the window.
6. The device for analyzing the electrolyte in real time under the working condition of the battery cell of claim 5, wherein the electrolyte analyzer comprises a Raman spectrometer and a lens, the lens is positioned between the Raman spectrometer and the window, and the Raman spectrometer is connected with the electrochemical workstation;
the Raman spectrometer is used for analyzing the surface components of the cells in the cell testing module through the lens and the window.
7. The device for real-time analysis under cell operating conditions according to claim 6, wherein the electrochemical workstation is specifically configured to:
based on preset battery working parameters, when the battery is reacted through the battery testing module, the gas analysis device detects the gas to be detected in real time, and the electrolyte analyzer analyzes the surface components of the battery in real time.
8. The device for real-time analysis under cell operating conditions of claim 1, wherein the battery testing module comprises a heating device for heating the battery and a cooling device for cooling the battery.
9. The device for real-time analysis under the working condition of the battery cell of claim 1, wherein the separation membrane is provided with an interlayer channel, and the interlayer distance of the separation membrane is between the size of the electrolyte gas molecule and the size of the gas molecule to be detected.
10. A system for real-time analysis under cell conditions, comprising the apparatus according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116879513A (en) * | 2023-09-07 | 2023-10-13 | 中碳实测(北京)科技有限公司 | Verification method, device, equipment and storage medium of gas analysis system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116879513A (en) * | 2023-09-07 | 2023-10-13 | 中碳实测(北京)科技有限公司 | Verification method, device, equipment and storage medium of gas analysis system |
| CN116879513B (en) * | 2023-09-07 | 2023-11-14 | 中碳实测(北京)科技有限公司 | Verification method, device, equipment and storage medium of gas analysis system |
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